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UOP

Fluid Catalytic
Cracking Process
Process Technology Manual

ORPIC
Sohar, Oman
September 2012

LIMITED DISTRIBUTION
This material is UOP LLC technical information of a confidential nature for use only by personnel within your
organization requiring the information. The material shall not be reproduced in any manner or distributed for any
purpose whatsoever except by written permission of UOP LLC and except as authorized under agreements with
UOP LLC.

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FCC PROCESS TECHNOLOGY

TABLE OF CONTENTS
I.

INTRODUCTION

II.

PROCESS FLOW
Reactor Regenerator
Main Column
Gas Concentration and Recovery

III.

PROCESS CONTROL
Reactor Regenerator
Main Column
Gas Concentration

IV.

EQUIPMENT
Process Equipment and Its Use
Metallurgical Corrosion

V.

FLUIDIZED SOLIDS
Theory
Applications to Fluid Catalytic Cracking

VI.

CATALYST
History
Modern FCC Catalysts
Time and Temperature Effects
Poisons
Catalyst Management
Catalyst Properties and Testing

VII.

PROCESS VARIABLES
Reactor and Regenerator Process Variables
Feedstock

VIII.

PROCESS CALCULATIONS
FCC Flow Corrections and Mass Balance
Liquid Product Cutpoint Corrections
Reactor and Regenerator Heat Balance
FCC Unit Mechanical Summaries
Additional FCC Unit Calculations

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IX.

FEED AND PRODUCT TREATING


Feed Treating
Product Treating Reasons and Methods

X.

ANALYTICAL METHODS
Minimum Sample Size
Typical Sampling Schedule
Outline of FCCU Laboratory Methods

XI.

PROCEDURES
Refractory Dryout
Startup
Shutdown
Emergencies
Catalyst Handling
FCC Unit Evaluation

XII.

SAFETY
General
Additional Safety Precautions for Entering Vessels
High Temperature Problems
Chemical Hazards

XIII.

ENVIRONMENTAL
Emissions Sources and Solutions

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Introduction
UOP Company History
For more than 80 years, UOP has been one of the worlds leading licensors of new
and innovative technology. Today, UOP continues in this role with 30 offices on 4
continents and 9 manufacturing facilities worldwide. UOP currently licenses and
designs more than 60 different processes and has a total of 5,500 units licensed
worldwide. For the last 50 years, the fluid catalytic cracking (FCC) process has
been an important and successful part of UOP's licensing activities.

The Early Years


UOP was founded in 1914 as the National Hydrocarbon Company on the strength
of patent rights developed from the pioneering work of Jesse A. Dubbs, a California
inventor. The company was financed by a noted Chicagoan, J. Ogden Armour. In
1915, the company name was changed to Universal Oil Products Company.
From the beginning, the goal of the company was to develop and commercialize
technology for license to the petroleum refining industry. Under the direction of C. P.
(Carbon Petroleum) Dubbs, son of Jesse Dubbs, research and development work
continued at the company's small site near Independence, Kansas, where the
famous Dubbs Thermal Cracking process was successfully demonstrated in 1919.
The then-revolutionary process became the foundation of UOP's rapid growth and
its early worldwide recognition by the industry. The early period of growth was ably
directed by its president, Hiram J. Halle, and by Dr. Gustav Egloff, one of the
worlds leading petroleum chemists.
In 1931, UOP established its headquarters in Chicago and its research laboratories
in nearby Riverside, Illinois. That same year the ownership of UOP passed to a
consortium of its major licensees, led by Shell and Standard Oil of California.

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During this stage, the company benefited immensely by the addition to its research
staff of Prof. Vladimir Ipatieff, a famous Russian scientist known internationally for
his work in high-pressure catalysis. His contributions in catalytic chemistry gave
UOP a position of leadership in the development of catalysis as applied to petroleum processing. The first project of Ipatieff and his research team was catalytic
polymerization. Other eminent scientists were also attracted to UOPs research
center in Riverside during this period.
With the outbreak of World War II, UOP scientists and engineers focused their
knowledge and talents on developing new catalytic processes, notably alkylation
that helped meet wartime energy requirements, especially for aviation fuel. UOP
also cooperated with other companies to develop the FCC process.
In 1944, the owners of UOP divested themselves of their holdings in the company,
and UOPs stock was placed in trust. The American Chemical Society was named
as the beneficiary. Thus, the Petroleum Research Fund was created with the
understanding that income from the trust was to be used for advanced scientific
education and fundamental research in the petroleum field.
In spite of some financial and legal setbacks suffered by UOP during this period,
strong management succeeded in steering the company back to its original course:
taking creative research from concept to commercial reality. UOP was recognized
as a company employing the worlds most knowledgeable scientific and technical
personnel, who understood petroleum refining and the need for improved processing methods and techniques.
In 1949, UOP's research staff developed a radically different refining process that
used a catalyst containing platinum. Called the Platforming process, it revolutionized the art of reforming to produce gasoline with substantially improved octane
number. The process was also instrumental in making benzene available in a
quality and quantity never before realized on a commercial scale. With the
Platforming process and other innovative processes, UOP became a vital
contributor to the emergence and growth of the petrochemical industry.

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In the early 1950s, UOP also began to manufacture its own proprietary catalysts
and a variety of refining chemicals at a newly constructed plant in Shreveport,
Louisiana. Later UOP built manufacturing plants at McCook, Illinois; Brimsdown,
U.K.; and other locations. In 1952, UOP moved its headquarters and engineering
activities to Des Plaines, a suburb of Chicago. Soon after, the construction of a new
research center at the same location was begun.

The Recent Era


In 1959, UOP assumed its fourth different corporate form when it was sold to the
public for the first time in its history. As a publicly owned company, UOP entered a
new era marked by growth and diversification. The 1960s saw UOP grow from
essentially a process-licensing company to a diversified corporation through many
acquisitions and mergers with other companies. By 1975, UOP Inc. included more
than 20 different divisions involved in such areas as aerospace and automotive
technology.
During the 1960s and 1970s, UOP's tradition of innovative process development
and commercialization continued with the licensing of the first Sorbex simulated
moving-bed countercurrent adsorption process in 1961 and the introduction of
UOP's CCR Platforming process early in the 1970s.
In 1975, Signal Companies Inc. acquired 50.5% of UOP and in 1978 acquired the
remaining 49.5%, making UOP a wholly owned subsidiary of the company. When
the Signal Companies merged with Allied Corporation in 1985, UOP Inc. became a
subsidiary of Allied-Signal Inc. As the result of reorganizations and restructuring by
its parent companies during the 1980s, UOPs business scope was refocused on
the development and licensing of process technology and the marketing of products
associated with its licensing activities. Of the 20 different divisions, only the Process
Division and UOP Management Services remain in the present UOP.

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In 1988, Allied-Signal entered into an agreement with Union Carbide Corporation


that resulted in the creation of a unique joint venture company called simply UOP.
The new UOP combined the resources of Allied-Signals UOP Inc. with the
Catalysts, Adsorbents and Process Systems (CAPS) Division of Union Carbide. The
joint venture brought together in synergistic union the strong R&D traditions of both
companies. The joint venture now contains the new materials R&D of the CAPS
Union Carbide researchers and the scale-up and commercialization skills of UOP
research. In addition, the joint venture brings together the commercial experience
and worldwide marketing presence of both partners. The result is unprecedented
growth for UOP and the development of valuable new technologies, products, and
services for its customers. Table 1 summarizes some of the historical highlights of
UOP as a process technology company.

Table 1
UOP's History
1914

National Hydrocarbon Company formed to hold Jesse Dubbs


patents for a process to recover heavy oil from water

1915

Name changed to Universal Oil Products Company -patents for Dubbs cracking process issued

1921

Dubbs continuous cracking process commercialized

1930

Ipatieff joins UOP beginning a wave of new process developments: alkylation, catalytic polymerization, C4 isomerization

1941

FCC technology developed

1949

Platforming introduced, many aromatics processes followed

Late 1950s
1961
Early 1970s

Hydrocracking introduced
First Sorbex unit licensed
CCR Platforming introduced

1988

UOP merged with the EP&P and CAPS groups of Union Carbide

1995

UOP acquires the Unocal hydroprocessing business

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In the last 20 years, UOP has developed and commercialized a variety of new and
innovative processes for the refining and petrochemical industry including the
Penex, Molex, BenSat, Oleflex, Ethermax, Merox, Styro-Plus,
Alkylene, Isal, Isomar and Detalprocesses.
UOP transfers this technology to its clients through its licensing activity. In the
technology transfer process, UOP licenses technology; assists in the planning,
design, engineering and commissioning of new installations; provides management
services and advises on the efficient performance of processing facilities throughout
the world.
Behind the successful performance record of UOP is a highly qualified and strong
team continuously at work on ideas and projects. The scientific disciplines are
strongly represented in UOP's team of personnel. UOP has about 4,000 employees
worldwide. With a wide array of highly specialized talents, UOP offers its clients the
complete capability necessary in meeting the demands of today, and the challenges
of the future.
UOP licenses or maintains a position of technical expertise for more than 60 different processes in the petroleum and petrochemical industry. Approximately 175
process units are licensed yearly, and to date UOP has licensed more than 5,500
individual process units and provided technical know-how in designs for more than
1,000 additional non-licensed units. UOP presently holds in excess of 9,000
unexpired patents.
UOP's worldwide licensing activities are supported by a network of offices and
representatives. UOP is centered in Des Plaines, Illinois, and has a district office in
Houston. UOP Limited, a 100% UOP owned subsidiary for operations in Europe,
Africa and the Middle East, has its main European office in Guildford (near London)
and district offices in New Delhi, Jakarta, Jeddah, Beijing and Moscow. UOP Asia
Pacific, located in Tokyo, is an affiliate company of UOP for the licensing of UOP
processes in Japan and certain other areas in the Far East and Southeast Asia.

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UOP has catalyst manufacturing facilities in the United States and in Europe. UOP
Asia Pacific operates a catalyst plant in Japan.
The international scope of UOP activities is evidenced by the fact that process units
have been designed for installation in more than 80 countries around the world.
UOP activities related to these installations have ranged from preparation of
engineering designs for single process units to extensive planning studies involving
market analyses, feasibility and optimization studies, designs for entire grassroots
refineries (both process units and offsites), and complete plant commissioning
services.
The services provided by UOP for these units includes plant design, inspection,
commissioning, performance testing, and training of refinery operating personnel.
Since 1955, UOP has provided, or is providing, engineering designs for more than
125 grassroots refineries and petrochemical complexes. UOP also provided design
specifications for all offsite equipment for many of these installations.

Historical Origins of FCC Technology


The advent of the petroleum refining industry can be traced to the rapidly increasing
demand for kerosene to fuel kerosene lamps for lighting in the latter half of the
1800s. With the invention of electric lighting and the automobile in the early 1900s,
the high value product of petroleum refining shifted from kerosene to gasoline. The
increasing demand for gasoline soon outstripped the availability of straight-run
gasoline from crude oil distillation. This shortage of gasoline provided the impetus
for the development of technologies to increase the gasoline yield from a barrel of
crude oil. Table 2 shows a summary of the progression of cracking technology
which has led to the FCC process as we know it today.

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Table 2
Historical Origins of Fluid Catalytic Cracking
1913 - 1936

Thermal cracking
Burton thermal cracking process (1913)
Dubbs thermal cracking process (1915)
Current use visbreaking, coking

1936 - 1941

Fixed-bed catalytic cracking


Houdry Process Company (1931)
- Multiple reactors -- cyclic process (1937)
- Silica-alumina catalyst (acid-activated clay)

1941 - 1955

Moving-bed catalytic cracking


Thermofor catalytic cracking (TCC) developed by
Socony-Vacuum (Mobil)
Houdryform catalytic cracking
- Continuous process
- Macro-catalyst, moving bed

1942 - Present Fluid catalytic cracking (FCC)


Joint development (1938)
- Continuous process
- Micro-catalyst, fluidized bed

Thermal Cracking
The first thermal conversion process was the Burton process first practiced
commercially in 1913 by Standard Oil of Indiana. In the original Burton process, oil
was exposed batch-wise to high temperature at elevated pressure to achieve
thermal conversion to lighter products. Because of the batch nature of the Burton
process, commercial units contained a large number of individual cracking stills in
order to achieve acceptable daily throughputs.

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Following the commercialization of the Burton process, the Dubbs thermal cracking
process was developed and patented in 1915 (UOP). The Dubbs process was a
continuous process for the thermal conversion of oil to lighter products at elevated
temperature and pressure. The Dubbs process was widely used in refineries
through the 1920s and into the 1930s.
Thermal cracking processes continue to be used in refining today. Examples of
currently used thermal processes are visbreaking and various forms of coking.

Fixed-Bed Catalytic Cracking


In the mid 1920s, a French mechanical engineer and racecar enthusiast named
Eugene Houdry became interested in gasoline quality. After the trial and error
screening of hundreds of catalyst formulations, Houdry found that acid-activated
clay (silica and alumina) was an effective catalyst for cracking heavy oil to lighter
products, particularly high octane gasoline.
In 1931, Houdry, in partnership with Socony-Vacuum (now Mobil), founded the
Houdry Process Company to develop Houdry's fixed-bed catalytic cracking process.
The Houdry catalytic cracking was a cyclic process which typically used four timephased reactors, each of which cycled through a sequence of steps outlined below:
1.
2.
3.
4.

Hot heavy oil is cracked by contact with a fixed bed of catalyst.


The reactor is purged to remove hydrocarbon.
Coke deposited on the catalyst is burned off with air.
The combustion gases are purged from the reactor and the reactor
is ready to begin the next cracking cycle.

A number of technical innovations were required to make the Houdry cracking


process successful. Among these were the development of automatic valves and
the use of control algorithms to control the reaction-regeneration cycles. Many of
the innovations associated with the commercialization of the Houdry cracking

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process were considered revolutionary in the field of process engineering at the


time they were first introduced.
The Houdry catalytic cracking process was first commercialized at the Sun-Marcus
Hook refinery in 1937. The Houdry process was technically attractive to refiners and
by 1940, 14 commercial Houdry units were in operation. Interest in the Houdry
process declined after 1941 because of further advances in catalytic cracking
technology.

Moving-Bed Catalytic Cracking


The next advance in catalytic cracking was the development of a continuous
moving-bed cracking process. The Thermofor Catalytic Cracking (TCC) and
Houdryform Catalytic Cracking (HCC) processes were developed in parallel in the
1940s and early 1950s. Both processes used a similar concept and had
approximately equal success.
In the TCC process, the catalyst pellets continuously move through the reactor to
the regeneration vessel and are then returned to the reactor. The key to the TCC
process was the Thermofor kiln used to regenerate the spent catalyst (the kiln had
been originally developed to burn coke off of Fullers earth used to filter lube oils).
In the TCC process, regenerated catalyst flows by gravity from a surge vessel
elevated above the reactor, into the reactor vessel where the catalyst contacts hot
oil and the cracking reactions take place. The air environment of the catalyst surge
vessel is buffered from the hydrocarbon environment of the reactor by steam
injected into the catalyst transfer line. Both the hydrocarbon vapors and catalyst
flow down through the reactor to a lower section where the cracked products exit
the reactor through separation pipes. The spent catalyst continues to flow by gravity
down through a steam stripping zone into the regeneration kiln where coke is
burned off the spent catalyst with air. The steam stripping zone also serves to
provide a barrier between air in the regenerator and hydrocarbon in the reactor. In
early TCC units, the hot regenerated catalyst pellets were mechanically conveyed

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back up to the catalyst surge vessel by bucket elevators. Later units employed
pneumatic air lift systems to transfer the regenerated catalyst back up to the surge
vessel.
Socony-Vacuum was the principle developer of the TCC process and the first semi
commercial unit started up at the Paulsboro refinery in 1941. The TCC units were
licensed and operated by Socony-Vacuum and others from 1941 to about 1955
when the TCC gave way to the more versatile FCC process developed in the during
the late 1930s and early 1940s. A few TCC units still continue to operate today.

The FCC Process


Early development of the FCC process took place late in the 1930s. A number of
motivations were behind the development of the FCC process. Among these were
the high fees required to license the Houdry cracking process, the diffusion and
heat transfer limitations associated with both the Houdry fixed-bed process and the
TCC process (both used large size catalyst pellets), and the increasing demand for
high octane aviation gasoline brought on by World War II.
Initial FCC process development efforts were led by Standard Oil of New Jersey
(now Exxon) in association with two researchers from the Massachusetts Institute of
Technology, Warren Lewis and Edwin Gilliland (consultants to Standard-NJ). Lewis
and Gilliland had found that under the proper aeration conditions, finely divided solid
particles (powders) could flow through pipes and in many respects act similarly to
liquids. This was the advent of fluidization. The use of finely divided cracking
catalyst offered a means of overcoming the diffusion and heat transfer limitations
encountered with the large size catalyst pellets used in the earlier catalytic cracking
processes.
In 1938, Standard-NJ and some of the other major oil companies, as well as M. W.
Kellogg Co. and Universal Oil Products (UOP), formed Catalytic Research Associates (CRA) to jointly develop a fluidized catalytic cracking technology. The first
commercial-scale (13,000 BPD) FCC unit, designated the Model I, started up at

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Standard-NJ's Baton Rogue refinery in May 1942. Two other Model I FCCs were
designed but were not built as the improved Model II FCC design came very
quickly. When Standard-NJ announced the construction and imminent startup of the
first FCC Model I, they also announced that Universal Oil Products (UOP) and M.
W. Kellogg would be designing and licensing the new FCC technology. In the threeyear period between 1942 and 1945, 34 new FCC units came on stream in the
refineries of 20 different oil companies. The installed capacity of these new FCC
units was over 500,000 BPD. Thirteen of these units were licensed from UOP.
Following the commercialization of the Model I and Model II FCC units within the
CRA partnership, the FCC unit design and development diverged with the partner
companies largely going their separate ways with regard to future FCC technology
development and commercialization.

UOP and Fluid Catalytic Cracking


During the 1940s, military requirements resulted in widespread commercialization
when UOP designed about 40% of the 34 units that were built and operated.
Following this period, UOP was in the forefront with commercialization of the
"stacked" FCC unit design which featured a low-pressure reactor stacked directly
above a higher pressure regenerator. The stacked design not only met the
economic needs of smaller refiners, it was a major step toward shifting the cracking
reaction from the dense phase of the catalyst bed to the dilute phase of the riser. In
the mid-1950s, UOP introduced the "straight-riser" or side-by-side design. In this
unit, the regenerator was located near ground level with the reactor to the side in an
elevated position. Regenerated catalyst, fresh feed and recycle were directed to the
reactor by means of a long, straight riser located directly below the reactor.
Compared to earlier designs, product yields and selectivity were substantially
improved.
A major breakthrough in catalyst technology occurred in the mid-1960s with the
development of the zeolitic catalysts. These catalysts demonstrated vastly superior
activity, gasoline selectivity and stability characteristics compared to the amorphous

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silica-alumina catalysts then in use. The availability of the zeolitic catalysts served
as the basis for most of the process innovations that have developed in recent
years.
The continuing sequence of advances in both catalyst activity and process design
culminated in the most significant concept to date in the field of the FCC process
the achievement of transport-phase cracking entirely in the riser, or all-riser cracking. The key to all-riser cracking is the design of a system that initiates a plug-flow
reaction and then stops the cracking reaction at the optimum yield of desired
products. UOP commercialized a new design based on this concept in 1971. This
design was also applied to existing unit revamps. Commercial results confirmed the
expected advantages of the system compared to the older designs. The quick
quench design provided the desired high selectivity to gasoline, reduced coke yield,
and a reduction of secondary cracking of desired products to lighter, less valuable
material.
The next major improvement in the FCC technology was the development of
catalysts and regenerator systems for the complete internal combustion of carbon
monoxide (CO) to carbon dioxide (CO2). In 1973, an existing UOP unit was
revamped to include a new combustor concept in regeneration technology to
achieve direct conversion of CO within the unit. This was followed by the start-up in
1974 of a new FCC unit specifically designed to incorporate the combustor
regenerator technology.
This development in regenerator design and operating technique resulted in
reduced coke yields, lower CO emissions which satisfy environmental standards
and higher circulating catalyst activity that improved product distribution and quality.
Table 3 summarizes some of the major achievements in UOP's FCC process
technology development and commercialization.

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Table 3
Milestones in FCC Technology
1942

UOP begins licensing the FCC Process

1945

13 Units licensed by UOP

1947

UOP commercializes stacked unit design


Economical for small refiners
50 Stacked designs over 10-year period

1950s

UOP commercializes side-by-side design


Straight riser
Better suited for larger units
Riser extension and termination
(more reaction in riser)

1973

First complete combustion regenerator

1983

First two-stage regenerator with external dense-phase


cooling for highly contaminated resid feed commissioned

1983

First elevated distributors commissioned

1991 - 1995

Newest generations of highly contained riser termination


devices commercialized (VDS and VSS)

1994

First Optimix feed distributor commissioned

1994

First MSCC unit commissioned

2006

First AF Packing commissioned

Recent Developments
Advances in riser termination devices occurred at a rapid rate in the 1980s to the
mid 1990s. Early riser termination devices such as the open Tee resulted in very
long residence times for the hydrocarbon products in the reactor vessel. This
extended residence time resulted in nonselective thermal cracking and secondary
catalytic cracking reactions. Recent improvements have resulted in better containment of the hydrocarbon vapor to the riser and therefore lower post riser residence
time. This reduced delta coke and dry gas and improved gasoline selectivity. Early
versions of these high containment riser terminations included the vented riser and

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SCSS (suspended catalyst solids separation) devices. In 1991, the first VDS
(vortex disengager stripper) was commissioned. This technology further minimized
the post-riser residence time resulting in further improvements in product yields. In
1995, the first VSS (vortex separation system) was commissioned.
Improvements in feed distribution systems also occurred rapidly in the late 1980s
and 1990s. Elevated, radially oriented feed distributors minimize nonselective
thermal cracking reactions by providing more uniform feed/catalyst contacting with
less back mixing than the earlier wye feed distributors. Acceleration zone
technology which pre-accelerates the catalyst into a uniform, moderate density flow
pattern for optimum oil penetration and uniform catalyst/oil contacting further
improved the performance of the elevated feed distributors. The first UOP elevated
feed distributors were commissioned in 1983. Developments in spray nozzle
technology resulted in the Optimix feed distributor which has a smaller, more
uniform oil droplet size and a spray pattern that distributes the oil uniformly over the
entire riser area for superior catalyst/oil contacting and performance. The first
Optimix feed distributor was commissioned in 1994. Since then, the number of
refiners using Optimix feed distributors has grown to over 80.
Resid processing in FCC units began in the mid-1970s. During this same period,
reactor temperatures were being increased to maximize gasoline octane. The need
for higher conversion, combined with the desire to process residue feeds significantly increased coke yields and ultimately limited the FCC regenerator capacity.
The RCC, or Reduced Crude Conversion, process was developed jointly by UOP
and Ashland Oil in the late 1970s to address residue processing. It is an extension
of UOP's FCC design experience that incorporates many innovations and modifications from the UOP-Ashland Oil development program. In addition to cold-flow
modeling work, a large-scale pilot plant was constructed at Ashland's Catlettsburg,
Kentucky refinery. Testing in this 200 BPSD plant examined processing variables
and new mechanical designs on a wide range of residual feedstocks. In 1983,
Ashland commissioned a 40,000 BPSD RCC unit at the Catlettsburg refinery.

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Several major innovations from the pilot plant testing and first commercial design at
Ashland have become the foundation of UOP's technical offering for catalytic
cracking of residue feedstocks, including the following.
Acceleration zone and feed distribution system
Higher containment riser termination devices for quick disengagement
Two-stage catalyst regeneration
Catalyst cooler
Since 1983, eight grass-root RCC units licensed by UOP have been commissioned.
In addition, resid feedstocks are being processed in more than 30 existing UOP
FCC units. In present times, the distinction between a gasoil FCC unit and a resid
FCC unit has blurred to the point where most modern FCC units are capable of
processing some level of resid. The term RFCC is used by UOP today to designate
a new unit utilizing a 2 stage regenerator designed for the specific intent of
processing resid feeds. Table 4 shows a brief summary of resid processing and
UOP's activity in the area of resid processing.

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Table 4
Resid Processing Milestones
1940s

Resid component added to feed

1950s

Resid processing diminishes

1975

Resid processing regains attractiveness


Market conditions favor increased efficiency in
gasoline production
Technology and catalyst advances increase resid
processing potential
UOP units begin processing resid/gasoil blends

1976

UOP and Ashland Oil Cooperation


Research and development for reduced crude
conversion
Semi-commercial demonstration

1983

First RCC unit commissioned

1984 - 2006

8 New RCC units operating ->30 Units processing resid

Commercial Experience
Since commercialization of the FCC process, UOP has licensed more than 210
units, or over 50% of all non-captive installations. More than 140 of these units
continue to operate throughout the world. The superior technology and operational
reliability built into UOP FCC units are some of the reasons why 58 refineries
worldwide have licensed new UOP FCC units since 1980, which is more than all
other licensors combined during this period. UOP's commercial activity in the
FCC/RCC/MSCC processes since 1980 is as follows:

63
40
330
180
30+

New units licensed


New units commissioned
Revamps
Major revamps
Units processing resid with UOP technology

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Revamp activity is of equal importance in demonstrating technical expertise. In the


period 1980-1998, UOP performed more than 330 unit revamps that encompassed
virtually every major section of the FCC unit. This activity is vital to UOP's continuing advances in both process and design engineering. The depth of both grass-root
and revamp experience gives UOP great capability to respond to the changing
needs of the industry.

FCC Process Description


The FCC process converts heavy crude oil fractions into lighter, more valuable
hydrocarbon products at high temperature and moderate pressure in the presence
of a finely divided silica/alumina based catalyst. In the course of cracking large
hydrocarbon molecules into smaller molecules, a non-volatile carbonaceous
material, commonly referred to as coke, is deposited on the catalyst. The coke laid
down on the catalyst acts to deactivate the catalytic cracking activity of the catalyst
by blocking access to the active catalytic sites. In order to regenerate the catalytic
activity of the catalyst, the coke deposited on the catalyst is burned off with air in the
regenerator vessel.
One of important advantages of the FCC process is the ability of the catalyst to flow
easily between the reactor and the regenerator when fluidized with an appropriate
vapor phase. In FCC units, the vapor phase on the reactor side is vaporized hydrocarbon and steam, while on the regenerator side the fluidization media is air and
combustion gasses. In this way, fluidization permits hot regenerated catalyst to
contact fresh feed; the hot catalyst vaporizes the liquid feed and catalytically cracks
the vaporized feed to form lighter hydrocarbon products. After the gaseous hydrocarbons are separated from the spent catalyst, the hydrocarbon vapor is cooled and
then fractionated into the desired product streams. The separated spent catalyst
flows via steam fluidization from the reactor to the regenerator vessel where the
coke is burned off the catalyst to restore its activity. In the course of burning the
coke a large amount of heat is liberated. Most of this heat of combustion is
absorbed by the regenerated catalyst and is carried back to reactor by the fluidized
regenerated catalyst to supply the heat required to drive the reaction side of the

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process. The ability to continuously circulate fluidized catalyst between the reactor
and the regenerator allows the FCC unit to operate efficiently as a continuous
process.
The FCC units are large-scale processes and unit throughputs are typically in the
range of about 10,000 to 130,000 barrels per day. This corresponds to catalyst
circulation rates of around 7 to 130 tons per minute. The largest commercial FCC
unit in operation was designed at 130,000 BPSD, pushed to ~184,000 BPSD, and
in 2005 was revamped to a nominal 200,000 BPSD with a catalyst circulation rate in
excess of 170 metric tons per minute. These large circulation rates of hot, abrasive
catalyst constitute a very significant challenge to the mechanical integrity of the
reactor, the regenerator and their associated internal equipment. Thus, mechanical
design considerations are critical to the ultimate success of an FCC unit as a
prominent refinery process unit. The main features of an FCC unit are:

Catalytic process
Mechanical process
Cracks heavy molecules to lighter ones
Pressure: 15-45 psig (1-3 kg/cm2g)
Temperature:
Reactor:
915-1050F (490-565C)
Regenerator: 1200-1450F (650-790C)
Reaction and regeneration sections intimately
linked by heat balance and catalyst circulation

FCC Process Feedstocks


FCC units process heavy oil from a variety of variety of refinery flow schemes.
Generally, the feed comes from either the refinery crude unit or vacuum unit and
constitutes the fraction of the crude boiling in the range of 650 to 1000+F (350 to
550+C). There may be additional feed preparation units upstream of the FCC unit
such as a hydrotreater or deasphalter. Figure 1 shows a schematic diagram of the
possible refinery flows providing feed to an FCC unit.

157048
Introduction
Page 19

In addition, the FCC units commonly process heavy fractions from other conversion
units as part of the combined FCC feed blend. Examples of these types of streams
are coker gasoil and hydrocracker fractionator bottoms. The types of heavy hydrocarbon streams that are commonly charged to an FCC unit are:

Atmospheric gasoil
Vacuum gasoil
Atmospheric resid
Coker gasoil
Demetallized oil
Hydroprocessed gasoil
Hydroprocessed resid
Lube oil extracts

157048
Introduction
Page 20

FCC Products
The products obtained from the FCC unit are light hydrocarbon gases (C2-) which
are normally used within the refinery as fuel gas, light olefins and paraffins (C3s
and C4s) also referred to as LPG, gasoline, LCO and clarified oil commonly
referred to as main column bottoms. In addition, flue gas is generated from the
burning of coke in the regenerator. Heat is recovered from the flue gas and is used
to make steam and in some cases power is also recovered from the flue gas in the
form of electricity via a power recovery expander coupled to a motor/generator.
Products produced from an FCC unit are:

Light gas
Light olefins
LPG
Light paraffins
Gasoline
Light cycle oil
Main Column Bottoms
Coke (burned in unit as fuel)

Most of the FCC product streams undergo further processing before leaving the
refinery as marketable products. Figure 2 shows typical routes for the FCC product
steams going to further processing and ultimately to blending into the refinery
product pools.

157048
Introduction
Page 21

Figure 2
Typical Use of FCC Products
Flue Gas
Reactor
&
Regen.

C3/C4
Paraffins
Fuel Gas

Alkylation

LPG
Merox
Gasoline Gasoline
Merox
LCO
CLO

Alkylate
Gasoline
Pool

C3/C4
Splitter
Main
Column
&
Gas Con

LPG Pool

MTBE
Distillate
Hydrotreater

Diesel
Pool
Heavy Fuel
Oil Pool

The light liquid products from the FCC process are LPG and gasoline. The LPG
from an FCC unit is highly olefinic and has become an increasingly valuable stream
for further processing in the present movement toward reformulated gasoline and
as petrochemical unit feedstocks. The FCC olefins are an important feedstock for
the production of MTBE and alkylate as gasoline blending components and for the
production of polypropylene. The FCC gasoline generally has good octane properties (90-95 RON and 80-83 MON) and may make up 30 vol-% or more of the
refinery gasoline pool. Some typical characteristics of light FCC products from highconversion operations (VGO Feed, 1.0 wt% sulfur) are:

157048
Introduction
Page 22

LPG:
500 - 1500 wppm total sulfur
30 - 40 vol-% C3 olefins
34 - 45 vol-% total C4 olefins

Gasoline: C5 - 380F 90% point (193C 90% point)


92 - 94 RONC
0.1 - 0.2 wt-% sulfur
30 - 40 vol-% olefins
25 - 35 vol-% aromatics
0.5 - 1.0 vol-% benzene

The heavy liquid products from an FCC unit are normally LCO and clarified oil. The
LCO product is normally used as a blending component in the diesel pool and/or in
the heavy fuel oil pool. It is becoming increasingly common for LCO destined for
diesel blending to be hydrotreated first for sulfur reduction. Clarified oil is usually
blended off to the heavy fuel oil pool. In some cases, the FCC unit clarified oil is
used in coker feed, for asphalt production or sold as feed for carbon black production. Some characteristics of heavy FCC products from high conversion operations
(VGO Feed, 1.0 wt% sulfur) are:

Light cycle oil: 600F 90% point (316C 90% point)


20 - 26 cetane index
1 1.5 wt-% sulfur
75 - 80 vol-% aromatics
3 - 3.5 cSt @ 122F (50C)

Clarified slurry oil:


2 - 3 wt-% sulfur
9 - 13 cSt @ 210F (100C)

Source: Middle Eastern light gasoil

157048
Introduction
Page 23

157048
Introduction
Page 24

Abbreviations and Definitions


ABD

average bulk density

ACFM

actual cubic feet per minute

activity

conversion of oil by test catalyst compared to standard


reference feed often referred to as MAT activity

adjusted

conversion or yields reported as corrected to standard


product cutpoints

afterburning

burning of CO above the dense bed in the dilute phase or


flue gas, characterized by temperature increase

AGO

atmospheric gasoil

Al

aluminum

Al2O3

alumina

APS

average particle size

AR

atmospheric column resid

ash

non-combustible particles remaining after burning of a


main column bottoms sample

as produced

conversion or yields reported as percent of fresh feed at


the actual product rates not adjusted to standard product
cut points

ASTM

American Society for Testing and Materials

Coefficient of thermal expansion at 60F, (1/F)

behind in burning

insufficient coke combustion in regenerator,


characterized by increased coke production in reactor
and dark grey regenerated catalyst (high carbon on
regenerated catalyst)

BPD

barrels per day

157048
Introduction
Page 25

BS & W

bottoms sediment and water, normally reported in vol-%

C1, C2

methane, ethane, ...

C3=

olefin (propylene)

caustic

sodium hydroxide

CCR

catalyst circulation rate

CFR

combined feed ratio (volume of fresh feed plus recycle,


divided by volume of fresh feed)

CN-

cyanide ion

CO2/CO

mole ratio of carbon dioxide to carbon monoxide,


indicates degree of partial combustion

cold regenerator

operation in conventional controlled regenerator


afterburning mode of regeneration

conversion

measure of the rate of gasoil disappearance (or


conversion) from feed to products defined as

COS

carbonyl sulfide

CRC

carbon on regenerated catalyst

CSO

clarified slurry oil

Cu

copper

DA, DS, DG

reactor or regenerator purges using air, steam or gas,


respectively

P, DP

pressure drop or pressure difference between two points

dry gas

gas from sponge absorber (usually refers to C2-)

EP

end point of distillation

F-1

research octane number (RON)

F-2

motor octane number (MON)

157048
Introduction
Page 26

Fe

iron

Fines

catalyst particles less than 20 microns diameter

Fm

feed metals factor

Gasoline efficiency

ratio of liquid vol-% gasoline to vol-% conversion,


indicates selectivity to produce gasoline

GC, GLC

gas chromatography, gas/liquid chromatography

Gb

Fluid gravity at base temperature (60F)

Gf

fluid gravity at flowing temperature

gpm

gallons per minute

H2/C1

ratio of moles hydrogen to moles of methane

H2S

hydrogen sulfide

HC

hydrocarbon

HCN

heavy cat naphtha product drawn from the side of the


main column

HCO

heavy cycle oil

HPS

high pressure separator

enthalpy (heat) difference

IBP

initial boiling point of distillation

K (UOP K)

measure of paraffinicity or aromaticity of hydrocarbon

lb/Bbl (#/Bbl)

pounds per barrel

LCO

light cycle oil

LV-%

liquid volume percent

prefix for thousand

MC

main column

157048
Introduction
Page 27

MCB

main column bottoms product

MON

motor octane number

MW

molecular weight

N (or N2)

nitrogen

Na

sodium

NH3

ammonia

Ni

nickel

NOx

nitrogen oxides

O (or O2)

oxygen

ppm

parts per million

Pf

Pressure at flowing conditions (absolute)

recycle

normally refers to heavy oil from main column which has


already passed through the reactor that is returned with
the fresh feed to the reactor, this could also refer to light
material such as LCO or gasoline; a stream which returns
to its source.

RE (or Re2O3)

rare earth (or rare earth oxide)

Rg

regenerator

RON

research octane number

RSH

mercaptan sulfur

RVP

Reid vapor pressure

Rx

reactor

SA

surface area

SCF/Bbl (SCFB)

standard cubic feet per barrel of fresh feed

157048
Introduction
Page 28

SCFD

standard cubic feet per day

selectivity

preferential towards specified goal or species

severity

combines different factors to give an overall qualitative


measurement of extent or difficulty in cracking and
regeneration

Si

silicon

Si2O3

silica

sintering

closure of catalyst pores

SOX

sulfur oxides

spillback

gas recycle, may also refer to liquid recycle

SS

stainless steel, also second stage

Tf

temperature at flowing conditions (absolute)

vanadium

VGO

vacuum gasoil

vol-%

volume percent

wt-%

weight percent

157048
Introduction
Page 29

UOP P&I Diagram Abbreviations


AR

Analysis Recorder

ARC

Analysis Recording Controller

DR

Specific Gravity Recorder

FA

Flow Alarm

FE

Orifice Flange Assembly

FFRC

Flow (ratio) Recording Controller

Fl

Flow Indicator

FIC

Flow Indicator Controller

FIF

Flow Indicator Flow Type

FQI

Flow Meter Displacement Type

FR

Flow Recorder

FRA

Flow Recording Alarm

FRC

Flow Recording Controller

FRCF

Flow Recording Controller Float Type

FRCQI

Flow Recording Controller Integrator

FRQI

Flow Recorder Integrator

FRQIA

Flow Recorder Integrator Alarm

HC

Hand Control

II

Current Indicator

LA

Level Alarm

LC

Level Controller

LG-B

Gage Glass Boiler TypeVisible Length Shown

157048
Introduction
Page 30

LG-R

Gage Glass Reflex TypeVisible Length Shown

LG-RLT

Gage Glass Reflex Type


Visible Length ShownLow Temperature

LG-T

Gage Glass Through View Type


Visible Length Shown

LG-TK

Gage Glass Through View Type


Visible Length ShownKEL-F

LG-TLT

Gage Glass Through View Type


Visible Length ShownLow Temperature

Ll

Level Indicator

LIA

Level Indicating Alarm

LIC

Level Indicating Controller

LR

Level Recorder

LRA

Level Recording Alarm

LRC

Level Recording Controller

PA

Pressure Alarm

PC

Pressure Controller

PDC

Pressure Differential Controller

PDI

Pressure Differential Indicator

PDIC

Pressure Differential Indicating Controller

PDR

Pressure Differential Recorder

PDRA

Pressure Differential Recording Alarm

PDRC

Pressure Differential Recording Controller

PDRCA

Pressure Differential Recording Controller Alarm

157048
Introduction
Page 31

PI

Pressure Indicator

PIA

Pressure Indicating Alarm

PIC

Pressure Indicating Controller

PR

Pressure Recorder

PRA

Pressure Recording Alarm

PRC

Pressure Recording Controller

SI

Speed Indicator

SR

Speed Recorder

TA

Temperature Alarm

TC

Temperature Controller

TDR

Temperature Differential Recorder

TDRA

Temperature Differential Recording Alarm

TDRC

Temperature Differential Recording Controller

TI

Temperature Indicator

TIC

Temperature Indicating Controller

TIX

Temperature Indicator Skin

TR

Temperature Recorder

TRA

Temperature Recording Alarm

TRC

Temperature Recording Controller

TRX

Temperature Recorder Skin

TW

Thermowell

Zl

Valve Position Indicator

157048
Introduction
Page 32

When Instruments Are Designated with an Alarm


H

Indicates High

HH

Indicates High-High, typically in association with an Emergency


Shutdown (ESD) system trip point

Indicates Low

LL

Indicates Low-Low, typically in association with an Emergency


Shutdown (ESD) system trip point

157048
Process Flow
Page 1

PROCESS FLOW
INTRODUCTION
The modern Fluid Catalytic Cracking unit is a large and complex process for
cracking heavy gas oil to lighter hydrocarbons. FCC has largely replaced the old
thermal crackers because it is a more efficient process, i.e. more production of
valuable products at a lower overall cost by using catalyst and heat instead of
simply heat.
In its simplest form, the process consists of a reactor, a catalyst regenerator, and
product separation. This is shown in Figure 1. Catalyst circulation is continuous, at
very large mass flow rates. For this reason, the reactor and regenerator are usually
discussed as one section. The product separation is usually divided into its low and
high pressure components, i.e. the main column section, and the gas concentration
and recovery section.

Figure 1:
Fluid Catalytic Cracking Process
Flue Gas

Regenerator

Air

Catalyst
Transfer
Lines

Products
Reactor

Raw Oil

Product
Separation

157048
Process Flow
Page 2

Reactor-Regenerator
This is the heart of the process, where the heavy feed is cracked. The reaction
products range from oil which is heavier than the charge to a light fuel gas. The
catalyst is continuously regenerated by burning off the coke deposited during the
cracking reaction. This provides a large measure of the heat required for the
process.

Main Column
The main column cools the reactor vapors and begins the separation process. A
heavy naphtha fraction and light and heavy fuel oils (LCO and CLO) come off the
tower as products; gasoline and lighter materials leave the top of the tower together
and are cooled and separated further into product streams in the gas concentration
section.

Gas Concentration and Recovery


This section separates the main column overhead into gasoline, liquefied petroleum
gas, and fuel gas streams. The composition of each stream is controlled for
maximum product value. Figure 2 shows a slightly more detailed schematic of an
FCC unit.

Raw
Oil

Catalyst
Section

MCB
HCO

Steam

Light
Naphtha

Fuel
Gas

Flue
Gas

FCC-PF002

LPG

Gas Con Section

Flue Gas
Cooler
BFW

Heavy
Naphtha

LCO

Main Column
Section

Power Recovery
Section

Figure 2
FCC Block Flow Diagram

157048
Process Flow
Page 3

157048
Process Flow
Page 4

PROCESS FLOW DESCRIPTION


Reactor-Regenerator
The FCC process was developed in the early 1940's. A number of companies
participated in the early stages of the work, so most of the early units were virtually
identical. The first design, the Model I, was installed at only three refineries and
quickly replaced by a more successful Model ll. Thirty-one of these were built,
thirteen designed by UOP. Figures 3 and 4 show the configurations of the Model I
and the Model II FCCs, respectively.
The Model II units had double slide valves and long standpipes, which were a prime
source of operating problems due to loss of catalyst fluidization in the standpipes.
The raw oil charge passed through a dense bed of fluidized catalyst in the reactor
vessel; however, evidence indicated that a large part of the desired cracking was
occurring in the transfer line where the hydrocarbon first contacted the catalyst.
The early units used low activity catalysts by today's standards, starting with natural
clay and later progressing to amorphous synthetic silica/alumina catalysts. Large
amounts of heavy oil were recycled back to the reactor in order to obtain the
desired conversion levels of 40-60 vol-%.
UOP introduced a major departure from the Model ll design in 1947. The
regenerator riser was eliminated and the regeneration air was injected directly into
the regenerator dense bed. Single slide valves and the more compact design cut
construction costs. An important feature of the design was a long reactor riser,
which was a major advantage as FCC technology advanced toward entirely riser
cracking. The UOP Stacked FCC design proved to be quite popular and UOP
designed about 50 Stacked FCC units. Figure 5 shows the typical arrangement of
the UOP Stacked FCC unit.

157048
Process Flow
Page 5

Figure 3:
Model I FCC
Cottrell
Precipitator

Flue Gas

Catalyst
Fines

Products to
Main Column

Cyclones

Hoppers
Air or
Steam

Steam

Standpipes

Regenerator
Reactor

Steam
Regenerator
Riser
Water

Catalyst
Recycle
Cooler

Raw Oil
Charge

Reactor
Riser

Fired
Heater
FCC-PF003

157048
Process Flow
Page 6

Figure 4
Down-flow Model II Catalytic Cracking Unit

Flue
Gas

Cottrell
Precipitator

Waste
Heat
Boiler

Multicyclones
Regenerator
Products to
Main Column

Reactor

Steam to
Stripping
Section
Raw Oil
Charge
MCB
Recycle

Air

FCC-PF004

157048
Process Flow
Page 7

Figure 5
UOP Stacked Fluid Catalytic Cracking Unit
To Main Column
Cyclone

Flue Gas

Reactor

Orific
Chamber
Spent Catalyst
Stripper

Flue Gas
Slide Valve

Stripping
Steam

Regenerator
Spent Catalyst
Slide Valve

Regenerated Catalyst
Slide Valve
Air
Slurry Recycle

Raw Oil
Charge

HCO Recycle
FCC-PF005

157048
Process Flow
Page 8

The next advance in reactor-regenerator design was the Side-by-Side unit, shown
in Figure 6. This design was better for larger units, where stacking the reactor on
top of the regenerator became more expensive. The Side-by-Side layout has also
been used for many of the new small units. The straight riser showed less erosion
than the curved riser of the Stacked unit. Some of the Side-by-Side units were
designed with a reactor dense bed. This bed was eliminated with the advent of
zeolite cracking catalysts, and the riser was extended within the reactor to minimize
thermal and catalytic cracking by reducing vapor residence time in the vessel.
Initially, cyclones were installed on the riser to separate the oil and catalyst, but this
was not particularly successful due to poor cyclone performance. The riser cyclones
were replaced by a "Tee" shaped termination at the top of the riser. The riser
cyclone could then be moved over to allow room for the addition of another cyclone
at the reactor outlet, providing two stages of cyclone separation. Later advances in
riser termination devices concentrated on maximizing hydrocarbon containment or
minimizing the post-riser residence time in the reactor shell where non-selective,
thermal and secondary cracking reactions occur. Side-by-Side units have won
good acceptance by the industry and over 75 UOP designed Side-by-Side FCC
units have been built.
Zeolite cracking catalysts were developed in 1963 and gradually accepted by the
industry over the next ten years. These catalysts proved to be much more active
than amorphous catalysts and were ideally suited for the short contact time riser
cracker. Conversion levels rose as high as 80% without requiring excessive reactor
temperature.
Another significant improvement in FCC reactor technology was the use of elevated
feed distributors. The older wye feed distributors injected the raw oil charge into a
highly back-mixed catalyst flow that resulted in non-uniform oil/catalyst mixing and
excessive light gas and coke formation. In newer systems, multiple, radially oriented
feed distributors elevated in the riser inject raw oil more uniformly to maximize
selectivity to desired products.

157048
Process Flow
Page 9

New regenerator designs were also developed over the years. The old perforated
plate air distributor was changed to a pipe grid for better air distribution. Two stage
cyclones replaced single stage cyclones and reduced catalyst losses.
The burning of coke in the old regenerators was not complete, i.e., not all the
carbon went to CO2, and the flue gas normally contained 6-10 vol-% CO. The unit
ran with no excess oxygen. This prevented afterburning in the cyclones and the
resultant heat damage to the cyclones. An extra furnace to generate steam, the CO
boiler, was added to utilize heat that would otherwise be lost. All of the excess CO
in the flue gas could be burned in the CO boiler, but capital costs were high. The
obvious solution to this problem was to burn all of the CO to CO2 in the regenerator,
where the catalyst can absorb the heat.
Although this could be done in a standard bubbling bed regenerator, a new, high
efficiency type regenerator design proved more efficient. In the high efficiency or
combustor style regenerator, shown in Figure 7, the air and catalyst is mixed in a
fast fluidized environment in the lower part of the regenerator or combustor. The
fluidized catalyst is then carried up the combustor riser to the upper regenerator.
The fluidization in the combustor provides excellent air/catalyst mixing and heat
transfer to maximize coke burning kinetics. The high efficiency regenerators on
stream average less than 100 ppm CO, and less than 40 ppm NOx in the flue gas.
This design enables refineries to get greater thermal efficiency from the unit while
simultaneously meeting more stringent air quality standards.

157048
Process Flow
Page 10

Figure 6
UOP Side by Side Fluid Catalytic Cracking Unit
Rxn Products to
Main Column

Reactor
Down-Turned
Arm

Flue
Gas

Flue Gas
Slide Valve

Stripping
Steam

Bubbling Bed
Regenerator

Spent
Catalys
Slide Valve

Main
Distributo

Air

Regenerated
Catalys
Slide Valve

Wy
Section
Raw
Oil Feed

157048
Process Flow
Page 11

Figure 7
Modern UOP Side by Side Fluid Catalytic Cracking Unit
With High Efficiency Regenerator, Elevated Feed Distributors and
Vortex Separation System Riser Termination

157048
Process Flow
Page 12

The process flow of the reactor and regenerator section of a typical, modern FCC
unit with a high efficiency regenerator can be described as follows:
Lift steam and/or light hydrocarbon is injected at the base of the riser or Wye to
accelerate the catalyst from towards the elevated feed distributors, which are
located about 1/3 the way up the riser. The preheated raw oil charge is pumped
through the feed distributors and atomized with the addition of steam then injected
into the regenerated catalyst stream. The heat from the catalyst and reduced
hydrocarbon partial pressure in the riser both act to help vaporizes the oil. The
catalyst, oil and steam travel up the riser to a region of lower pressure in the reactor
where the cracked hydrocarbon products are separated from the catalyst in the riser
termination device and cyclones before going to the main column for initial product
separation.
During the cracking reaction, a carbonaceous by-product called coke is deposited
on the circulating catalyst. This catalyst (referred to as spent catalyst) drops from
the reactor disengager and cyclones into the stripping section where a
countercurrent flow of steam is used to remove both interstitial and some adsorbed
hydrocarbon vapors. The stripped catalyst flows from the reactor stripper through
the spent catalyst standpipe to the regenerator, where the coke is continuously
burned off. The catalyst flow through the spent catalyst standpipe is controlled to
balance the circulating catalyst flow by maintaining a constant catalyst level in the
reactor.
In the regenerator, the spent catalyst mixes with air and hot regenerated catalyst
from the recirculation catalyst standpipe at the base of the combustor. Here the
coke deposited during in the reactor is burned off to reactivate the catalyst and
provide heat for the net endothermic cracking reactions. The heat of combustion
raises the catalyst temperature in the regenerator to a range of 1200F-1375F
(648C-746C). The catalyst and air flow up the combustor riser and separate at a
"Tee" shaped head. The flue gas is further "cleaned" of catalyst in the cyclones in
the upper regenerator. The recirculation catalyst standpipe returns some of the hot
regenerated catalyst to the combustor either on temperature or density control to
provide heat for initiation of the carbon burn. The remainder or the regenerated

157048
Process Flow
Page 13

catalyst flows down the regenerated catalyst standpipe on reactor temperature


control to the riser Wye to complete the cycle.
The flue gas exits the regenerator through the flue gas slide valves on pressure
control to the regenerator. An orifice chamber located downstream of the slide
valves acts to reduce the pressure drop and velocity across valves to minimize
mechanical deflection of the body and erosion to the internals. Many units have a
power recovery unit in place of the slide valve and orifice chamber to recover
electrical energy by letting down the high volume, moderate pressure flue gas
across a turbo-expander connected to a motor/generator. Finally the sensible heat
energy in the flue gas is recovered through steam generation in either a CO boiler
or flue gas cooler depending on the mode of operation in the regenerator. Many
units also have an electrostatic precipitator or wet gas scrubber to remove catalyst
fines from the flue gas before it is discharged to the atmosphere.
The reasons and methods for varying the high efficiency regenerator operation will
be discussed in more detail later in the PROCESS VARIABLES section.
RFCC Regenerator
As a result of the crude oil embargoes and oil price rises of the 1970s, interest in
processing heavier feeds in FCC units grew. However, FCC technology at that time
could not handle highly contaminated heavy feeds while maintaining a reasonable
degree of conversion. In the mid 1970s, UOP and Ashland Oil Company embarked
on a joint development project to develop catalytic cracking technology capable of
processing very heavy, highly contaminated feeds, i.e. feeds with high metals and
Conradson carbon contents. The result of this development program was the
commercialization of the RCCSM (Reduced Crude Conversion) process at Ashlands
Catlettsburg refinery in 1983.
The main feature of the RCC unit is a two stage regenerator equipped with a
catalyst cooler to remove heat from the regenerator. The upper or first stage
regenerator burns approximately 2/3 of the coke from the catalyst in partial
combustion mode to limit the heat of combustion and therefore the temperature of

157048
Process Flow
Page 14

the catalyst. A portion of the partially regenerated catalyst entering the lower or
second stage regenerator flows through the catalyst cooler(s) where heat is
removed from the catalyst to generate steam. The cooled catalyst and the
remainder of the hot catalyst from the first stage regenerator mix in the second
stage regenerator where the coke burning is completed under conditions of
complete CO combustion in the presence of excess O2. Carbon is burned off the
catalyst to low levels in the second stage regenerator at moderate temperature to
maximize catalyst activity. The combustion gases from the second stage
regenerator pass into the first stage regenerator where the pre-heated excess O2
improves coke burn kinetics, and is completely consumed. The combined flue gas
exits through two stages of cyclones in the first stage regenerator and out through a
single common flue gas line. The overall mode of combustion for the two stage
regenerator is partial burn with the additional benefit that all of the catalyst returning
to the reactor is fully regenerated due to the full burn environment of the second
stage regenerator.
Figure 8 shows the arrangement of the regenerator of an RFCC unit. The reactor is
the same as the modern Side by Side unit shown in Figure 7.
Figure 9 shows the process flow for a catalyst cooler. Although catalyst coolers are
not a new idea for FCC service, past attempts to employ catalyst coolers on FCCs
have been largely unsuccessful from both mechanical and process points of view.
UOPs catalyst cooler represents an improved design developed and refined to
provide both mechanical reliability and a wide range of heat removal flexibility. Heat
removal varies with the rate of fluidization air injected to the cooler and the catalyst
slide valve opening.
The operation of the catalyst cooler is as follows; catalyst enters the cooler shell
where the tube bundle is immersed in hot fluidized catalyst. Fluidization air is
injected at the bottom of the cooler shell to control the fluidization and heat transfer.
Annular bayonet type water tubes are used in the tube bundle. Water entering the
bundle flows up through the inner tube, flows out the top of the inner tube and down
through the annular space between the inner and outer tubes where heat transfer
occurs and water is vaporized to steam. In flow-through style coolers cooled
catalyst exits the cooler shell through a standpipe and slide valve and is returned to

157048
Process Flow
Page 15

the regenerator to allow hot catalyst to enter the top of the cooler to maximize the
cooler duty. Back-mix type coolers rely only on fluidization and back-mixing to
transfer hot catalyst from the regenerator rather than using catalyst flow through a
standpipe. Back-mix coolers have a simpler mechanical configuration but can only
remove approximately 70% of the heat transfer capable through a flow-through
cooler.
A large excess of water is circulated through the tubes where heat transfer
generates steam to ensure that the tube walls are always wet and cooled. The
steam and water mixture returns from the cooler bundle to a steam drum where the
steam and water are separated. Water from the drum is circulated back to the
cooler and the saturated steam from the steam drum is routed to the refinery steam
system.

157048
Process Flow
Page 16

Figure 8
UOP RFCC Regenerator Process Flow
Flue Gas

Spent Catalyst
from Reactor

1st Stage
Regenerator

Vent Tubes

Catalyst
Cooler

First
Stage Air

2nd Stage
Regenerator

Water/
Steam
Water

Recirculation
Catalyst
Standpipe
Regenerated
Catalyst to
Reactor
Second Stage
Air

157048
Process Flow
Page 17

Figure 9
UOP FCC Catalyst Cooler Process Flow
Water and
Steam
Saturated
Steam to
Superheater
Fluffing
Air

Makeup
BFW
Blowdown

Cooled Catalyst
Slide Vlave

Circulating
Water

FCC-PF009

157048
Process Flow
Page 18

Main Column
The main column is the first step in the separation and recovery of the cracked
hydrocarbon vapors from the FCC reactor. The reaction products enter the column
at high temperatures, 900-1022F (480-550C). The main column is similar to a
crude tower, with two important differences: 1) The vapors must be cooled before
fractionation can begin, and 2) a large quantity of lighter gas passes overhead with
the gasoline. Figure 10 shows the general process flow for an FCC main column.
Large quantities of heavy oil are circulated over a series of disc and doughnut trays
to cool the vapors and wash down entrained catalyst. The heat removed by the
main column bottoms and the heavy cycle oil is used for feed preheat, steam
generation, reboiler heat in the rest of the unit, or some combination of the three.
The catalyst washed out of the reactor is concentrated in the main column bottoms
stream.
Most of the bottoms flow is directed through exchangers for heat removal and
returned to the disc and doughnut trays. The return line must be free draining to
avoid plugging problems with catalyst fines settling in low points. Some of the
cooled bottoms material from the steam generators may be returned directly to the
bottom of the tower as quench to reduce the temperature of the liquid and minimize
coking and fouling in the bottoms system. Figure 11 shows a typical process flow
for the main column bottoms pumparound and product circuit.
Many older units used a slurry settler to separate and return catalyst fines to the
reactor with a slurry stream off the bottom of the settler. The main column bottoms
product comes off the top of the settler and is normally called clarified slurry oil. In
reactors with two stages of cyclones and in units with modern riser termination
devices, the use of slurry settlers has normally been discontinued. Heavy bottoms
product comes directly from the main column bottoms circulating stream, as does
any slurry recycle to the reactor.

157048
Process Flow
Page 19

Figure 10
UOP FCC Main Column
To Wet Gas
Compressor
CW

To Sour
Water

To Primary
Absorber

1
5
6

Gas
Concentration
Unit

FI
7

19
21

FI
22

Equalizing
Line to/from
Feed Drum

Steam

26
27
29

30

Heavy
Naphtha
Product
Gas
Concentration
Unit

Steam

32

Light Cycle
Oil Product

33

Flushing Oil

34
35

Gas
Concentration
Unit

36

Flushing Oil
37

Torch Oil
38

Reactor
Vapors

Steam

BFW

Main Column
Bottoms Product
CW

Raw Oil from


Surge Drum

Raw Oil to
Reactor

157048
Process Flow
Page 20

Figure 11
UOP FCC Main Column Bottoms Process Flow

6
Minimum
Spillback

MCB Product Circuit


Minimum Flow Valve

E
FRC

Main Column

Rx
Overhead

MCB
Product
Pumps

Tempered
Water

Quench

Steam

Steam
Main Column
Bottoms Circulation
Pumps

MCB
Product

MCB
Steam
Generators
Water

Raw
Oil
Water

Circulating
Bottoms/
Raw Oil
Exchanger

Raw
Oil

Net
Bottoms/
Raw Oil
Exchanger

157048
Process Flow
Page 21

As previously mentioned, most FCC units with modern riser terminations and
reactor cyclones do not require the use of a slurry settler and new units currently
being designed do not include settlers. If a refiner has strict specifications on the
ash content of the main column bottoms product, then more advanced alternate
fines removal equipment is usually employed to reduce the catalyst fines to very low
levels. The two most common types of catalyst removal equipment used today are
the micromesh filter and the electrostatic separator. Cyclonic separation devices
have also been used, but are typically limited to smaller capacity installations.
A typical micromesh filter system will have 2 or 3 vessels with up to 100 filter
elements in each. When multiple filtration vessels are used, each filtration vessel is
sized for 100% of the design flow rate. One vessel is typically in filtration mode
while another is in backflush mode to remove the filter cake from the elements.
When enough catalyst fines have deposited on the filter elements to increase the
pressure drop across the filter to a pre set limit, the vessel is taken off line for back
flushing. Once the filter vessel is off line and drained the vessel is filled with
backflush liquid, either HCO or LCO, and allowed to soak to help dissolve any
heavy aromatic compounds on the elements. The top of the vessel is then
pressured up with either fuel gas or nitrogen to provide the driving force for a high
velocity back flush. The back flush material is collected in a receiver vessel and
pumped back to the reactor riser. A typical process flow for the micromesh filtration
system is shown in Figure 12.
A typical electrostatic slurry oil filtration unit consists of 4-16 skid mounted
cylindrical shells (modules) depending on the volume of filtrate to be process. Each
module contains a high voltage cylindrical electrode surrounded by conductive glass
beads, with a ground rod located in the center of the module assembly. During the
separation cycle, the glass beads are ionized in an electrostatic field. As catalyst
particles flow between the beads, they are electrostatically collected on the surface
of the beads. Each module is sequentially back-flushed while the remaining
modules in the system continue the separation. In the backflush cycle, the electrode
is de-energized and the beads are fluidized, resulting in a circulating motion up
through the center of a 9-inch annular electrode and down the outside. The
circulation up the center annulus and down the walls of the module creates a
scrubbing action, to mechanically scrub the beads clean. Mechanically scrubbing

157048
Process Flow
Page 22

the beads as opposed to solvent soaking as with the micro-mesh filters, raw oil
feed, or any compatible oil can be used as the backflush medium to an electrostatic
filter. The back flush material is directed back to the reactor riser.

Figure 12
Main Column Bottoms Product Filtration System
Backwash Gas
(N2 or Fuel Gas)

Clean MCB
Product to
Storage

Filter
#1

Filter
#2

Filter
#3

N2 or Fuel Gas
Vent

Back Flush
Liquid
(LCO/HCO)
MCB
Product

Receiver
Vessel

Catalyst
Backwash
to Reactor

157048
Process Flow
Page 23

There are typically three side-cuts withdrawn from the main column, heavy cycle oil
(HCO), light cycle oil (LCO), and heavy naphtha (HCN). The refiner may withdraw
all three, only two or one, depending on product needs and tower design. On
relatively rare occasions, the main column is designed with a fourth side-cut to
discretely fractionate a heavy LCO cut and a light LCO cut. The side-cut streams
that go out as product are usually stripped to meet flash-point specifications.
Pumparound loops from these side-draws are used to heat balance the main
column by exchanging heat with the gas concentration unit reboilers, the raw oil
charge or boiler feed water. The heat removed in the bottom and side pumparounds determines the amount of reflux in each section of the tower and must be
properly balanced for proper column operation. Gasoline and light gases pass up
through the main column and leave as vapors. After being cooled and condensed,
unstabilized gasoline is pumped back to the top of the column as reflux to control
the top temperature in the column. Figures 13, 14, 15 and 16 show typical process
flows for the HCO pumparound, the LCO pumparound, the Heavy Naphtha
pumparound and the Main Column Overhead system, respectively.

157048
Process Flow
Page 24

Figure 13
Main Column HCO Pumparound

Main Column

LIC

Gas Con Unit


Debutanizer
Reboiler

HCO Internal
Reflux
(Pumped)

To MCB/Feed
Exchanger Outlet
(for startup)
Filling Line
(from feed pump)

Heavy Cycle Oil


Circulation
Pumps

To Feed
Surge Drum
(normally no flow)
To Pump
Flushing Oil
Supply Header

157048
Process Flow
Page 25

Figure 14
Main Column LCO Pumparound and Product

FI
FIC
LIC
Steam

FIC
LCO
Product

BFW
CW
Preheater

FIC

LCO to
Flushing Oil

Debutanizer Feed
Exchanger

FIC
Stripper
Reboiler
Rich Oil from
Sponge Absorber
Lean Oil to
Sponge Absorber
FCC-PC403

157048
Process Flow
Page 26

Figure 15
Main Column Heavy Naphtha Pumparound and Product

Main Column
C3/C4 Splitter
Reboiler

Circulating Naphtha/
Debutanizer Feed
Exchanger

Steam
E
FRC

Heavy
Naphtha
Stripper

LCO
Stripper

Reflux
(Gravity Flow)

LIC

Heavy Naphtha
Circulation
Pumps
Heavy Naphtha
Product Pumps
Heavy Naphtha
Product Cooler
HeavyNaphtha
to and from
NHT Unit
Signal from HCN
Hydrotreater

CW
FRC
E

Hydrotreated
Heavy Naphtha
Product

157048
Process Flow
Page 27

Figure 16

Main Column Overhead System

FCC/DS-R00-37

157048
Process Flow
Page 28

The raw oil feed system is included in the main column section for better process
efficiency, i.e. to take advantage of the heat from the main column. Feed enters the
unit from storage or directly from upstream processes, such as a vacuum tower or a
hydrotreater. The latter scheme is more efficient because the feed will not have to
be cooled before storage and then reheated flowing into the FCC. The number and
type of exchangers used will depend on cost and process factors that will vary with
each refinery.
Most newer units do not use fired charge heaters. Fired charge heaters have
become unpopular due to the increases in fuel costs, operational safety and impact
on overall refinery stack emissions. The feed goes directly to the riser after the raw
oil/main column bottoms exchanger. Figures 17 and 18 show typical process flow
schemes for the FCC feed preheat system without a fired charge heater and with a
fired charge heater, respectively.

Figure 17
Feed Preheat
Equalizing
Line To/From
Main Column

Raw Oil Surge


Drum

Raw Oil from


Crude Unit/
Hydrotreating

To
Reactor
LCO
Product

MCB
Product

Circ.
MCB

MCB
Recycle
HCO
Recycle
FCC-PF401

157048
Process Flow
Page 29

Figure 18
Feed Preheat with Fired Heater

Equalizing Line
To/From Main
Column

Raw Oil Surge


Drum

Fired
Heater
Raw Oil from
Storage/
Upstream Unit

MCB
Product

To
Reactor

Circ.
MCB

Fuel
Gas

FCC-PF401

157048
Process Flow
Page 30

Gas Concentration and Recovery


This section further separates the main column overhead products into stabilized
gasoline, LPG and fuel gas. The normal configuration is shown in Figure 18.
Unstabilized gasoline from the main column overhead receiver is pumped to the
primary absorber, where it is used to adsorb C3s and C4s in the gas stream at
much higher pressure than the main column. From here the liquid stream goes to
the high pressure receiver (separator), then the stripper column, where H2S and
C2- are removed. The gasoline off the bottom of the stripper is pressured to the
debutanizer for separation of LPG and gasoline and vapor pressure adjustment of
the gasoline. The overhead of the debutanizer is olefins rich LPG which is often
further processed, for C3 and C4 separation and propylene recovery.
The gas from the main column overhead receiver goes first to the wet gas
compressor. From here it is pressured to the HPS, the primary absorber, and finally
the sponge absorber. Valuable light products such as LPG are removed in the first
of two vessels by absorption into the gasoline. The second vessel is the sponge
absorber which uses a LCO pumparound from the main column as a final
absorption stage before the gas goes out as fuel.
Wash water, typically clean condensate, is injected into the inlet to the wet gas
compressor interstage condenser. From the interstage receiver it is pumped to the
high pressure receiver then to the main column overhead condensers. This water
washes out salt forming and corrosive and species such as H2S, NH3, cyanides and
phenols. The wash water flow is shown in Figure 19.

D
HPR
IR
PA
SA
S
WGC

HPR

Wash Water to MC
OVHD Receiver

IR

Debutanizer
High Pressure Receiver
Interstage Receiver
Primary Absorber
Sponge Absorber
Stripper
Wet Gas Compressor

Legend:

Wash
Water

WGC

Gas from
MC Overhead
Receiver

Gasoline from
MC Overhead
Receiver

40

P
A

Rich Lean
Oil Oil

S
A
36

Typical Gas Concentration Unit Process Flow

Figure 19:

40

Stabilized
FCC Gasoline

HCO

LPG

Fuel
Gas

157048
Process Flow
Page 31

Main
Column

Hydrocarbon
Water

Condensate

To Sour Water
Stripper
WGC
1st Stage

Main Column
Receiver

Interstage
Drum

Wash Water Flow

Figure 20:

WGC
2nd Stage

High Pressure
Receiver

157048
Process Flow
Page 32

157048
Process Control
Page 1

PROCESS CONTROL
Reactor-Regenerator Control Systems
Most of the control systems in a Fluid Catalytic Cracking unit are similar to those used
elsewhere in the refinery.
Good control of the catalyst circulation through the reactor and regenerator is critical for
stable operation. The catalyst circulation control scheme is shown in Figure 1. This
figure shows a side by side unit with a bubbling bed regenerator but the catalyst
circulation control between the reactor and regenerator is the same on all FCC and
RFCC units.
The circulation of hot regenerated catalyst from the regenerator to the reactor is
controlled to maintain a constant reactor temperature with the regenerated catalyst slide
valve. The circulation of spent catalyst from the reactor to the regenerator is controlled
to maintain a constant catalyst level in the reactor with the spent catalyst slide valve.
The controls on both the spent catalyst and regenerated catalyst slide valves also
include a low differential pressure override. If the differential pressure across either slide
valve drops to a very low or negative value the override will close the slide valve. This
minimizes the possibility of reverse flow in the standpipes, either air entering the reactor
or hydrocarbon entering the regenerator, which are hazardous situations.
Figure 1 shows signals from the reactor temperature controller and level controllers
going to low level selectors (LSS). The low signal selectors also receive signals from the
differential pressure controllers on the corresponding slide valve. If the differential
pressure across the slide valve is greater than the override setpoint, typically 2 psi (0.14
kg/cm2) the LSS will select the process variable (level or temperature) to control the
slide valve. If the slide valve pressure drop falls below the override setpoint the LSS will
send that output to the slide valve which will start closing. The low differential pressure
override controllers should always be in automatic.

157048
Process Control
Page 2

Figure 1
Catalyst Circulation Controls
Products to
Main
Column

TIC
PDIC

Reactor

Riser
Termination
Device

HSS

>
LIC

Flue
Gas

PIC

Regenerator

LSS

LI

<
PDIC

XI
(Density)

Spent
Catalyst
Slide Valve
LSS

<
PDIC

Raw
Oil

Air

Regenerated
Catalyst Slide
Valve
Lift Gas/
Steam

FCC-PC001

157048
Process Control
Page 3

For steady control of the catalyst circulation between the reactor and regenerator the
differential pressure across the slide valves must be constant. To ensure steady slidy
valve DPs the differential pressure between the reactor and regenerator is controlled
with the double disc flue gas slide valves on the outlet of the regenerator. In addition to
the slide valves an orifice chamber is also used to take approximately 2/3 of the total
flue gas system pressure drop to minimize erosion in the flue gas slide valves.
A typical flue gas system without power recovery is shown in Figure 2. The reactor
pressure is not controlled directly and floats on the main column overhead pressure.
The reactor-regenerator differential pressure controller allows the regenerator pressure
to change along with the reactor pressure. Pressure control for units with power
recovery is discussed later.

Figure 2
Regenerator Pressure Control/
Flue Gas System
HSS
>

PIC

PDIC

Signal from
Reactor
Pressure Tap

Flue Gas

Flue Gas
Slide Valves

Orifice
Chamber
Steam

CO Boiler
Air
Air

Electrostatic
Precipitator

Water

FCC-PC002

157048
Process Control
Page 4

Reactor Control (Figure 3)


Reactor temperature is controlled by the flow of hot regenerated catalyst as described
above. The temperature controller may be located in the reactor vapor line or in the
upper vapor space of the reactor vessel depending on the type of riser termination
device.
The reactor pressure is not directly controlled. Reactor pressure floats on the main
column overhead pressure. Thus, the reactor pressure is the sum of the main column
overhead receiver pressure plus the pressure drop through the main column and MC
overhead condensers plus the pressure drop through the reactor cyclones and reactor
vapor line.
The reactor catalyst level is controlled by the flow of spent catalyst to the regenerator as
described above. Modern reactor designs include a wide range level indicator and a
more accurate, narrow range level controller. Also, the density in the spent catalyst
stripper is measured to allow compensation of the level indication for actual catalyst
density. The level is typically controlled off of the wide range LIC because the signal has
less noise but a switch is included in newer unit designs to allow use of the more
accurate narrow range LIC if desired.
Steam is used to atomize the feed in the elevated Optimix feed distributors (Figure 4).
The amount of steam used determines the both the pressure drop and extent of
atomization as well as the velocity out of the distributor tip and penetration into the
catalyst. During normal operation the steam and oil enter the nozzle separately and are
mixed internally near the tip. The steam flow is normally set at design rates, typically1-2
wt% of the design charge rate. During operation at turndown additional steam may be
used to maintain the optimal pressure drop across the nozzles (typically 50-75 psig) to
ensure adequate atomization is maintained. An alternative that allows maintaining near
design pressure drop and atomization at turndown with minimal additional steam is to
mix a small amount of steam directly with the oil before it enters the nozzle. This results
in a large increase in pressure drop with minimal increase in velocity out of the tip. The
oil and steam flows to each nozzle have restriction orifices with pressure drop indicators
and globe valves to ensure that the flows to each nozzle are equal.

157048
Process Control
Page 5

Figure 3
Reactor Control and Instrumentation
PDI
TIC
LIC

LIC

SWITCH

LI (Density
Compensated)

XI
(Density)
XI
(Density)

Prestripping
Steam

PDIC

< LSS

Stripping
Steam

MPS

Fluffing
Steam

Spent
Catalyst
LSS
PDIC

Regenerated
Catalyst

<

Atomizing
Steam
For Feed/Steam
controls see Figure 4
Raw Oil

FIC
Lift Gas
FIC

Lift Steam

MPS
FIC
Start-up/Emergency
Steam

FCC-PC003

157048
Process Control
Page 6

The feed bypass system is also shown in Figure 4. When a situation requiring a quick
shutdown is encountered, a control board mounted switch is activated which trips a
solenoid valve controlling the pneumatic signals to the feed bypass valves, causing
these valves to move to their failure positions, i.e. the valve in the line to the riser closes
and the valve in the bypass line to the main column opens. Normally, the next course of
action is to open the emergency steam to the riser to either maintain catalyst circulation
if the regenerated catalyst slide valve remains open or to clear the riser of catalyst if the
regenerated catalyst slide valve is closed.
On units with elevated feed distributors, another important operating variable affecting
the yield pattern is the lift zone velocity. The lift zone velocity is a function of the lift
steam and/or lift gas flow rates which are controlled on straight flow control. As the lift
zone velocity is increased the catalyst density at the point of the feed injection
decreases allowing better penetration of the atomized oil droplets into the catalyst. The
optimum lift zone velocity is typically in the range of 10 15 ft/sec (3 4.5 m/sec).
Either lift gas, lift steam or a combination of both may be used to achieve the optimum
lift zone velocity.
Stripping steam flows are also controlled on straight flow control. The optimal total
stripping steam rate is typically 1.7 2.5 lb/M-lb catalyst circulation but this can vary
significantly with depending on the unit design. The stripping steam rate should be
changed when any process conditions are changed that result in a significant change in
the catalyst circulation rate. The stripping steam rate should also be tested occasionally
to ensure that the optimum steam rate is used.

157048
Process Control
Page 7

Figure 4
Feed/Atomizing Steam Control

FI

FI
FI

To other
nozzles

PI

Steam
FO

Local PI must be
readable from valve
PI

Local FI must
be readable
from valve

FI
FI

To other
nozzles

Local FI must
be readable
from valve
To other
nozzles

NORMALLY
NO FLOW
HEADER
PURGE

HS

Feed Bypass
Switch

Raw Oil to Main


Column

S
Instrument
Air

FO
Vent

FC

Raw Oil from


Preheat

FCC-PC004

157048
Process Control
Page 8

Bubbling Bed Regenerator Control


In full combustion units without a catalyst cooler the regenerator temperature is not
directly controlled and is a function of a number of process variables. In simple terms,
the regenerator temperature is a function of delta coke, i.e. the wt% coke on spent
catalyst entering the regenerator minus the wt% coke on regenerated catalyst leaving
the regenerator. The concept of delta coke is discussed in more detail later in the
section of this book covering Process Variables.
The regenerator may be operated to burn the coke on catalyst completely to CO2
(complete combustion mode) or may be operated so that some of the coke is burned to
CO (partial combustion mode).
In units that operate in partial combustion mode the CO2/CO ratio of the flue gas may
be controlled to adjust the heat of combustion and therefore adjust the regenerator
temperature. The CO2/CO ratio is controlled primarily with the amount of combustion air
entering the regenerator. Partial combustion operation is discussed in more detail in the
Process Variables Section.
In units with a catalyst cooler, the regenerator temperature may be controlled by
controlling the amount of steam generated in the cooler. The controls of the catalyst
cooler are discussed in more detail later in this chapter.
The regenerator catalyst inventory serves as the surge capacity for catalyst in the
system and there is no control instrumentation on the regenerator catalyst level. A level
indicator is provided to monitor the regenerator catalyst level. The regenerator catalyst
level changes with catalyst additions, withdrawals and losses. In most units the level is
controlled by intermittent withdrawals of equilibrium catalyst. It is important that the level
be maintained above the terminations of the cyclone diplegs and below the level that
would cause the catalyst in the cyclone diplegs to back up into the cyclone dustbowl.

157048
Process Control
Page 9

The air rate to the regenerator is controlled either to maintain a minimum of excess
oxygen in the flue gas (typically 2%) for full combustion operation or to control the
CO2/CO ratio and therefore the heat of combustion and regenerator temperatures in
partial combustion operation.
High Efficiency Regenerator
The instrumentation and controls for a FCC unit with a high efficiency, combustor style
regenerator is shown in Figure 5.
The pressure, regenerated catalyst temperature and combustion air rate for the high
efficiency regenerator are the same as the bubbling bed regenerator described above.
The difference between the high efficiency regenerator and a conventional "bubbling
bed " regenerator is that the regenerator is divided into two sections. The lower section
is called the combustor and is where the spent catalyst and air mix and coke
combustion occurs. The combustor operates in the fast fluidized regime of fluidization.
All the catalyst entering the combustor is transported up the combustor riser into the
upper regenerator where the regenerated catalyst disengages from the flue gas. The
upper regenerator holds the cyclones, provides volume for the regenerated catalyst to
disengage from the flue gas and provides the surge capacity for catalyst in the system.
An important feature of the high efficiency regenerator is the recirculating catalyst
standpipe and slide valve. The recirculation of hot regenerated catalyst from the upper
regenerator to the combustor is important in controlling the coke combustion rate. By
controlling the amount of catalyst recirculated, the following parameters are controlled in
the combustor: the pre-combustion mixing temperature, the catalyst density, catalyst
flux and catalyst residence time. This, in turn, allows the coke combustion rate and
catalyst regeneration to be optimized. The recirculating catalyst slide valve is controlled
through a low signal selector and a slide valve PDIC, similarly to the other slide valves.
On early designs, this slide valve position was set on hand control. In current designs,
the recirculation slide valve position is controlled by a temperature or density controller
located in the upper section of the combustor. A switch is used to select the input signal
to the recirculation slide valve low signal selector.

157048
Process Control
Page 10

Figure 5
High Efficiency Regenerator Controls and
Instrumentation
>

TI's
(1 Each Cyclone)

PIC

PDIC
Signal from
Reactor Pressure
Tap

LI

XI
(Density)

Recirculating
Catalyst Slide
Valve

FIC
Fluffing Air
Regenerated
Catalyst to Reactor

PDIC
TIC
LSS

XIC
(Density)
Spent Catalyst
from Reactor

<

SWITCH

FCC-PC005

157048
Process Control
Page 11

In a high efficiency regenerator the dense bed catalyst level in the upper regenerator
provides the surge volume for the unit and is not controlled directly except by catalyst
additions and withdrawals.
A small flow of fluffing air to the upper regenerator on straight flow control is required to
ensure proper fluidization and flow into the regenerated and recirculation catalyst
standpipes.

RFCC Two Stage Regenerator Control


The regenerator control systems for the RFCC unit with a 2 stage regenerator are
shown in Figure 6. The reactor control systems are identical to those described above
for the conventional reactor-regenerator.
The principal difference is that the coke combustion is completed in 2 stages. The upper
regenerator, or 1st stage, is a bubbling bed regenerator operating in partial combustion
mode without excess oxygen. The catalyst exiting this stage still contains a significant
amount of coke which is burned off in the 2nd stage operating in full combustion mode
with excess oxygen. This allows the benefits of both partial combustion (lower
regenerated catalyst temperature) and full combustion (very low carbon on regenerated
catalyst for maximum activity).
In the RFCC the catalyst level in the second stage is controlled by the flow of catalyst
from the first stage to the second stage through the recirculation catalyst standpipe and
slide valve. This slide valve has a differential pressure override which closes the slide
valve if the pressure drop across the valve drops to low as described above for the
other slide valves. The level in the first stage regenerator is the surge volume for the
unit and is typically controlled by periodic withdrawals of equilibrium catalyst.
Since RFCC units are designed for heavily contaminated feed stocks one or more
catalyst coolers are included in the design and are used to control the temperature of
the regenerated catalyst circulated back to the reactor. The total air rate which controls

157048
Process Control
Page 12

the CO2/CO ratio in the flue gas and therefore the heat of combustion is also used to
adjust the temperature of the regenerated catalyst.

Figure 6
RFCC Regenerator Controls and Instrumentation

LI
Spent Catalyst
from Reactor
XI

Side View

Vent Tubes
PDIC

PDIC
LIC

First
Stage Air
LSS

LSS

<

<
TIC

Recirculation
Catalyst
Standpipe

Cooled
Catalyst
Standpipe

Regenerated
Catalyst to
Reactor
Second
Stage Air

Second
Stage Air

FCC-PF006

157048
Process Control
Page 13

Air Blower Control


The control system for the main air blower depends on whether the blower is an axial or
centrifugal machine and whether it is turbine or motor driven. The most common
configuration built today is a turbine driven axial blower because these are generally
more efficient, but the choice is unit specific.
Figure 7 shows a conventional control scheme for a turbine driven axial blower. Flow is
measured by the venturi in the discharge line and is controlled by varying the speed of
the turbine. Alternatively, the air rate may be controlled by varying the stator vane
position for a fixed speed, axial blower.
A variable vent line, called a snort, is located on the air blower discharge and is used to
prevent air blower surge. An anti-surge system control system constantly monitors the
flow through the blower and the discharge pressure and compares the operating
condition to the surge line on the blower curve. If conditions close to the surge line are
detected the anti surge-controller opens the snort valve to increase the flow to
atmosphere and reduce the discharge pressure of the blower. Modern anti-surge control
systems available from specialized vendors continuously monitor a number of process
variables and calculate deviation from surge to allow operation closer to the surge line
while providing better protection for the equipment. The process variables monitored by
the modern anti-surge controllers are shown in Figure 7.
Occasionally, on older partial combustion units, an additional, smaller vent is used to
fine tune the air flow to the regenerator. This may be tied into a differential temperature
controller (DTC) which controls the temperature difference between the regenerator
dense and dilute phases to limit or control afterburn in partial combustion units.
On RFCC units control valves are used on the air lines to the first and second stages of
the regenerator (Figure 8). Typically the air to the second stage is set at ~25-30% of
the total air flow. In some units an additional control loop is included to minimize the
discharge pressure and thereby minimize the energy consumed by controlling the axial
air blower stator vane position. This control loop minimizes the blower discharge
pressure until one of the 2 flow control valves on the discharge is nearly wide open.

157048
Process Control
Page 14

Figure 7
Main Air Blower Control
Vent to
Atmosphere

Silencer
Snort
Valve

Low Flow
Shutdown

FO

FIC
(Temp, Pressure Corrected)

Instrument
Air

XIC
(Anti-Surge)

Steam

Vent

ST
SIC
Suction
Filter
Housing

T
TT PT

Air
Cylinder FT

TT PT

TT PT

FT

Air to
Regenerator

Special Check
Valve

FCC-PC007

Figure 8
RFCC Main Air Blower Control
(Anti Surge and Special Check Valve Details Not Shown)
Vent to
Atmosphere

Silencer

FIC (Press, Temp


Corrected)

TT PT

ZIC

ZT
To First Stage
Regenerator

XIC
(Anti-Surge)
Steam

Suction
Filter
Housing

FO

Special Check
Valves

FIC (Press, Temp


Corrected)

T
TT PT

ZT
To Second Stage
Regenerator

Stator Vanes

FCC-PC008

157048
Process Control
Page 15

The check valve in the air blower discharge line isolates the blower from the regenerator
if the blower trips. This minimizes the possibility of hot catalyst backing up into the
blower and minimizes the volume of air in the piping if surging occurs. The closing
action is assisted by a spring loaded air cylinder, which operates when the air flow falls
below a certain limit. When the flow drops below the low limit a solenoid valve deenergizers and vents the air from the cylinder allowing the spring to move a cam which
bumps the check valve to assist it in closing. An air line from the catalyst hoppers or
plant air is used to provide plant air to clear catalyst from the discharge line if the blower
is down. It can also be used to supply warm blower air to the catalyst hoppers.

Power Recovery Controls


A typical process flow and control scheme for the flue gas system on an FCC with a
power recovery unit is shown in Figure 9. On units with a power recovery turbine,
butterfly valves are used in the flue gas line instead of slide valves for pressure control.
The butterfly valves operate on a single, split range controller which first opens the
valve on the line to the expander inlet then opens the butterfly valve on the bypass
around the expander if the capacity of the expander is exceeded. The bypass valve may
also be controlled to limit the speed of the expander or the pressure in the expander.
In the past, flue gas power recovery systems were designed with regenerator pressure
held steady to minimize fluctuations to the power recovery expander-motor/generatorair blower train. With this control strategy, a regenerator pressure controller output
signal was used to control the power recovery butterfly valve positions. In this control
scheme, the regenerator pressure is fixed and the reactor-regenerator differential
pressure is allowed to float within reasonable limits.
Recently, the control system for flue gas power recovery pressure control has been
modified so that the reactor-regenerator differential pressure is controlled with a
differential pressure controller as in conventional flue gas systems. The objective of this
change in pressure control strategy is to insure that the reactor-regenerator pressure
balance and catalyst circulation are maintained at steady conditions. Now the output
signals of the reactor-regenerator PDIC and the regenerator PIC are fed to a high signal

157048
Process Control
Page 16

selector (HSS). The high signal selector directs the appropriate control signal (normally
the PDIC) to set the positions of the expander inlet and bypass butterfly valves via a
split range signal. The expander turbine is discussed further in the section covering
Equipment.
Modern power recovery controls, while controlling in the same manner, are more
complicated than discussed here. Power recovery controls and anti-surge controllers
are provided by specialized vendors. The additional functions performed by these
controllers are beyond the scope of this manual.
On units with power recovery, a steam turbine may be used for startup of the air blower.
The turbine can also provide auxiliary power if necessary. The motor/generator imports
or exports power to maintain a constant speed on the power recovery train. If more
energy is being supplied to the expander and the turbine than is required by the blower
there will be surplus electricity generated and exported. If the blower needs more power
than the expander is providing then electricity will be consumed to hold the train at
normal speed.
The flue gas leaving the regenerator flows through a series of small cyclonic devices in
the third stage separator for catalyst fines removal to minimize erosion in the expander.
The underflow catalyst stream from the third stage separator, carried by a small gas
flow, bypasses the expander and typically leaves the system with the main flue gas
stream downstream of the expander turbine. The underflow from the bottom of the
separator is controlled by a restriction orifice called the critical flow nozzle.
A flue gas quench system is also included on units with power recovery. If the flue gas
temperature exceeds the design temperature of the expander a flow of cooling steam is
started to the regenerator plenum through a split range controller. If the steam fails to
cool the flue gas sufficiently a flow of cooling water, typically BFW, is started to the
plenum. Most power recovery vendors also include an emergency steam quench at the
inlet of the expander for additional protection.

157048
Process Control
Page 17

Figure 9
Power Recovery Controls
Quench Connection See Detail Below

TIC
>
PIC

HSS

Split
Range

Flue
Gas

Orifice
Chamber

PDIC

Butterfly
Valves

Third
Stage
Separator

Flue Gas
Cooler

Critical
Flow
Orifice

Motor/
Air Blower
Generator
M

Electrostatic
Precipitator

Steam
T

Steam
Turbine

Expander
Air

Regenerator Plenum Chamber Quench Detail


HighTemperature
Signal Opens This
Control Valve First

TIC

Split
Range

LPS

Atomizing
Steam
FC

Purge
Steam

FI
BFW

Signal From
Regenerator
Temperature
Transmitter

To Other
Nozzles
FC

RO

Concentric
Sleeve Purge

Stuffing
Box

Plenum
Shell

Retracta
ble Tip

FCC-PC009

157048
Process Control
Page 18

Catalyst Cooler Controls


Catalyst coolers provide FCC operating flexibility, permitting direct control over the
regenerated catalyst temperature. The regenerated catalyst temperature is a major
variable impacting cracking reactions since it sets both the catalyst to oil ratio and
determines the temperature of the catalyst surface at its first contact with the oil feed.
Both of these variables are important in determining the overall conversion and yield
pattern in the FCC.
Figure 10 shows a schematic of a flow-through catalyst cooler installed on a high
efficiency regenerator with the associated cooler fluidization air, water circulation, steam
drum and control instrumentation. As already discussed, hot catalyst from the upper
regenerator flows through the cooler shell, around the water tubes of the inserted tube
bundle and out of the cooler through a cooled catalyst standpipe and slide valve into the
combustor. The fluidization air lance system delivers fluidization air to the cooler shell to
maintain catalyst fluidization and mixing in the shell and to ensure that catalyst flows
smoothly through the cooler and out through the standpipe. The combination of mixing
and net catalyst flux through the cooler provide the driving force for heat transfer by
maintaining contact of hot catalyst with the tube wall.
The cooler duty is therefore controlled by controlling the amount of fluidizing air and the
flow through the cooled catalyst standpipe. Minimum and maximum fluidizing air rates
are typically specified to ensure that the air lances do not plug with catalyst and that
high velocities in the cooler do not cause erosion on the tube surface. In back mix type
coolers without a standpipe and slide valve the cooler duty is controlled only with the
fluidizing air.
To protect the tubes from thermal damage and oxidation, a large excess of water is
circulated through the tubes to ensure that the tube walls remain wetted. The ratio of
water circulated to steam generated is typically in the range of 20:1 to 25:1 lbs water
circulation per pound of steam generated. In the most recent designs the water
circulation rate is determined by the pump curve and no control valve is provided. In
earlier designs water circulation is controlled by a control valve. A low flow signal from
the flow indicator or controller activates a spare water circulation pump autostart. A low
low flow signal from the water circulation flow indicator or a low low steam drum level

157048
Process Control
Page 19

effectively causes the cooler to shutdown by closing the cooled catalyst slide valve and
closing the fluidization air control valve.
The mixture of steam and water exiting the cooler tube bundle flows to the steam drum
where the steam and water are separated. The saturated steam flow from the drum is
metered and flows out to the refinery steam system. Normally the saturated steam
leaving the steam drum is superheated in some type of downstream steam superheater.
The water returned to the steam drum is recirculated back to the cooler tube bundle. A
small continuous blowdown flow of water is removed from the drum to control
accumulation of impurities in the circulating water. The outputs of the steam product
flow meter and the steam drum level indicator are summed and control the flow of boiler
feed water (BFW) makeup entering the steam drum.

157048
Process Control
Page 20

Figure 10
Catalyst Cooler Controls
Steam and
Water

Low Low Flow or


Low Low Level
Fluffing Air Trip

Steam

Low Low
Level (2/3
Voting)

LG

LT

FI

LI
PI

VENT

FIC

LT

TI

DE

PG

STEAM
SEPARATOR

Air

LIC

LT

TI

FI

Low Low Flow or


Low Low Level
Slide Valve Trip

Intermittent
Blowdown

Continuous
Blowdown

Low/Low
Low Flow
(2/3 Voting)

FIC

FI

Low Flow
Pump Auto
Start
FT

Makeup
BFW
VENT
S
DE

To Motor
Control
Circuit

To Motor
Control
Circuit

Steam

FO

FCC-PC010
I

Interlock System

157048
Process Control
Page 21

Emergency Interlock Systems


For many years automated interlock systems that removed feed from the FCC were not
used because it was assumed that a well trained operator would make a better decision
regarding stopping feed to the unit than any logic system looking at only a limited
number of inputs. Also, since many of the inputs into the interlock system relied on
pressure taps around the reactor and regenerator which were prone to plugging, the
threat of spurious trips was too great.
Recently, however, many refiners understand the value of a properly designed interlock
decision to automatically remove feed from the FCC and place it in a safe condition.
Also, in many refineries the turnover of operations personnel has increased so that
many FCC operators have limited experience. There have been a number of incidents
where operators tried to keep the unit running during upset conditions warranting
shutting down the unit only to greatly increase the mechanical damage done to the unit.
Instead of a shutdown lasting only a few hours an extended shutdown resulted.
UOP now includes an emergency interlock system on all new units and major revamps.
The purpose of this system is to move the unit to a safe condition during an abnormal
event while permitting a safe, fast restart of the unit once the problem is resolved. This
system automatically performs the steps necessary to accomplish these goals that were
once left to the operator. The system is also designed to minimize the risk of spurious
trips or shutdowns resulting from false indications when no abnormal condition existed.
The emergency interlock system monitors the air flow rate, regenerated and spent
catalyst slide valve pressure drops and valve positions, feed flow rate, reactor
temperature, and reactor stripper level to determine and verify the existence of an
abnormal event warranting a shutdown of the FCC. Once the abnormal event is
detected and verified by 2 out of 3 voting systems or a by a combination of abnormal
process readings the following actions are automatically initiated:

157048
Process Control
Page 22

The feed is bypassed to the main column


Raw oil flow rate is reduced (now going to the main column)
The spent and regenerated catalyst slide valves are closed
Steam is increased to the riser
All related controllers are placed in manual as required

Torch Oil Nozzle Control


Figure 11 below shows a typical torch oil arrangement for an FCC regenerator. The
torch oil nozzles provide a means of injecting heavy oil, usually raw oil feed or HCO,
into the regenerator when extra heat is needed, e.g. during startup. Details of the nozzle
will be described in the section covering equipment. Control of the torch oil flow and the
torch oil atomization steam is often by hand control on older units. New unit designs
usually use a flow controller with a split range output to the torch oil flow and the torch
oil atomization steam to ensure that the atomizing steam is commissioned before the
oil. The torch oil assembly is provided with a continuous steam purge to the annular
space around the torch oil nozzle to keep it clear of catalyst. This purge steam flow is
regulated to less than 50 lb/hr (25 kg/hr) steam with a restriction orifice. In addition, a
small flow of steam is sent to the nozzle tip through a restriction orifice when torch oil is
not in use to help cool the nozzle and keep it from plugging with catalyst.

157048
Process Control
Page 23

Figure 11
Torch Oil Control
Atomizing
Steam

PI
FC

Steam

Annular Sleeve
Purge Steam

STRAINERS

Split Range
(Steam Valve
Opens First)

Manifold
Purge Steam

FI MUST BE
READABLE
FROM CONTROL
VALVE

PI

RO

FI

FC

FIC

Regenerator
Shell and
Lining

PI MUST BE
READABLE FROM
CONTROL VALVE

Stuffing Box

Instrument
Air

FC
VENT

DE

Emergency Interlock
Unit Shutdown Logic

From Raw
Oil Pumps

From HCO
Oil Pumps
FCC-PC011

157048
Process Control
Page 24

Direct Fired Air Heater (DFAH)


Figure 12 shows the control system of a modern direct fired air heater, present on all
FCC units between the main air blower and the combustion air inlet to the regenerator.
The air heater is used for refractory curing and dry-out following repair or renewal of
regenerator linings as well as during normal startup to heat the regenerator catalyst
inventory. The DFAH outlet temperature is controlled by the fuel gas rate. A high
temperature shutdown trips the fuel gas to the heater to prevent damage to the air grid
in the regenerator. Modern air heater controls trip the fuel gas on a flame out signal
from a flame sensor or on low air flow rate. Separate shutoff valves are provided so that
the tight shut off of only the fuel gas control valve is not relied upon for emergency trip
conditions.

Figure 12
Direct Fired Air Heater Control
To
Regenerator

Air
Ignitor
Start
Flame
Sensor

High Temperature
Shutdown
I

PDI Must Be
Readable
From Damper

TIC

Damper

Ignitor

Sight
Port

Burner

Pilot/
Ignitor

Sight
Port

Pilot Gas
PI

Sight Port
(sighting
flame)

PI

Sight Port
(sighting
opp. wall

PI
Pressure
Control
Valve
PI

PI

PIC

S
S

Interlock Shuts Down the Air Heater on:

VENT

DE

FC

INSTRUMENT
AIR

Fuel
Gas

Low Air Flow


High Outlet Temperature
Loss of Flame Detection

FCC-PC012

157048
Process Control
Page 25

Catalyst Addition Controls


Continuous additions of fresh catalyst are required to maintain the activity of the catalyst
in the reactor and regenerator and to replace catalyst fines lost from the unit through the
cyclones. Regular additions of small batches of catalyst results in more stable operating
conditions and yields than larger batches added less frequently. The typical UOP
catalyst addition system uses a volume pot and automated valve sequence to add a
constant volume of catalyst at timed intervals. This system is shown in Figure 13.
Specialized valves, designed to close on the catalyst transfer lines when they are full of
catalyst, are required to ensure reliable service. Other systems are available including
weight addition systems which include a load cell to add weighed batches of catalyst on
a regular interval.

157048
Process Control
Page 26

Figure 13
Catalyst Addition Control
Fresh Catalsyt
Hopper
INSTRUMENT
AIR

VENT

FC

Instrument
Air

Plant Air
Vent

Plant Air
FC

RO

Volume
Pot

RO

Instrument
Air

Plant Air
Vent

FC

FI
FI
Plant Air

Sight Flow Indicator

To Regenerator

FCC-PC013

157048
Process Control
Page 27

Main Column Control


The main column is the first step in the product separation sequence. The superheated
reactor vapors need to be cooled so that fractionation can be conducted. In large
measure, operation of the main column becomes an exercise in controlled heat removal
coupled with sufficient liquid-vapor contacting to effect the desired degree of
fractionation into desired product streams, typically main column bottoms (MCB), light
cycle oil (LCO), heavy naphtha (HCN), unstabilized gasoline and wet gas. MCB, LCO
and HCN are drawn as products directly from the main column, although on many FCC
units HCN is not removed from the unit as a product stream. On some units, Heavy
Cycle Oil (HCO) is drawn as a product from the main column between the MCB and
LCO products. Main column sidecut products are often steam stripped in sidecut
strippers for flash point adjustment. The unstabilized gasoline and wet gas are further
separated in the gas concentration section. The arrangement and integration of heat
exchange from an FCC main column varies from refinery to refinery based on the
specific requirements and economics of a given installation. The following discussion
describes typical heat exchange circuits used on an FCC unit. Figure 14 shows a
simplified FCC main column schematic.

157048
Process Control
Page 28

Figure 14
Main Column Overview
Wash Water

WGC Spillback
OVHD Vapor
to WGC

CW

Net OVHD Liquid


to Gas Con

HCN from
Gas Con

Sour Water

LCO from
Gas Con
Steam
HCN
Product

HCO from
Gas Con
Steam

LCO to
Flushing Oil
LCO
Product

HCN to
Gas Con
LCO to
Gas Con
HCO to
Gas Con
Reactor
Product
Vapor
Steam
Raw Oil to
Reactor

BFW

MCB
Product

FCC-PC400

157048
Process Control
Page 29

Main Column Bottoms Pumparound Circuit


The main column bottoms circulation system (Figure 15) is designed to desuperheat
the reactor vapors, condense the bottoms product and scrub entrained catalyst fines
from the reactor product vapor. Main column bottoms (MCB), also commonly called
slurry oil, is removed from the bottom of the main column and typically pumped to a
circulating bottoms/raw oil exchanger and one or more steam generators. MCB may
also be used to provide heat to reboilers. The reactor vapors are desuperheated by
contact with a large stream of cooled slurry oil on the disk and donut trays. The bottoms
flow over the disc and donut trays also washes catalyst fines out of the reactor vapors.
The total bottoms circulation rate over the disc and donut trays is normally set at 150%
to 200% of the feed rate or 6 gpm per ft2 of column area (15 m3/hr per m2 of column
area), whichever is greater. A minimum spillback valve is provided to maintain this
minimum flow during turndown operation. This ensures enough circulating MCB is
returned to the main column to adequately wet the disc and donut trays, thereby
cleansing the reactor vapors of catalyst fines and preventing coke formation on the disk
and donut trays due to insufficient liquid flow over the trays.
Typically the bottoms temperature is maintained at 670-700F (354-370C) to minimize
coking and fouling in the slurry circuit. The bottoms temperature is controlled by the
LCO product draw rate (or HCO product draw rate if HCO is withdrawn as a product).
This flow is adjusted manually by the operators. If the bottoms temperature is too high
the LCO product rate is reduced to drop more LCO to the bottom of the column which
lowers the bubble point of the MCB product. Alternatively, if a higher LCO endpoint is
desired than can be achieved while controlling the bottoms temperature in this manner,
a stream of cooled bottoms from the steam generator (quench) may be returned directly
to the bottom of the column to sub cool the liquid there. In this manner the temperature
in the bottom of the column is no longer composition dependent and the LCO/MCB
cutpoint may be varied independently of the bottoms temperature.

157048
Process Control
Page 30

Figure 15
Main Column Bottoms and HCO Flow and Control

FIC

FIC

LIC

HCN Stripper
Reboiler

Debutanizer
Reboiler

Torch Oil
Pump Flushing Oil

MCB
Quench

Disc and Donut


Minimum Flow

FIC

Reactor
Product
Vapor

Steam
FI

FIC

LIC

Raw

FIC

BFW
FIC
FIC

MCB
Product
CW

Raw

FCC-PC401

157048
Process Control
Page 31

During normal operations the heat input from the circulating main column bottoms to
reboilers and preheat exchangers will be set by product and process considerations.
This is true of the heat removed in the other pump around loops as well. Heat input to
the steam generators is generally the only variable available to the operator for
adjustment of the column heat balance and reflux rates. Increasing the bottoms flow
through the steam generators will cause more heat to be removed. This will reduce the
amount of hot vapor traffic up the column and eventually will reduce the overhead reflux
rate and the heat removed in the overhead system.
Each exchanger in the main column bottoms pumparound circuit is designed for oil
containing catalyst particles. Main column bottoms flows through the exchanger on the
tube side and the velocity should be kept between 3.75 ft/s and 7.0 ft/s (1.14 m/s and
2.13 m/s) for straight tubes and between 3.75 ft/s and 5.75 ft/s (1.14 m/s and 1.75 m/s)
for U-tubes. Below the minimum velocity, catalyst can accumulate on the tube walls
and slowly plug the tube while greatly reducing heat transfer. If the velocity is above 7
ft/s (2.13 m/s), there is a risk of erosion on the tube walls. If the circulating MCB is very
low in ash content (<0.15 wt-%) the risk of erosion is greatly reduced. The rates
required to meet these velocities must be calculated for each exchanger before startup.
Bottoms product is withdrawn on straight flow control adjusted manually by the operator
to maintain a steady bottoms level in the main column. The product is cooled, typically
in cooling water exchangers before being sent to tank. In many cases the bottoms
product is also exchanged with the raw oil.
Removal of catalyst fines from the bottoms product by filtration, settlers or hydroclones
is an option which may be included depending on the end use of the bottoms product. If
a slurry settler is used to reduce catalyst fines in the bottoms product, the settler inlet
flow is drawn upstream of any bottoms product coolers. Hot main column bottoms
enters the settler tangentially and the swirling motion imparted distributes the heavy oil
evenly as it moves up to the outlet. Settler superficial velocity is limited to 30 BPD/ft2
(50 m3/d/m2) or less in the settler so that the fines can settle to the bottom of the
vessel. Clarified oil product (CLO) leaves from the top of the settler. Diluent (cooled
main column bottoms, raw oil or HCO) is added at the bottom of the settler to carry the

157048
Process Control
Page 32

fines back to the riser. The diluent addition rate is always equal to or slightly less than
the slurry flow to the riser and the settler feed rate is normally equal to or greater than
the clarified product from the from the top of the settler so that net flow is downward
carrying the settled fines out of the settler. Figure 16 shows the slurry settler flow and
control. Slurry settlers are not as common today because of the improvement in reactor
riser terminations and cyclones.
Filtration of the slurry product is becoming more common either to produce carbon
black feed stock (which typically requires less than 100 wppm solids), to minimize
downstream problems in fired heaters or to minimize tank cleaning cost. Figure 17
shows a typical flow and control for a bottoms filtration unit.

Figure 16
Slurry Settler Flow and Control
FIC
Clarified
Slurry Oil
Product

PSV

FIC

Return to
Main Column

Main Column
Bottoms

Slurry
Settler
FI

FIC

Diluent
(HCO or
Raw Oil)
FIC

Sewer
Slurry
to Riser

FCC-PC402

157048
Process Control
Page 33

Figure 17
Main Column Bottoms Filter Flow and Control
PIC

Backwash Gas
(N2 or Fuel Gas)

FIC

Clean
MCB
Product to
Storage
Bypass
(normally
closed)

PDI LS

LS

Filter
#1

PDI

PDI LS

Filter
#2

Filter
#3

Split
Range

N2 or Fuel Gas
PIC

Solvent Fluid
(LCO/HCO)

Vent

Receiver
Vessel

MCB
Product

LIC

FIC

FI

FIC

Catalyst
Backwash
to
Reactor

Valve sequencing controlled by programmable logic controller(PLC)


Signals to/from PLC not shown for clarity
FCC-PC412

157048
Process Control
Page 34

HCO Pumparound Circuit


HCO is withdrawn from the column and commonly used to provide heat to the raw oil
preheat exchanger and the debutanizer reboiler as shown in Figure 15. Occasionally,
HCO is also used to generate steam and reboil side cut strippers such as a heavy
naphtha stripper. HCO flow to each of these exchangers is regulated by a flow
controller. Each controller is set by the operator to achieve desired product or process
specifications. If a steam generator is used, then the HCO pumparound heat removal
may be varied to some extent independently of process or product requirements. The
HCO reflux to the column is typically pumped back to the column on flow control reset
by the HCO draw tray level.
A decrease in heat removal from the HCO circuit will require an increase in heat
removal elsewhere in the column. For example, if less heat is removed in the
debutanizer reboiler then fewer vapors will be condensed in this part of the column
increasing the amount of vapor rising up the column. If the excess heat is not removed
in another pumparound circuit the overhead duty and reflux to the top of the main
column will increase to remove this heat.
HCO product (if any) can be removed through a stripper for flash point adjustment. The
amount of HCO product produced will depend on reactor operating conditions, feed
quality and catalyst type. The plant operator will make adjustments in HCO, LCO and
naphtha draw off rates to maintain target cut points or end points for these products. If
HCO is taken as a product it would typically be cooled against raw oil in a charge
preheat exchanger and then sent through a water cooled product cooler on flow control.
The HCO circuit also provides torch oil to the regeneration section for start-up and
emergencies and flush oil to the main column bottoms pumps.

157048
Process Control
Page 35

LCO Pumparound and Product Circuit


Circulating LCO normally provides heat to the gas concentration unit stripper reboiler
and the debutanizer feed exchanger as shown in Figure 18. Flow to each exchanger is
regulated by a flow controller which is set according to process requirements. A stream
of LCO, after heat exchange at the stripper reboiler, is sent to the sponge absorber as
lean oil to adsorb light gasoline range components from the light gas in the gas
concentration section. The rich oil from the sponge absorber is returned to the main
column with the cooled LCO circulation stream, providing internal reflux for the main
column LCO section. On many units this reflux steam is circulated from a total trap tray
by gravity through a flow meter to provide additional column process information.
Most units contain an LCO stripper for LCO product flash point adjustment. Depending
upon the plant arrangement, light ends in the LCO can be removed either by steam
stripping or by refluxing the liquid using heat from the circulating HCO. The LCO product
may exchange heat with the raw oil feed stream before being cooled with water in a
product cooler and being sent to storage. Flow to storage is set by a flow controller. The
amount of LCO sent to storage is typically varied to control the temperature in the
bottoms of the main column as described previously. Alternatively the LCO product rate
may be adjusted to maintain a constant temperature at the draw tray and therefore
maintain a constant endpoint. Stripped LCO is available for use as emergency quench
to the riser, instrument flush and pump gland seal oil.

157048
Process Control
Page 36

Figure 18
LCO Flow and Control

FI
FIC
LIC
Steam

FIC
LCO
Product

BFW
CW
Preheater

FIC

LCO to
Flushing Oil

Debutanizer Feed
Exchanger

FIC
Stripper
Reboiler
Rich Oil fromSponge
Absorber
Lean Oil to Sponge
Absorber

FCC-PC403

157048
Process Control
Page 37

Heavy Naphtha Pumparound and Product Circuit


A heavy naphtha (HCN) product is typically withdrawn through a side cut stripper
column in order to remove light ends for vapor pressure adjustment. The product may
be either steam stripped or reboiled with HCO. The naphtha stripper bottoms product is
cooled with water in a product cooler and then sent to storage or treating on flow
control. The HCN product flow rate is adjusted by the operator to maintain a constant
draw temperature and therefore endpoint at the draw tray. The portion of the naphtha
draw from the main column which is not stripped as product is pumped and used for
heat exchange with raw oil feed, the C3/C4 splitter reboiler, water or other low
temperature streams and returned to the main column as internal reflux for the main
column naphtha section. Figure 19 shows the flow and control for the naphtha
pumparound circuit.

Figure 19
HCN Flow and Control

FI
FIC
LIC
HCO FIC
HCN
Product
CW

FIC

C3/C4 Splitter
Reboiler

FCC-PC404

157048
Process Control
Page 38

Main Column Overhead System


Reactor product vapors contain large quantities of light gas and gasoline vapors which
pass through the entire main column as gases. A portion of these products are
condensed in the overhead condenser, the trim condenser and separated in the main
column overhead receiver. A quantity of the condensed hydrocarbon liquid (unstabilized
gasoline) is pumped to the main column as reflux (Figure 20).
Reflux to the main column controls the overhead vapor temperature. This temperature
determines the endpoint of the debutanized gasoline product from the gas concentration
unit. The reflux also heat balances the column. If heat removal from one section is
changed the overhead reflux rate will respond in the opposite direction to maintain a
constant top temperature. For example, if more heat is required in the feed to the
debutanizer, LCO circulation will be increased to provide the heat. The increased heat
removal from the LCO circulation will condense more vapors rising up the column. Less
heat will reach the top of the column. The top temperature controller will then reduce the
reflux flow to maintain the column top temperature, thus heat balancing the column.
The unstabilized gasoline liquid in the receiver not used as reflux is pumped to the
primary absorber in the gas concentration unit on receiver level control. Gas flows to the
suction drum of the wet gas compressor in the gas concentration unit. Water from the
overhead receiver water boot is pumped to the waste water treating unit.
The main column pressure, and therefore the reactor pressure, is controlled at the
overhead receiver by the amount of gas removed through the wet gas compressor. This
control must be very steady because swings in this pressure will affect the pressure
balance between the reactor and regenerator and therefore will affect the catalyst
circulation. The wet gas compressor control system depends on the type of driver and
the compressor design.
Regardless of the primary pressure control system, a backup control system is present
in case the wet gas compressor trips or can not handle all of the gas produced in the
reactor. This is shown in Figure 20. In this case an overpressure control valve, typically

157048
Process Control
Page 39

set at 0.3-0.5 psi (0.02-0.035 kg/cm2) above the setpoint for the primary pressure
controller will open venting some of the gas to flare or a low pressure fuel gas system.
This control system allows the unit to continue operating during a short duration
compressor failure and is useful during startup before sufficient gas is produced in the
reactor to run the compressor.

Figure 20
Main Column Overhead Flow and Control
Wet Gas
Compressor First
Stage Spillback
Signal to Wet
Gas Compressor
Controls

Cooling
Water
FC

PSV
Wash
Water

PRC

PIC

To Flare
Header
To Wet Gas
Compressor
Suction Drum

LIC

TIC

LIC

FIC

FIC

Net Overhead
Liquid to High
Pressure
Receiver
FI

Sour
Water
FCC-PC405

157048
Process Control
Page 40

Wet Gas Compressor Control


Steam Turbine Driven Wet Gas Compressor Control
The compression of the wet gas from the main column overhead receiver to the gas
concentration section is done in two stages, with external cooling and liquid knockout
between the stages. A variable speed steam driven centrifugal compressor is shown in
Figure 21. The control system is set up to hold pressures steady and to prevent the gas
compressor from surging, which can cause serious damage to the wet gas compressor.
The pressure control signal from the main column overhead receiver has a split range,
to the low signal selector controlling the spillback, and to the governor on the steam
turbine. The second stage spillback to the first stage compressor discharge is controlled
by a low signal selector which is fed by the interstage suction drum pressure signal and
the second stage flow signal. The low signal selector will ignore one of the two inputs,
whichever is higher, and transmit the lower output signal intact.
The system works as follows:
1.

Normal flow - at lower charge rates, the main column overhead receiver signal
will control the first stage spillback to hold receiver pressure constant. The
second stage spillback will be controlled by the anti-surge controller to satisfy the
minimum flow requirements of the surge curve. The turbine will be running at
minimum governor speed. As the charge rate is increased, there is a greater net
flow of gas, so the two spillbacks are gradually closed by the controllers. When
the spillbacks reach the fully closed position, the output signal from the overhead
receiver pressure controller will be high enough to begin increasing the
compressor speed. The speed will then be continuously varied to remove the gas
from the main column and hold the pressure constant. Throughout this, the flow
controllers will have no effect as long as there is sufficient gas flow to keep the
machine out of surge.

157048
Process Control
Page 41

2.

Abnormally low flow - there would be two main reasons for low gas flow. The first
would be insufficient gas from the main column, such as when the feed was
suddenly cut out. The second reason would be an abnormally high second stage
discharge pressure, caused by problems in the gas concentration unit. Whatever
the cause, when the flow falls below the point set by the operator on the FRC,
the output signal falls, which would then be transmitted by the low signal selector.
This opens the spillback valves to recycle gas back to the suction, allowing the
gas to be moved through the machine in sufficient quantities to keep it out of a
surge condition. When normal conditions are restored, the flow controller output
will rise, and the low signal selector will return the spillbacks to pressure control.
If the low flow is caused by high pressure in the gas concentration unit, opening
the first stage spillback will overpressure the main column. This condition will
open the overpressure control valve to flare, holding the receiver pressure at the
overpressure set point.

3.

Abnormally high flow - the main cause for very high flow rates would be operating
the FCC unit in such a fashion that the compressor could not handle the gas
flow. The machine would be at maximum governor speed with both spillbacks
closed. Pressure in the main column would rise, opening the overpressure
control valve to flare.

Modern anti-surge and pressure control systems take advantage of faster transmitters
and computer technology to allow monitoring of multiple variables and rapid calculation
of corrected flow rates to allow more efficient operation closer to the surge line with less
spillback. These inputs to the anti-surge controllers are shown in Figure 21.

157048
Process Control
Page 42

Figure 21
Wet Gas Compressor Control
Signal
from Main
Column
Overhead
PRC

From
Main
Column
Overhead
Receiver

FI

FI

Antisurge
Controller

Antisurge
Controller

To High
Pressure
Receiver

Antisurge
Signal Opens
Control Valve
TT

Nirogen
Purge

Nirogen
Purge

FO

FO
Steam

TT

TT

TI
SI

SC

PT

PT

PT

Antisurge
Signal Opens
Control
Valve

TT

PT

Speed
Sensor

First Stage
Spillback to
Main Coulumn
Overhead

To Surface
Condenser

First
Stage

Second
Stage

FCC-PC407

Steam Turbine, Variable Speed

157048
Process Control
Page 43

Motor Driven Wet Gas Compressor Control


This case would be for a constant speed centrifugal compressor. The instruments,
controls, and actions are essentially the same as discussed above, except that the
governor speed control is replaced by a suction butterfly valve to throttle the gas flow to
the compressor. This valve normally stays partially closed, against a limiting stop. As
more flow is required, after the spillbacks have closed, the butterfly valve will open
allowing more gas to move through the compressor. The action on low gas flow is to
move gas through the compressor spillback valves in the same manner as described
above for the variable speed machine.
Reciprocating Wet Gas Compressor Control
Older FCC units occasionally used reciprocating wet gas compressors. These are rarely
used today because of the better efficiency of the centrifugal compressors.
Reciprocating compressors are normally constant speed machines. At normal flows and
pressures, the spillbacks open or close to hold the overhead receiver and interstage
suction drum pressures at the point set by the operator. Abnormally low flow rates, such
as when the charge is cut, will cause a drop in pressure, opening the spillbacks. High
second stage discharge pressure will have the same effect. Reciprocating machines
may also have clearance pockets and suction valve unloaders which can be varied to
control flow, but this will depend on the individual machine.
Variations
There are other control schemes which are in use today, depending on the individual
refiner's needs. Some plants have been designed with only one spillback, from second
stage discharge to the main column overhead receiver. This does not allow the same
freedom of action as that offered by two spillback valves. Excess pressure drop through
one part of the system caused by such things as exchanger fouling, is one reason why it
is better to have the extra freedom of two spillbacks.

157048
Process Control
Page 44

Main Column and Gas Concentration Section Water Wash


The overhead stream from the main column contains a number of contaminants which
can cause corrosion, plugging and fouling. These contaminants include ammonia,
sulfides, cyanides, chlorides and phenols. A wash water stream is used to remove the
contaminants. The wash water should be clean, preferably steam condensate, to
prevent adding more problems such as salts or dissolved oxygen to the system. Wash
water is effective in removing most of these impurities because most of them are ionic
or polar species which tend to be readily soluble in water.
Figure 22 shows the preferred arrangement of the water wash system for an FCC
fractionation and gas concentration section. Clean water is pumped into the first stage
discharge of the wet gas compressor at the inlet to the interstage cooler. The water from
the interstage receiver is pumped out on level control to the wet gas compressor
discharge at the inlet of the high pressure cooler. Water collected in the high pressure
receiver water boot is pressured on water boot level control to the inlets of the main
column overhead condenser and trim condenser. Sour water is then pumped to
disposal from the main column receiver water boot on receiver water boot level control.
The recommended water wash rate is 6.5 to 7.0 vol% of feed or about 2 gpm per 1000
BPD feed (approximately 1.15 liters/min of water per 1 m3/hr of fresh feed rate). The
drain water from both the overhead receiver and the high pressure receiver should be
checked regularly for pH. The main column overhead receiver water should be in the
range of pH 8.0 to 8.5. The high pressure receiver drain water should also be slightly
alkaline, pH 7.5 8.0.

157048
Process Control
Page 45

Figure 22
Wash Water Control
Main Column
OVHD Vapors
FI

CW

Main Column
OVHD Rec.
CW

Liquid from
Primary Absorber
Vapor from
Stripper
To Primary
Absorber

Sour
Water

High Pressure
Receiver
M
First
Stage

Second
Stage

Wet Gas Compressor

LIC

To Stripper

To Primary
Absorber

LIC

FIC

Condensate
Water Break
Drum

Water Flow Indicated by Bold Lines

FCC-PC409

157048
Process Control
Page 46

Feed Preheat Train


There are two basic raw oil preheat schemes used in FCC units. One uses a fired
heater to supply some or all of the feed preheat duty. Fired feed preheaters are
expensive to build and operate by today's standards so fired preheaters are mainly in
use on older FCC units. The other feed preheat scheme uses extensive heat integration
to provide feed preheat duty. Most new FCC units use this heat exchange scheme and
do not employ fired feed preheaters. Figures 23 and 24 show FCC feed preheat
schemes with and without fired heaters, respectively.
In both preheat trains, the raw oil flows to a feed surge drum directly from the crude unit,
vacuum unit, hydrotreating or from storage. The surge drum pressure rides on main
column pressure through a vent line connected to the lower section of the main column
just above the HCO draw. The surge drum level is normally controlled by controlling the
flow of one of the feed sources into the unit.
The charge is pumped from the surge drum on flow control through heat exchangers
before reaching the feed distributor at the reactor riser. The only significant difference
between the two schemes is the presence of the fired heater. Both schemes use a TRC
to control the raw oil outlet temperature from the circulating main column bottom/raw oil
exchanger by bypassing some of the raw oil around the exchanger. The flow of main
column bottoms through the exchanger is varied to keep the temperature controller in a
good operating range. With the fired heater, each heater pass is also controlled by a
TRC.

157048
Process Control
Page 47

Figure 23
Feed Preheat System
Equalizing
Line To/From
Main Column
FIC

LIC

Raw Oil Surge


Drum

FIC

High Temperature
Closes Control
Valve

Split
Range

TIC
To
Reactor

FIC LSS

<
Split
Range
FIC

Raw Oil from


Raw Oil from
Storage
Crude Unit/
Level Control
Hydrotreating
Signal from
Upstream
Unit

LCO
MCB
Product Product
Low Temperature
Closes Control
Valve

High Level Closes


this Valve First

Circ.
MCB
MCB
Recycle
HCO
Recycle

FCC-PC411

157048
Process Control
Page 48

Figure 24
Feed Preheat with Fired Heater
Equalizing Line
To/From Main
Column

Raw Oil Surge


Drum

LIC

FIC

TIC

TIC
Fired
Heater

Raw Oil from


Storage/
Upstream Unit

MCB
Product

To
Reactor

Circ.
MCB

Fuel
Gas

FCC-PC410

157048
Process Control
Page 49

Gas Concentration Unit Control


A typical flow scheme for the overall gas concentration unit is shown in Figure 25. It is
convenient to discuss the controls in 2 sections - the absorber section and the
fractionation section. The absorber section removes LPG and light material from the
gases and recycles them back to the high pressure receiver. The fractionation section
strips C2 and lighter material as well as H2S from the LPG and gasoline and recycles
them back to the high pressure receiver. The fractionation section also separates the
LPG and gasoline.
Because the absorbed and stripped material are recycled back to the high pressure
receiver good control of the gas concentration unit requires a good balance of stripping
and absorption. If excessive stripping is occurring then excessive absorption will also be
required to achieve reasonable C3 and C4 recoveries from the fuel gas. This is at a
minimum a waste of utilities and in severe cases can result in increasing recycle flows,
or snowballing, until one or more of the columns flood.

157048
Process Control
Page 50

Figure 25
Gas Concentration Unit Flow
Lift Gas to
Reactor

Lean Gas
KO Drum

Unstabilized
Gasoline from
Main Column
OVHD

Wet Gas
Compressor
Discharge

Sponge
Gas to
Treating

CW

CW

Primary
Absorber

Sponge
Absorber

Rich Oil
to Main
Column
CW

High Pressure
Receiver

Stripper
Wash Water to
Main Column
OVHD Receiver

LCO from
Main
Column

Wash Water
from Interstage
Receiver

LPG to
Treating

Debutanizer

Circ.
HCO

Stabilized Gasoline to
Treating
CW

FCC-PC703

157048
Process Control
Page 51

Absorber Section - Primary Absorber


LPG and heavier hydrocarbons are recovered from the light gas (also called sponge
gas or fuel gas) in this section of the gas concentration unit shown in Figure 26. Gas
from the high pressure receiver enters the primary absorber below the bottom tray and
is contacted by counter current flow with unstabilized gasoline on level control from the
FCC main column overhead receiver.
Many units also recycle stabilized gasoline (debutanizer bottoms) on flow control to the
top tray to increase recovery of the C3 and C4 hydrocarbons. Unstabilized gasoline is
typically fed to the 6th tray from the top when recycle gasoline is used. Heat is removed
from the column to maximize adsorption efficiency with two pumparound inter-coolers,
one about one third the way down the column and another about two thirds of the way
down from the top. The rich oil flows from the bottom of the column to the high pressure
condenser on level control cascaded to a flow controller. The overhead gas stream
flows into the sponge absorber.
Absorber Section - Sponge Absorber
The sponge absorber is typically a packed column which serves to recover nearly all the
remaining C5 and C6 material and some C3 and C4 hydrocarbons. Circulating light cycle
oil on flow control from the stripper reboiler is heat exchanged with the rich oil and then
cooled before being pumped to the top of the absorber as lean oil. The gas from the
primary absorber flows upward from the bottom of the column. Rich oil leaves the
bottom of the column on level control. The rich oil is heated in the rich oil/lean oil
exchanger before returning to the main column with the circulating LCO stream. Lean
sponge gas leaving the top of the sponge absorber is cooled and any condensed liquid
drops out in the lean gas knockout drum. The liquid is periodically drained to the LCO
return line.
Gas from the lean gas knockout drum is normally sent on pressure control to a fuel gas
amine treater before being sent to the refinery fuel gas system. In FCC or RCC units
using lift gas technology, a portion of the lean sponge gas (before amine treating) is
recycled to the reactor riser on flow control for use as lift gas. The sponge gas pressure

157048
Process Control
Page 52

controller sets the pressure for the knockout drum, the sponge absorber, the primary
absorber, the high pressure receiver and the stripper column. The pressure of each
vessel depends upon the pressure drop between the vessel and the lean gas knockout
drum.

Figure 26
Gas Concentration Unit Absorber Section
Lift Gas to
Reactor

Lean Gas
KO Drum

Unstabilized
Gasoline from
Main Column
OVHD

Wet Gas
Compressor
Discharge

Sponge
Gas to
Treating

CW

CW

Primary
Absorber

Sponge
Absorber

Rich Oil
to Main
Column
CW

High Pressure
Receiver

Stripper
Wash Water to
Main Column
OVHD Receiver

LCO from
Main
Column

Wash Water
from Interstage
Receiver

LPG to
Treating

Debutanizer

Circ.
HCO

Stabilized Gasoline to
Treating
CW

FCC-PC703

157048
Process Control
Page 53

Fractionation Section - Stripper Column


Removal of light hydrocarbons from the LPG and gasoline is accomplished in the
stripper column (see Figure 27). Liquid from the high pressure receiver is heated with
debutanized gasoline before entering the top of the stripper. Heat to the stripper is
provided from the debutanized gasoline reboiler and the LCO reboiler. The LCO flow to
the reboiler is controlled on a cascade loop to maintain a constant vapor rate from the
top of the column. A bypass around the debutanizer bottoms to the lower reboiler is
provided in case the demand for LCO to the upper reboiler is less than the required flow
to the sponge absorber. The stripping rate is varied to reject all of the C2 and lighter
material and in some cases to control the amount of H2S going to the debutanizer and
therefore into the LPG product. Stripper overhead vapors return to the high pressure
condenser. Liquid leaves the bottom of the stripper on level control and is pressured to
the debutanizer column feed exchanger.
Fractionation Section - Debutanizer Column
Gasoline vapor pressure adjustment and separation of the C5 and heavier components
from the LPG is achieved in the debutanizer column. Circulating LCO provides heat to
the debutanizer feed before the feed enters the column at tray 20. LPG leaves the top of
the column as a gas and is cooled in the condenser before collecting in the overhead
receiver. The pressure in the column is controlled by controlling the amount of vapor
entering the condenser. A hot vapor bypass around the condenser is used to control the
pressure drop between the column and the receiver to ensure that the opening of the
pressure control valve stays in a good operating range. If the hot vapor bypass valve is
fully open then the temperature, and therefore the pressure, in the receiver is too low
indicating that less cooling is required at the condenser and that either the fan speed
should be reduced or one or more fans should be shut off. Likewise, if the hot vapor
bypass valve is fully closed then the fan speed needs to be increased or additional fans
turned on.
Liquid from the overhead receiver is returned to the column top as reflux to control the
column temperature at tray 6. Net overhead liquid is pumped to the LPG treating unit to
control the level in the receiver.

157048
Process Control
Page 54

Heat to the debutanizer reboiler is typically supplied by circulating HCO. The flow of
HCO is adjusted by the operator to adjust the reflux rate in the column and the quality of
fractionation. The temperature controller is adjusted to control the RVP (Reid Vapor
Pressure) of the gasoline. Stabilized gasoline flows from the column bottom to supply
heat to the stripper reboiler and then to the stripper feed exchanger. Gasoline from the
stripper feed exchanger can be split into two streams. Recycle gasoline is cooled and
pumped to the primary absorber on flow control. Net debutanizer bottoms (i.e., gasoline)
is cooled and pumped to the treating unit. The net gasoline flow controller is reset by the
debutanizer bottoms level controller to maintain the column bottom level.

157048
Process Control
Page 55

Figure 27
Gas Concentration Unit Fractionation Section
PIC

Vapor
to HPR
Debutanizer

LIC

FIC
Stripper

PDIC

TIC
18
19

LPG to
Treating

19
20

Circulating
LCO To/
From Main
Column

36

35
36

TIC
FIC

40

FIC
LIC
Circulating
HCO To/From
Main Column

Liquid
from
HPR
Split
Range

FI

FIC
Stabilized Gasoline
to Primary
Absorber
CW

FIC
Stabilized
Gasoline to
Treating

FCC-PC700

157048-1
Equipment
Page 1

EQUIPMENT
INTRODUCTION
The Fluid Catalytic Cracking unit is exposed to severe temperature, erosion and
corrosion effects. The equipment has been designed to withstand these conditions
for an acceptable mechanical life, but the life can be drastically shortened by abuse
or poor operations. Proper control and operation will avoid the unnecessary
problems which lead to premature failure.
The FCC unit should be inspected every turnaround. The inspection can be done by
a UOP inspector, the refinery inspection department, or both. Adequate record
keeping of these inspections is necessary to develop the unit history which will aid
the refiner to judge equipment life, determine potential problems and evaluate the
effect of different metallurgy and process conditions related to the equipment.
A good inspection will include the following:
1)

An evaluation of the equipment which has experienced erosion and/or


corrosion

2)

A list recommending minor repair work

3)

An assessment of mechanical problems caused by the operating


conditions of the previous run

4)

A list of spare parts required for the next turnaround

Erosion and corrosion are not always obvious. A thorough inspection of the
equipment will reveal the extent of any damage and help determine the cause and
effect relationship. Also, because no equipment lasts forever, the inspection will
help the refiner determine when equipment must be replaced so advance orders
can be made.

157048-1
Equipment
Page 2

Minor repair work can prevent small problems from expanding to larger problems. It
is difficult to predict the amount of minor work which will be required. The desired
length of the next run will determine the extent of the repairs.

PREPARATION for INSPECTION


Preparation for inspection should begin well before the shutdown. Proper
scheduling of inspection and maintenance will avoid delays and wasted time. As
soon as an inspector finds a problem, parts can be ordered and work can be
scheduled so the completion of the turnaround will not be delayed.
The normal shutdown procedure will remove most of the catalyst from the unit and
cool the vessels to 200-250F (90-120C). The manways should be opened on
both the reactor and regenerator to air cool the vessels. Vacuum connections are
provided to remove any remaining catalyst. The vacuuming operation can begin
while the manways are being opened, if there is sufficient manpower. When the
vacuuming is complete, water washing can be started. This will remove the dust
and fines which would hinder a complete inspection. A simple water spray is usually
sufficient, with the water draining out of the reactor and regenerator at the bottom of
each vessel. The water will not cause any problems with the vessel internals, even
stainless steel. A high-pressure blast could obviously damage the refractory;
common sense is required. Clean, potable water with less than 50 ppm chlorides
should be used. Excess water should not be allowed to stand on the equipment for
long periods of time. An air hose can be used to blow away these puddles. There
are a few areas that are difficult to drain, such as the regenerator plenum chamber.
These can be cleaned with a heavy-duty vacuum cleaner. Because there are
different reactor and regenerator designs, the exact cleaning method should be
determined by the refiner.
The main column and gas concentration section should also be cleaned for
inspection after the normal shutdown procedures have been completed.
Hydrocarbon and sour water should be pumped or pressured out of the unit. Gas
and vapors are removed by steaming out the vessels. Any remaining material can

157048-1
Equipment
Page 3

be removed as necessary by water washing the equipment. Do not allow any water
in the wet gas compressor. Normal refinery safety practices should be followed for
toxic vapors, explosivity, oxygen content of vessels, etc. The refinery safety
engineer should follow the turnaround carefully.

AIR BLOWER
The main blower of an FCC unit supplies large quantities of air to the regenerator.
Advances in rotating machinery technology have led to the replacement of the old
positive displacement reciprocating air compressor with centrifugal and axial
machines. Blowers can be driven by steam or gas turbines, electric motors, or flue
gas turbines, usually referred to as power recovery expanders. Depending on the
mode of operation and other factors such as feed quality, the FCC unit needs 1014.5 pounds of air per pound of coke, which is approximately 2000-3000 SCF/bbl
(330-500 Nm3air/m3FF). Air is filtered through a screened suction housing that
should be designed for noise abatement. Compressed air leaves the blower at
about 300-450F (150-230C) and 30-60 psia (2.1-4.2 kg/cm2(a)).
CENTRIFUGAL MACHINE
Air flow rates on a centrifugal machine are controlled by varying the speed of
rotation, throttling the suction, or venting off excess air. Four to six stages are
common, with labyrinth seals used to prevent leakage between stages. These
machines normally use forced lubrication systems for the bearings and may be
equipped with temperature and vibration probes for early detection of mechanical
problems.

157048-1
Equipment
Page 4

AXIAL MACHINE
An axial blower, shown in Figure 1, uses rotating blades to move the air. The air
flows through the machine in a straight line, each successive stage adding pressure
energy much like a propeller blade. The air flow rate is most often controlled by
varying the shaft speed. This can be accomplished either through a turbine driver,
or by including a Variable Speed Drive (VSD) unit on a motor. If the machine is
designed for constant speed, other means of flow control must be provided. One
option is to snort (vent) excess air to atmosphere. However, for normal control this
would require power to compress air that is vented back to atmosphere, and is
simply not energy efficient. Practical options include the use of small variable pitch
blades known as stators on the blower housing. The variable pitch stators redirect
the air flow into the path of the rotating elements. When this redirection is at a
steeper angle, more air is transferred. These machines use forced lubrication
systems and are normally equipped with temperature and vibration probes.
Another option to control air flow from a fixed speed blower is to include a suction
throttle valve. This mode of operation is very common in older machines, but as
with a snort valve, it is not an energy efficient system. The suction throttle valves
on motor driven air blowers can be eliminated through the installation of a VSD unit
onto the motor.
Axial compressors are generally more efficient at larger capacities than centrifugal
machines. They are smaller and lighter than an equivalent size centrifugal unit.
Choice of machine depends on the individual refiner, but axial blowers are more
common for larger units.
Specific operation of these large machines is too complex to describe in this
manual. Individual manufacturer's instructions should be followed for each unit.

157048-1
Equipment
Page 5

Figure 1
Axial Compressor

BLOWER PROBLEMS
The problems encountered with an FCC blower can be divided into two groups;
operational and mechanical. Examples of mechanical problems are vibration, shaft
displacement and noise. These may result from manufacturing defects, construction
mistakes such as misalignment of the driver and blower, and routine wear of the
bearings. In most cases, however, mechanical problems are caused by operational
difficulties. An example is surge, which occurs when the air blower is not able to
produce enough head to overcome downstream resistance. A centrifugal
compressor curve, shown in Figure 2, gives a typical head-flow relationship, while
Figure 3 shows a curve for an axial machine.
At a fixed speed the compressor will follow the curve. Flow decreases with
increasing head, similar to a pump. Unlike a pump, however, the characteristic
curve begins to turn down toward the zero capacity region after reaching a peak in

157048-1
Equipment
Page 6

pressure. This peak is called the stability limit or surge point. The machine will thus
produce less head at the decreased capacity. The pressure downstream of the
machine is higher and the flow reverses through the blower. When the downstream
pressure is relieved, normal flow is restored. Resistance quickly builds again and
the machine surges. The condition can be recognized by a characteristic cycling
sound and a rapid rising and falling of the flow between normal and zero. When the
gas moves back into the machine, the rotor tends to stall, which can cause serious
damage as the machine is subjected to large unusual forces and increased gas
temperature across each surge cycle. Surge cycles can result in damage to the
thrust or axial bearings and labyrinth seals. In severe cases the rotor itself may
crack or rub against the casing. On an axial blower the blades may break.
To prevent this backflow condition, many blowers are fitted with an anti-surge
controller. The controller essentially compares pressure rise and flow against a
programmed operating map of the blower. The operating map includes a calibrated
surge line. As the machine approaches the surge line a blow-off valve, commonly
referred to as a snort valve, is opened slowly. Opening the snort increases flow
through the machine and prevents surging. Surge is generally considered more
dangerous to axial blowers than to centrifugal, but should be avoided for either.
Choke, or stonewalling, is a low pressure, high flow condition where the gas velocity
approaches the speed of sound. Dangerous vibrations result and can cause the
rotor to crack. This condition may also be seen on the characteristic curve at low
head. The line becomes almost vertical as the capacity increases and air velocity
approaches the sonic value. This condition is infrequent but care must be taken to
avoid it. Choke is more of a problem for axial than centrifugal machines. Rotating
stall is a somewhat rare phenomenon, indicated by an inability to build pressure
while the flow is more or less normal. It results when air moves around the axial
rotor, rather than through it. The best cure is to back down to starting conditions and
restart increasing the flow again.
The air blower suction line should be inspected for cleanliness. The suction hood or
housing should be cleaned. Except for vibration from the blower, this section of the
plant is not subject to any unusual stresses, and normally lasts for many years.

157048-1
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Inspection and maintenance on the blower and associated systems should follow
the manufacturer's recommendations. Replacement of the bearings, seals,
lubricating oil, etc. is required at certain intervals. The air filters on the suction
housing should be inspected during normal turnarounds and replaced or repaired
as required.
Performance (capacity) of the blower can diminish over time due to fouling of the
blades. Foulants may include dust and chemical contaminants drawn into the
machine through the filter housing. Episodes of blade fouling have been associated
with sudden and heavy rains, washing contaminants off of the suction filters and
into the blower. Performance decline of up to 10% of rated flow have been
associated with blade fouling. Most vendors offer a surfactant or solvent injection
system that can be added to the suction line of the machine to help remove blade
foulants from the blower.
The air blower discharge line is not subject to corrosion or metal loss. All air snort
valves should be checked by the instrument department; few problems are ever
encountered with the air snort valves.
In the event of an emergency trip, many modern machines require that they be
rotated while cooling down. If this procedure is not followed when required, serious
rotor deflection can result. Excessive rotor deflection can result in serious
mechanical damage to the compressor, requiring a major overhaul of the machine.

157048-1
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Figure 2
Centrifugal Air Blower Performance Curve

Figure 3
Axial Air Blower Performance Curve

157048-1
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POWER RECOVERY
The power consumed by the air blower is a significant part of an FCC unit's
operating expense. Utility costs continue to rise, only partially offset by more
efficient motors and turbines. Recovery of the energy in the hot flue gas from the
regenerator can increase the overall efficiency of the unit. This was first done with
steam generation systems. The flue gas exchanges heat with a circulating water
stream. A 30,000 BPD (195 m3/hr) FCCU without a CO boiler can produce 40-70 Mlb/hr (18-32 t/hr) of 600 psig (42 kg/cm2) steam. Heat recovery in this scheme is
somewhat limited by a minimum allowable flue gas temperature. Sulfur oxides and
water vapor in the stack gas can cause corrosion of the equipment if they condense
in the flue gas duct. The temperature at which the condensation occurs is known
as the acid gas condensation point, which shifts depending on the concentration
and distribution between the different oxides. The acid gas condensation point is
typically in the range of 400-600F (200-315C), although it may be higher for some
units. The maximum temperature limit of the flue gas is typically a function of
metallurgical design limits for downstream equipment, which may include an
electro-static precipitator, flue gas scrubber, and/or stack.
The major disadvantage of a straight steam generation energy recovery scheme is
that no power is recovered from gas pressure, normally 10-40 psi (0.7-2.81 kg/cm2)
above atmospheric pressure at the regenerator outlet. Another approach to
recovering energy from the flue gas was tried in 1950. This was a turbo expander,
driven directly by hot flue gas. Initial results were unsatisfactory; after only 750
hours of operation catalyst fines in the flue gas had substantially eroded away the
turbine blades and casing. The fines problem was solved by placing an additional
catalyst separator, known as a Third Stage Separator (TSS) outside of the
regenerator.
In the TSS, flue gas moves through a large number of small cyclone assemblies in
which the catalyst is centrifugally separated from the flowing gas stream. To
remove the separated catalyst fines from the TSS, a small amount of gas, typically
3% of the regenerator flue gas, is used to pneumatically sweep the catalyst fines

157048-1
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out the bottom of the vessel. The clean flue gas is then directed to the inlet of the
power recovery expander.
UOP has been designing power recovery systems since 1973. Between 1973 and
2004, UOP licensed 33 TSSs with 22 placed into operation. The original units were
designed by UOP under license from Shell. Over the years, UOP improved upon
the original design by implementing several modifications. Even with these
modifications incorporated into the base design, very little had actually changed in
the overall design of the TSS in 25 years. These TSS designs still suffered from the
limitations imposed by radial flow gas distribution and reverse flow in the cyclone
elements.
In 1996, UOP launched a development program to design and offer a smaller, more
economic, high efficiency TSS that could not only be utilized in power recovery
installations, but also be a viable alternative to electrostatic precipitators and wet
gas scrubbers for environmental applications.
The cold flow modeling (CFM) test program extended over 2 years, during which
both dimensional variables and process flow variables were studied. Based on a
thorough understanding of cyclone theory, and drawing on other sources of cyclone
expertise, the UOP program investigated the contribution of many variables on
catalyst separation efficiency. These variables included:

Cyclone diameter and geometry


Inlet velocity
Length to diameter ratio
Outlet velocity
Catalyst loading
Gas distribution

Over 200 individual tests were conducted on single and multiple cyclone models to
determine the highest efficiency and highest capacity design cyclone. The tests
were conducted with commercial FCC catalyst fines. Computational fluid dynamic
(CFD) computer modeling was used to validate and benchmark the CFM work, and
to quickly investigate potential improvements and guide the physical modeling
program.

157048-1
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The development work culminated in the new UOP TSS design (see Figure 9). The
most significant improvement in the design is that the UOP TSS utilizes axial flow
for catalyst/gas separation. The flue gas flow is maintained essentially in one
direction - in the top and out the bottom of the unit. Axial flow distribution minimizes
the potential for solids re-entrainment resulting from gas flow direction change and
resultant eddy current formation. The older style TSS utilizes radial flow distribution
in which the flue gas is distributed from the centerline of the TSS, radially outward
between the two tube-sheets. As such, the inner tubes see a higher gas and dust
loading than the outer tubes. The mal-distribution of flue gas and fines inherent in
this design results in varying efficiency across the older style TSS.
The new UOP TSS is about 40% smaller than other TSS offerings for the same
capacity; making it less expensive to fabricate, easier to install, and better suited
where plot space is a premium.
The first UOP TSS was commercialized in April 2002. Performance testing on the
unit was performed twice in 2002, following the unit startup in April and again in
December. The initial test showed that the UOP TSS discharged between 36-50
mg/Nm3 of particulates, depending on flue gas rate. The NSPS compliance testing
resulted in a particulate matter emission of 0.6 lbs/1000 lbs of coke burn, only 67%
of that allowed by NSPS standards. This performance showed that the UOP TSS
could not only provide power recovery expander erosion, but could also be used as
in the refiners particulate emission control strategy, by replacing more traditional,
costly, and hazardous means (electrostatic precipitators and wet gas scrubbers) of
controlling particulates exiting the flue gas stack.
A comparison of the older style TSS and newer style TSS is shown in Figure 4.
Both vessels are carbon steel vessel with 4" (100 mm) of refractory lining and
stainless steel internals. The cold-wall construction is more effective on both
erosion and cost basis than the early hot-wall stainless steel separators. A coarse
screen, or grate, covers the flue gas outlet entrance to trap large chunks of
refractory or other debris.
The overall efficiency of the separator depends on the efficiency of the regenerator
cyclones and the quantity of catalyst fines being generated in the reactorregenerator system. The separator should remove >70-90% of the particles for high

157048-1
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and low regenerator cyclone efficiency, respectively. Most of the fines which pass
through the separator are smaller than ten (10) microns. These small particles do
not cause much erosion to the expander blades but the smallest particles can
deposit on the expander blades and casing, causing vibration problems.
The pressure drop across the expander is on the order of 10-30 psi (0.7-2.1
kg/cm2), with a temperature drop of 200-250F (110-140C). After driving the
turbine, the flue gas goes to a steam generator for further energy recovery.
The majority of the catalyst is removed from the flue gas with the underflow from
the third stage separator which is typically routed back into the flue gas downstream
of the expander. If required, an electrostatic precipitator or flue gas scrubber may
be placed downstream of the steam generator to remove any remaining catalyst
fines before the flue gas is exhausted to atmosphere. Alternatively the underflow
may be filtered to achieve ~99.99% removal of the catalyst fines, or routed to a 4th
stage cyclone separator to achieve ~60-90% removal of the catalyst fines from the
underflow stream, depending on local environmental restrictions.
The power recovery train usually consists of five parts; the expander turbine,
motor/generator, air blower, and a steam turbine, and is commonly referred to as a
5-Body Train, see Figure 5. In this arrangement the expander turbine is coupled
to the main air blower shaft to directly supplement the power requirement of the
blower. The 5-body train requires a steam turbine or motor to get it started; in some
cases only one of them is provided.
The expander, shown in Figures 6 and 7, is a single stage machine because of the
low pressures involved. The gas to the expander is accelerated over a parabolic
nose cone. Pressure energy is converted to velocity energy, and the high velocity
gas drives the turbine.
Expander turbines designed in the past were generally limited to an inlet
temperature of 1200-1250F (650-675C) to prevent heat damage. This generation
of expanders however, still required quench injection systems in the regenerator
plenum chamber to protect the expanders in the event of a regenerator temperature

157048-1
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excursion. Quench systems essentially dumped steam and water into the
regenerator plenum to cool the flue gas. While this provided for thermal protection
of the expander, the increased steam and water in the flue gas often resulted in
sticky catalyst that agglomerated in cement-like deposits that increased blade
fouling on the expander. Newer expander turbines normally have a design
temperature in excess of 1375F (750C) and do not require a quench control
system.
For units with a power recovery system, butterfly valves in the flue gas line control
the differential pressure between the reactor and regenerator. The PDIC sends a
signal to the large butterfly valve which is located at the inlet to the expander. A
smaller butterfly valve will allow flue gas to bypass the expander when the large
butterfly valve is fully open because of an excessive flue gas rate or when the
expander is off line. This prevents over pressuring the regenerator.
In the traditional five piece power recovery train, the motor/generator is usually a
constant speed induction type machine that provides extra power to the blower
shaft when needed. If the expander produces more energy than is required by the
blower, the machine will act as a generator and feed power into the electrical grid.
This acts as a braking mechanism and provides some over-speed protection for the
machine.

157048-1
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Figure 4
Third Stage Separator
Old Style TSS

New Style TSS

11' 6" OD
48 Tubes

29'

70 Tubes

23'

19' 3" OD

Figure 5
5-Body Power Recovery Train
Flue
Gas
Exhaust
Flue
Gas
Inlet

Air to
Air
In Regenerator
Inlet
Guide
Vanes

Steam
Turbine

Main Air
Blower
Expander
Steam
Inlet

Gear
Box

Motor /
Generator

Exhaust
Steam
Outlet

Electrical
Connection to
Power Grid

157048-1
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Figure 6
Flue Gas Expander

Because power recovery trains are generally fitted on larger units, the blowers used
are of the higher efficiency axial type. The blower is a constant speed machine in
most cases, especially if used with an induction type motor/generator. Varying the
angle of the stator blades in the blower is the most economical control scheme.
Because the motor/generator has a large startup electrical power requirement, a
steam turbine may be used to bring the train up to speed. The turbine will normally
provide 50-75% of the power needed for the blower. Once the train is close to
design speed, the motor can be started without using excessive amounts of
electricity. This in turn decreases the size of the transformers and switch-gears
needed. When the expander is running the turbine is allowed to freewheel, or may

157048-1
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be used to provide extra power. If there is no steam turbine, the expander turbine
may be used to "bootstrap" the train up to speed.
In unit revamp situations where the main air blower is not to be replaced, the power
recovery train can be reduced to 3 parts; the expander, gear reducer and generator.
This configuration is known as a Gen Set power recovery installation. In this
configuration, the power recovery system is completely isolatable from the
remainder of the FCC unit. The electrical power generation from the system is
routed directly into the refinery power grid. The net power recovery capable through
a Gen Set system is lower than a 5-body train due to efficiency losses in the switch
gear, and motor. However, the capital expenditure of Gen Set systems is lower,
and they can be completely isolated from the remainder of the FCC unit should
there be any equipment problems with the power recovery system.

157048-1
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Figure 7
Flue Gas Expander
Outlet

Blades
Rotor

Bearing
Coupling

Inlet

Shaft

FCC-E001

157048-1
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Page 18

A typical power recovery expander performance map is illustrated in Figure 8. The


power recovery system achieved commercial success in 1963. More than 30 units
are in operation or under construction. It has proven to be a valuable tool in
increasing efficiency and decreasing costs for Fluid Catalytic Cracking units.

Percent Expander Horsepower

Figure 8
FCC Power Recovery
1300 F (704 C)

1600 F
(871 C)

1200 F (649 C)
1100 F (593 C)
1000 F (538 C)
44.7 psia
(3.14 kg/cm2a)

40 psia (2.81 kg/cm2a)


36 psia (2.53 kg/cm2a)
32 psia (2.25 kg/cm2a)

28 psia (1.97 kg/cm2a)


26 psia (1.83 kg/cm2a)

Percent Flue Gas Mass Flow Rate

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CHECK VALVE
The check valve is installed on the discharge of the air blower. It prevents backflow
of air or catalyst, which could cause serious damage to the blower. Fluidized
catalyst will easily flow back through the air heater if pressure is lost. If the blower
starts to surge, the large volume of the regenerator must be isolated from the
blower. Figures 9-11 show the check valve and its associated equipment.

Figure 9
Blower Discharge Check Valve

157048-1
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Page 20

Figure 10
Blower Discharge Check Valve - Side View

The special check valve is a swing style check valve with a spring loaded air
cylinder that provides spring force assisted closing. An oil filled dash pot provides a
damping action on opening. Construction is of heavy wall steel to resist temperature
and pressure stresses, with 11-13% Cr or stainless trim. The stainless steel shaft is
supported by hardened stainless steel bushings, with graphoil packing used to
prevent leakage. Older designs have incorporated asbestos packing that may need
to be addressed with the appropriate abatement procedures. The shaft is connected
to the dashpot and to a lever arm that has counterweights that support 75% of the
disc weight. These weights minimize the pressure drop through the valve, but
should never hold the disc open when there is no air flow. The lever arm is usually
cut to the proper length in the factory, and the weights set in the field.

157048-1
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The air cylinder consists of a small piston opposed by a spring. Under normal
conditions, air is supplied to the piston, which moves up to compress the spring.
The piston rod moves freely between two small lever arms attached to the check
valve shaft. As the piston rod rises, the valve is free to open. Air flow from the
blower forces the valve open. The air to the piston is supplied through a three-way
valve that will vent off cylinder pressure when actuated. For older units, a shutdown
of the blower would signal the valve to cut off the air supply. For the new units that
have venturi meters on the blower discharge line, a low flow signal will signal the
valve to cut off the air supply. A shutdown on the blower itself, low blowerregenerator differential pressure, or low air flow can all be configured to cut off the
air supply to the piston and activate the special check valve. Instrument air failure
will also vent off pressure from the cylinder. Upon initial venting, the spring provides
a sharp thump to the valve shaft to help free the disc in the event that it has become
slightly stuck in the open position. The force of the spring is not enough to close
against the normal operating air flow from the main air blower. As such, a spurious
activation of the special check valve, i.e., a loss of instrument signal to the solenoid
valve, would result in a higher pressure drop through the check, but would not force
a unit shutdown.
After initial actuation, with no air pressure to oppose it, the spring provides a
constant load on the valve shaft. As the piston rod comes down, it pulls on the lever
arms, which exert a closing force on the shaft. This provides a starting boost to
close the check valve and will bring the valve closer to the seat before the air flow to
the regenerator actually stops.
Following a solenoid trip, the three-way valve must be manually reset in the field.
This functionality is included in the system design to help ensure that movement of
the check valve disc is controlled and stable, rather than a sporadic situation that
would result if the air cylinder was pressured and depressured in a random fashion
during an upset.
Typical turnaround maintenance on the special check valve includes maintenance
of the air cylinder, refilling the dashpot oil, repacking of the stuffing box hinge

157048-1
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assembly, replacement of the accordion type protective piston rod cover. After the
check has been reassembled, the flapper should move freely and close normally
under its own weight. Proper seating of the check disc should be confirmed
internally with visual inspection. If the main air line is too small to facilitate internal
visual inspection, the approximate position of the disc can be verified by the position
of the counter-weight arm.

DASHPOT
The dashpot provides a resistance to a sudden opening of the check valve. It has a
loose fitting piston that rides in an oil filled cylinder. The valve in the bypass line
restricts oil flow from the top of the dashpot to the bottom as the piston moves up.
This restriction prevents the check valve from opening too quickly. As the piston
moves down on the check valve closure, the valve in the bypass on the dashpot
opens wide to allow rapid closing of the check valve. Some snubbing action remains
to prevent excessive slamming. The dashpot should be filled with a light lubricating
oil such as SAE 10W. It is also important to provide a "volume leg" in the oil piping
to account for the volume of the piston shaft in the closed position. The setting on
the oil dash pot needs to be verified on initial installation and subsequent
turnarounds by opening the disc and allowing it to fall closed. Proper setpoint of the
oil valve should result in a smooth controlled closure of the disc with no substantial
impact on the valve seat.
If the check valve is thrust open under low air flow conditions, it may fly up too far,
and then slam back onto the seat. This can cause damage to the valve seating
surfaces. As a result, the check valve should be examined for any unusual wear,
such as impact erosion on the seat during the turnaround.

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DIRECT FIRED AIR HEATER


The direct fired air heater (Figure 12) is a carbon steel, internally insulated vessel
that heats the air to the regenerator primarily during startup. A pilot burner, as well
as one main burner (two - on rare occasion), are used to fire fuel gas, LPG, or oil on
heater discharge temperature control. The pilot for the burner is lit by a high energy
electrical electrode igniter. Air is directed to the burner by a large damper, controlled
externally with a hand crank. Sight ports are provided for flame observation. Air
purges to the sight ports keep the glass cool and can be used to blow catalyst out of
the ports if it backs up from the regenerator. A block valve is provided to shut off
and isolate the ports when the burner is either being ignited, or not being used. On
heaters that are mounted vertically, directly beneath the regenerator, there are
several stainless steel baffles spaced approximately three inches apart at the outlet.
The baffles prevent flame impingement on the air grid in the regenerator, which
could cause extensive damage to the grid. The baffles should be routinely
inspected during each turnaround.
The extent of the direct fired air heater repair work required during a turnaround will
depend on the hours and type of use. Over-firing and burner misalignment are the
two main causes of refractory spalling and reduced equipment life.
On low Coke operating units, the regenerator temperature can be cool enough to
adversely affect regenerator performance. On occasion, some refiners supplement
the regenerator temperature by Auxiliary firing of the air heater during normal
operation. While this has proven effective for some refiners, care must be taken not
to exceed maximum recommended exit velocities on the main air distributor.
Operating with distributor jet velocities too high can result in excessive erosion to
the main air distributor as well as excessive catalyst fines generation in the unit.
The fuel source to the DFAH needs to be maintained within the fuel specifications
outlined by the vendor. Improper fuel/air/burner combinations can result in severe
mechanical damage to both the DFAH and the regenerator internals; i.e., accidental
injection of liquefied LPG through a fuel gas burner.

157048-1
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Figure 12
Direct Fired Air Heater

Air Splitting Damper


with Limit Stops

Air
Inlet

Air
Outlet

TI's
(2 Required)

Pilot/Ignitor
Assembly

Air
Purge

Air
Purge

Main
Gas
Sight Port
(2 Required Must Sight Pilot
and Main Burner)

Air
Purge

Air Purge and


Blast Connection

Baffle

4" (100 mm)


Vibrocast Insulating
Refractory

Sight Port
Sighting
Burner

Sight Port
Sighting
Opposite Wall

4" Vacuum
Cleanout
Connection
Manway

FCC-E002

157048-1
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Page 25

AIR GRID
The original design for a conventional regenerator air distribution system was a
perforated plate. Air entered the base of the regenerator and then passed through a
large number of small holes in a large metal plate. In the late 1970's and early
1980's, the processing of more contaminated feedstocks increased air demand and
regenerator temperatures. Increased incidents of erosion, full CO combustion, and
the introduction of new regenerator designs lead to significant changes in the
design of the air grid.
The bubbling-bed regenerators feature a high catalyst entry point into the dense
bed relative to the air grid. Two basic types of air grid designs are used by UOP in
this style of regenerator: pipe grid and mushroom grid. The high-efficiency
regenerators have a low catalyst entry point relative to the air grid. On this design,
UOP uses a pipe grid.
The mushroom grid with extension arms is used in situations where a standpipe
inlet is below the air grid. A dome grid was used previously, but an exit in the grid
was needed to transfer catalyst to the regenerator standpipe. The mushroom air
grid with extension arms distributes air through jets located in the dome and arms.
A side view of the grid is shown in Figure 13. Figure 14 shows a plan of the
mushroom grid with arms.
The mushroom grid is constructed with 1" (25mm) lining on the dome and " (19
mm) lining on the extension arms. The lining minimizes the thermal stresses on the
grid wall resulting from the temperature differential between the inlet air and
regenerator.

157048-1
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Figure 13
Mushroom Air Grid with Extension Arms

157048-1
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Page 27

Figure 14
Plan View of Mushroom Air Grid with Arms

Plugged Nozzle
Open Nozzle

157048-1
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Page 28

The dome air grid distributes air through jets located on its dome. A side view of the
grid is shown in Figure 15.

Figure 15
Dome Air Distributor

157048-1
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Some dome-type air distributors have experienced jet erosion. UOP believes that
the erosion on this type of air grid is due to catalyst from the spent and recirculating
catalyst standpipes impacting directly onto the surface of the distributor. When the
catalyst impacts the air grid in this fashion, the catalyst can be forced into the jets
resulting in erosion as the catalyst is blown out of the jets. Erosion can also occur
on the external portion of the jet from the catalyst impact.
Several methods of combating this type of erosion have been developed. One
method is to install extended catalyst deflectors, which distribute the catalyst over a
wide cross-sectional area of the regenerator to minimize the localized impact of
catalyst onto the grid. Another modification is to cover the surface of the air grid with
an abrasion-resistant lining so that the outlet of the jets is flush with the abrasionresistant lining. The dual-diameter jets have also been replaced with singlediameter, higher velocity jets.
Because of mechanical reliability the pipe grid is the most commonly designed type
of air grid today. The pipe grid distributes the air through two to four large laterals
into a number of small branches. A side view of the grid is shown in Figure 16.
Figure 17 shows a plan of the pipe air grid. Modern air grids use a dual diameter jet
(Figure 18) with a restriction orifice at the inlet. This allows a higher pressure drop
for better air distribution while minimizing the velocity out of the jet for minimum
catalyst attrition.
Air grids are designed for a total pressure drop between 0.8 and 1.2 psi (0.06-0.085
kg/cm2). The pressure drop must be maintained above 0.5 psi (0.035 kg/cm2) to
achieve even distribution and should be below 1.5 psi (1.05 kg/cm2) to minimize
main air blower discharge pressure.
Many of the pipe grid and supports designed for partial combustion units were low
alloy, such as 5% chrome. The higher temperatures encountered in a most modern
full CO burning units require 304 SS.

157048-1
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Pipe-grids designed by UOP in the early 1970's had experienced cracking at certain
butt welded joints, but otherwise worked well. UOP has modified the pipe-grid
design and the advantages of this style of air grid are as follows:
1)

by using a 90 elbow (instead of a 45 lateral arm), thermal stress in the air


grid is greatly reduced because the elbow has greater flexibility

2)

the 90 elbow is attached to the header arms and main hub with extruded
connections which moves the welds away from the highly stressed junction

3)

the branch arms pass through the header arms which increases the strength
of these joints

4)

external abrasion resistant lining protects against erosion and also provides a
smooth thermal gradient

Figure 16
Pipe Air Grid

157048-1
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Figure 17
Plan of Pipe Air Grid

Figure 18
Dual Diameter Jet Detail

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A pipe grid is subject to severe catalyst erosion on the upper surface of the
branches. For this reason, older units had stainless steel retaining dams, Figure 19,
welded on top of each lateral. These dams held an insulating layer of catalyst which
alleviated both erosion and possible heat damage problems. Currently, UOP
designs the air distributor so the entire surface of the branches have abrasion
resistant lining. The lining provides both the erosion resistance and the thermal
barrier required.

Figure 19
Coffer Dam
Stiffener

Branch

157048-1
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The jets on the pipe air grid and on the arms of the mushroom grid point down to
avoid channeling the catalyst bed, as seen in Figure 18. It should be noted that
some of the jets are normally plugged. This is done for three reasons:
1.

To prevent a blast of air from impinging directly on an air pipe or the


regenerator wall.

2.

To increase the pressure drop to the proper level if the grid has too many
holes (future design case).

3.

To properly distribute air across the full regenerator cross section to


compensate for spent catalyst maldistribution.

The pressure drop across the air grid can be calculated with the equation:
P =

2.238 * W2
P * V2
=
Cd2 * Ah2 *
2200 * T

where:
P
P
T
V

=
=
=
=

W =
Cd =
Ah =

Grid pressure drop, psi


Air pressure to grid, psia
Air temperature to grid, R
Velocity of air through jets: flow rate of air/total cross sectional area
of all open jets, ft/sec
Air Flow, lb/sec
Orifice Coefficient
Orifice Cross Sectional Flow Area, in2

Flowing Air Density, lb/ft3

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REGENERATOR
The regenerator is an internally lined carbon steel vessel. The lining, called
refractory, is a concrete type material which is gunned onto reinforcing support
anchors. This lining is necessary to protect the metal wall of the vessel from the
high temperatures at which the regenerator operates and should keep the outer
shell of the regenerator below 650F (343C) at all times. The refractory is applied
over stainless steel hexmesh or steerhorn anchors. Different grades and depths are
applied depending on the service. In general, four - five inches (100 - 125mm) is
used in the regenerator when insulation is of primary importance.
Abrasion resistant refractory lining are used on all internal surfaces in the
regenerator to protect the base metal from the erosive environment. - 1 inch (19 25mm) of lining is typically used and is anchored by stainless steel hex mesh
anchors. This refractory is much harder and denser than the insulating refractory so
that it is provides more erosion protection but does not offer the same insulating
properties.
Instrument connections are inserted through the refractory. Thermowells, which are
used to measure catalyst or gas temperatures, are hard surfaced with a cobaltchrome stellite hard surfacing to protect them from the erosive conditions. Pressure
taps (and pressure taps used as level indicators) are protected by steam, gas, or air
purges. These are discussed later in this section. The purges provide a buffer
between the catalyst bearing gas in the regenerator and the small instrument taps
which can easily plug.
Figure 20 shows a conventional (bubbling bed) regenerator in detail. The air flows
from the grid up through a dense bed of catalyst where the carbon is burned off.
The catalyst enters the vessel from the spent catalyst standpipe, at the end of which
is a deflector baffle to distribute the catalyst evenly over the bed, not straight down
to the outlet. The design shown does not have an internal catalyst hopper, which is
a large diameter cone above the regenerated catalyst standpipe. The higher density
catalyst in the cone provides extra head pressure in the standpipe if needed by a
particular unit.

157048-1
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Combustion gases, excess air, and catalyst particles traveling from the dense
phase to the dilute phase are separated using two-stage cyclones. Flue gas leaving
the cyclones enters a plenum chamber at the top of the regenerator. The hot gases
travel through the double-disc slide valves, which are set to regulate the reactorregenerator differential pressure. The flue gas then travels through the orifice
chamber, where its pressure is dropped through a series of perforated plates.
Finally, the energy of the flue gas is recovered in a CO boiler (or steam generator
for a full combustion unit) where the CO is burned along with auxiliary fuel gas and
air to generate steam (or simply cooled to generate steam in a full combustion unit).

157048-1
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Figure 20
Conventional Regenerator
THERMOCOUPLES
(1each cyclone)
CYCLONE SUPPORTS
REGENERATOR PLENUM

REFRACTORY
LINING

MANWAYS

LEVEL AND
PRESSURE TAPS
TIs
FIRST STAGE
CYCLONES
REFRACTORY
LINING

SECOND STAGE
CYCLONES

EXTERNAL
LINING
TRICKLE
VALVES
TORCH OIL

OPEN PRIMARY
CYCLONE DIPLEG
TERMINATIONS

SPENT CATALYST
DEFLECTOR

SPENT CATALYST
STANDPIPE
LEVEL AND DENSITY
PRESSURE TAPS

MANWAY

AIR DISTRIBUTOR

CATALYST
WITHDRAWAL

REGENERATED
CATALYST
STANDPIPE

FCC-E003

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TWO STAGE REGENERATOR


The two-stage regenerator (RFCC) is used for units with heavily contaminated resid
feed stocks. The coke deposited on the catalyst is burned off by air distributed
through a grid mounted at the bottom of each stage. The spent catalyst enters the
upper, first stage regenerator which operates in partial combustion mode to
minimize the heat of combustion. Approximately 70% of the coke on the spent
catalyst is burned off in this stage. The catalyst is then transferred to the lower,
second stage regenerator through the recirculation catalyst standpipe. The second
stage operates in full combustion mode with excess oxygen to completely remove
the remaining carbon from the catalyst. This combination provides the heat balance
advantages of partial combustion operation with the advantage of low carbon, high
activity regenerated catalyst.
In the second stage regenerator, air is typically distributed through pipe grid
distributors although dome air distributors can also be used. In the upper
regenerator, the air distributor is typically the mushroom-and-arm type. Arms are
radially arranged around a central dome. The skirt which holds the upper air
distributor in place physically separates the two stages. Vent tubes in the skirt allow
the transport of combustion gasses and excess oxygen (with some catalyst) from
the second stage to the first stage. A two-stage regenerator is shown in detail in
Figure 21.
The recent RFCC design uses multiple pipe air grids in the first stage regenerator
entering through the cone rather than a single dome grid entering through the
second stage. This is a mechanically simpler design which eliminates the need for a
complex expansion joint on the air line. This also allows individual control to the air
grids in each section of the first stage. This configuration is shown in Figure 22.

157048-1
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Figure 21
Two Stage Regenerator
Flue Gas

Primary
Cyclone

Secondary
Cyclone

Mushroom
Grid
Distributor

Spent
Catalyst

First Stage
Regenerator
Spent Catalyst
Distributor
Ski-Jump

Recirculation
Catalyst
Standpipe

Catalyst
Cooler

Second Stage
Regenerator
(Side View)

Vent Tubes
First Stage Air Inlet

Second Stage
Regenerator

Cooled
Catalyst
Standpipe

Regen
Standpipe
Hopper

Regenerated
Catalyst

Pipe Air Grid


Distributor
2nd Stage Air

157048-1
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Figure 22
Updated RFCC First Stage Air Grid Design

1st Stage Regenerator

First Stage
Air In

2nd Stage Regenerator

FCC-E004

157048-1
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RFCC units will also have one or more catalyst coolers. The catalyst cooler slide
valve position is set by the signal from the second stage regenerator temperature
controller or the slide valve differential pressure controller over-ride via a low signal
selector. The recirculating catalyst slide valve position is set in a similar manner, by
signals from the lower regenerator level controller or the slide valve differential
pressure controller through a low signal selector. Each slide valve packing is steam
purged like the regenerated catalyst slide valve.
In the first stage the flue gas and catalyst are separated by two-stage cyclones. The
catalyst falls down the cyclone diplegs which are submerged in the catalyst bed to
provide a seal against gas passing up the diplegs. The primary cyclone diplegs are
typically open ended pipes with a splash plate and the secondary cyclones have
trickle valves. The catalyst flows into the annular zone around the mushroom air
distributor and into the recirculation catalyst standpipe and catalyst cooler(s). Air is
directed through nozzles on the underside of each arm of the upper air distributor to
help maintain proper fluidization of catalyst in this area.

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HIGH EFFICIENCY REGENERATOR


The high efficiency regenerator approximates a plug flow burning profile for the
catalyst as opposed to the back-mix regime of the standard bubbling bed design.
Because the high efficiency design burns essentially all of the CO in the
regenerator, there is no need for a CO Boiler and there is typically very little
afterburning. The plug flow burning profile also results in much lower NOx
emissions than a bubbling bed.
The spent catalyst from the reactor mixes with the blower air and roughly an equal
amount of recirculating regenerated catalyst at the bottom of the regenerator
(combustor). The recirculating flow of catalyst is necessary because the spent
catalyst at 925-1025F (495-550C) is not hot enough to initiate and complete
burning in a reasonably sized vessel. The mixing takes place in the lower part of the
regenerator, called the combustor or in a mixing riser, depending on the design.
Figures 23 and 24 show the two designs. These were developed to obtain the best
regeneration, with vessel cost and maintenance considered. The coke burns off the
catalyst as it travels up the combustor riser with the air. There is a rough separation
at the top of the riser through a "tee" shaped outlet. The flue gas goes up to a twostage cyclone system and out to energy recovery. The catalyst is returned to a
dense phase. From here the flow splits, part of the catalyst going to the base of the
reactor riser, and the rest back to the combustor.
The high efficiency regenerator has most of the same fittings as the conventional
bubbling bed design. The torch oil nozzles, instrument connections, and catalyst
loading lines are positioned differently because of the different regenerator
configuration, but function in the same manner as those in a conventional unit. If the
unit is equipped with a flue gas power recovery system, there will be spray nozzles
in the plenum chamber for emergency cooling if the temperature at the inlet to the
expander exceeds the safe limit of the machine.

157048-1
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Figure 23
UOP Fluid Catalytic Cracking Process
High Efficiency Regenerator System

Cyclones

Upper
Regenerator
Combustor
Riser

Combustor

Regenerated
Catalyst
Fluffing Air Ring
Spent
Catalyst

Mixing Zone
Air Grid

Spent Catalyst Distributor


(Ski Jump)

157048-1
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Figure 24
High Efficiency Regenerator with External Mixing

Upper
Regenerator

Combustor
Riser

Combustor
Recirculation
Catalyst
Standpipe

Regenerated
Catalyst
Catalyst/Air
Distributor
Spent
Catalyst
Lift Riser

Air

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COMBUSTOR CONE
Figure 25 illustrates the changes in regenerator cone design that have taken place
since the mid-1980s. UOP has developed a new cone detail (see Figure 26) that
eliminates the radial and axial constraint imposed by the hard refractory lining and
cold regenerator shell. The resulting stress is dissipated by incorporating a flexible
soft pack ceramic lining that permits both radial and circumferential expansion.
Additionally, the new cone detail minimizes thermal stresses due to radial
expansion by providing a flexible skirt section that connects to the regenerator wall.
The key feature of the new internal combustor cone design is the air space
incorporated between the cone skirt and the regenerator shell. The air space is
required to provide the optimal heat transfer medium between the cone and the
regenerator shell. By using this air space, it has been proven that the thermal
stresses in the cone are less than the stresses compared to other internal cone
designs that have experienced deformation.
In order to maintain this air space, it is mandatory to keep the air gap free of
catalyst. The catalyst seal device achieves this objective (see Figure 27). Some
characteristics of the catalyst seal are as follows:
1)
2)
3)

the seal is not tight; the gap operates at regenerator pressure


the seal design supports the weight of the catalyst within the regenerator
the seals allows thermal expansion of the cone

157048-1
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Figure 25
Combustor Cone Modifications

UOP 1906H-7
UOP 3110-4

157048-1
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Figure 26
Detail of Combustor Cone Design

Fiberfrax
Moist Pak-D
Abrasion
Resistant Lining

Refractory
Lining

Catalyst Seal Device


(Figure 26)

Ceramic Fiber
Blanket Insulation

Retaining Ring
Air Space

157048-1
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Figure 27
Detail of Catalyst Seal Device
Ceramic Fiber
(2 layers)

3.5 Sch. 10S Pips

4
(Cold Position)
2
(Hot Position)

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COMBUSTOR RISER ARMS


Several old-style high-efficiency regenerators have experienced excessive
deformation of the regenerator riser arms. The rectangular openings in the bottom
of the arms have "ovaled" and sagged. The arms have rotated at the leading edge
of the opening and have sagged 1 ft. to 2 ft. (300-600 mm) below the guides on the
regenerator wall.
The primary cause of the deformation is attributed to high-temperature creep
relaxation. During the late 1970's, the original circular openings in the arms were
enlarged to rectangular openings to improve catalyst separation efficiency. This
larger opening significantly decreases the inherent bending strength of the arm.
Several modifications to existing units have been implemented. The first method is
to install stiffeners to the arm to reinforce the opening. The second method is to
install a tension member from the riser to prevent excessive deformation.
The new-style riser arms have a modified geometry. The arms have been designed
as oblong members to improve strength. Additionally, a greater number of shorter,
smaller diameter arms are used (Figure 28). The shorter arm reduces the bending
stress resulting from weight. The increase in the number of arms improves the flow
characteristics in the regenerator by more uniformly discharging the catalyst across
the regenerator's cross-sectional area.

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Figure 28
New Style Combustor Riser Arms

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FLUFFING AIR DISTRIBUTOR


To improve fluidization in the upper regenerator and flow into the standpipes a
fluffing air ring (Figure 29) is installed in the cone. An alternate source of fluffing air
other than the main air blower is now specified for the upper air distributor. On
designs where the fluffing air was provided by the main air blower, circumstances
could arise where insufficient P was available for good fluidization of the catalyst.

Figure 29
Fluffing Air Distributor

STANDPIPES

ABRASION RESISTANT
LINING

ABRASION RESISTANT
RESTRICTION
ORIFICE

LINING
PIPE

3/4 " XX-STRONG PIPE


DISTRIBUTOR JET

157048-1
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TORCH OIL NOZZLES


The torch oil nozzles shown in Figure 30 provide a means of injecting heavy oil into
the regenerator when extra heat is needed (e.g. during the startup). The oil is
sprayed into the regenerator with atomizing steam through a special nozzle made of
tungsten alloy to withstand the high temperature. These nozzles may be retracted
through a packing gland if they need to be cleaned. Steam is continuously injected
through a 1/8" (3mm) restriction orifice to the annular space around the nozzle to
keep the area clear of catalyst, which could pack up and prevent retraction of the
nozzle. Steam is also continuously injected through the nozzle tip to keep it cool
and prevent plugging with catalyst. Excess steam may contribute to erosion and
catalyst breakup.
The nozzle should be marked so that after cleaning it can be returned to its proper
position - recessed " (6 mm) back from the refractory face. This position allows
the oil spray to miss the regenerator wall, yet protects the nozzle.
During a turnaround, the various steam and torch oil nozzles should be inspected. If
there has been too much purge steam around the barrel there may be erosion
problems in the refractory surrounding it. The nozzles should be checked for wear
and cleanliness. If the nozzle was not recessed the proper " (6mm), there will
probably be severe metal loss. Refractory damage may indicate the nozzle was
recessed too much. Nozzle positions should be checked when they are replaced.

157048-1
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Figure 30
Torch Oil Nozzle

SPRAY NOZZLES
Spray nozzles are used to inject water through an atomizing nozzle to cool off the
flue gas in the plenum chamber if the unit has power recovery. The spray water
should be clean, such as steam condensate. Contaminants such as sodium will
cause problems by deactivating the catalyst or contributing to its breakup.
Mechanically, the spray nozzles are similar to the torch oil nozzles.

CATALYST COOLER
The ability to control and vary the amount of heat removed from the regenerator
creates an additional degree of freedom by moderating the regenerator temperature
as a limiting constraint. The catalyst cooler provides a variable heat sink, which

157048-1
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allows the refiner to vary the catalyst/oil ratio, reactor temperature, and feed
temperature independently of one another.
The catalyst cooler tube bundle is inserted into a refractory lined shell off the side or
bottom head of the regenerator. The tubes of this exchanger are the bayonet type.
The boiler feed water enters the cooler through the inner tubes and the mixture of
water and steam exits the cooler through the annulus between the inner and outer
tubes. The outer tubes are 3 inch (75mm) O.D. made from 1 Cr, Mo seamless
tube material. The inner tubes are 1-3/8 inch (35mm) O.D. made from carbon steel
seamless tubing.
The stainless steel fluidizing air lances distribute air into the cooler near the bottom
of the tubes. The air creates turbulence and increases heat transfer coefficient as
the bubbles travel upward. The backmixing created by the bubbles also brings hot
catalyst into the cooler from the regenerator. The air is delivered to a common
manifold supplying all the lances through a flow controller. The lances contain a
restriction orifice, located near the piping header at the top of each lance, to help
distribute the air uniformly over the cross sectional area of the cooler. The
countercurrent fluidizing air improves heat transfer by creating turbulence and
mixing in the region of contact between the hot catalyst and the tubes. A differential
pressure transmitter, with taps located above and below the cooler, gives a direct
indication of the density of the fluidized catalyst at various conditions of catalyst flow
and air injection.
Mechanical reliability is achieved by locating the cooler in the dense phase of the
regenerator. In the dense phase, the heat transfer coefficient is higher which
permits lower catalyst and fluidization air velocities. Lower velocities minimize
erosion within the cooler. In addition, the cooler tubes are located in the vertical
plane. This feature generates a uniform heat transfer coefficient over the entire tube
surface thereby preventing uneven surface temperatures which cause localized
stress.
Catalyst coolers have been designed and built to fit virtually every regenerator
configuration, including single-stage bubbling beds, high-efficiency combustors, and
two-stage regenerators. Three basic styles of UOP catalyst coolers are currently
available:

157048-1
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Flow-through catalyst cooler The catalyst flows downward into the cooler shell
and exits into the cooled catalyst standpipe near the bottom of the tube bundle. The
standpipe transports the cooled catalyst through a slide valve and expansion joint
into the combustor on a high efficiency regenerator or to the second stage
regenerator on an RFCC. In a single stage bubbling bed regenerator the catalyst
can be lifted back into the regenerator with air through a lift riser. Both the catalyst
flow through the cooler and the fluffing air rate are used to control the cooler duty.
Backmix catalyst cooler This style contains no catalyst exit standpipe. Hot
catalyst enters the cooler by backmixing as a result of fluidization air injected near
the bottom of the tube bundle. The major advantage of this cooler design is that no
slide valve, expansion joint, or standpipe is required. This configuration also permits
the cooler to be lower to the ground if elevation is a limiting constraint. The duty of
a back mix cooler is ~60% of an equal sized flow through cooler and is controlled
only with the fluffing air.
Hybrid catalyst cooler The combination of flow-through and backmix operation
constitutes the hybrid catalyst cooler. In a hybrid, the catalyst exits into a standpipe
located at the midsection of the tube bundle (instead of at the bottom as in flowthrough coolers). In the hybrid cooler, the upper portion of the bundle operates in
the flow-through mode, and the bundle length below the catalyst outlet operates in
the backmix mode. This configuration achieves somewhat less heat-removal
capacity than a full flow-through cooler but still transfers cooled catalyst down to the
lower portion of the regenerator.
The catalyst cooler steam generation circuit includes the cooler, steam drum, and
circulation pumps. Boiler feedwater is pumped to the bottom head, enters the inner
tubes, then flows down through the annulus between the inner and outer tubes
where it absorbs heat to generate steam. The steam-water mixture leaves the
catalyst cooler to be separated in the steam drum. Makeup boiler feed water is
delivered to the steam drum through a flow controller which is cascaded to signals
from the drum level and steam generation flow transmitters. Steam flows from the
drum through a stop check non-return valve and a superheater (either part of the
flue gas cooler or a fired heater) before entering the refinery steam header.

157048-1
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Figures 31-35 show some examples of catalyst coolers and catalyst coolerregenerator configurations that have been constructed.

Figure 31
Flow Through Catalyst Cooler
UOP Catalyst Cooler General Arrangement

157048-1
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Figure 32
UOP Backmix Catalyst Cooler

157048-1
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Page 57

Figure 33
Examples of Bubbling Bed Regenerators
with Catalyst Coolers

Flow Through

Backmixed

Aeration
Air

Aeration
Air

Lift Riser
Cooled
Catalyst
Standpipe

Water and
Steam

Water and
Steam

Water

Water
Air

Lift Air
Distributor

157048-1
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Page 58

Figure 34
Examples of High Efficiency Regenerators
with Catalyst Coolers

Cone Mounted Flow Through

Side Mounted Hybrid

Cone Mounted Backmix

157048-1
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Figure 35
RCC Regenerator with Catalyst Coolers
Example of an RCC Regenerator with Multiple Catalyst Coolers

Fluffing Air

Fluffing Air
Air

Backmix
Catalyst Cooler

Flow-Through
Catalyst Cooler

Air

UOP 2119-27

157048-1
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Operating the catalyst cooler with sufficient water circulation to ensure that the tube
walls are always wet so that they can not overheat and limiting the fluffing air so that
the tubes are not subjected to erosion are critical in ensuring mechanical integrity
and long life of the cooler. In new units the flow controller regulating the water flow
to the cooler has been eliminated so the water flow is set by the pump curve. The
spare pumps are instrumented to start automatically on low water flow. If the water
flow is not recovered by the auto start the cooler is shutdown by closing the cooled
catalyst slide valve and the fluffing air control valve. The fluffing air rate should
never exceed a flow that will result in a superficial velocity in the shell of more than
1 ft/sec (0.3 m/sec).
In recent years, as catalyst cooler reliability has improved, UOP has shifted from a
reactive to a proactive approach to catalyst cooler design. Several design
modifications have been developed recently.
Tie Rod Support
Previous designs had the tie rods, which support the eggcrate bracing, protrude
through a hole in the upper tubesheet. The tie rod was welded to the tubesheet on
the steam (bottom) side. While this method was acceptable under normal operating
circumstances, the tie rod could potentially push through the tubesheet if tie rod
growth was restricted due to an obstruction or thermal binding. This would create a
path for the steam to enter into the catalyst side of the cooler, having the same
effect as a tube leak. The current design eliminates the hole through the tubesheet,
using instead a cup into which the tie rod is inserted (see Figure 36). This cup is
countersunk and welded into the catalyst (top) side of the tubesheet. The tie rod is
welded around the rim of the cup above the refractory face providing easy access
for bundle maintenance or refurbishment. This design eliminates the possibility of
the tie rod creating a steam leak.

157048-1
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Figure 36
Modifications to Tie Rod Supports

Tie Rods

Bracing Bars

Egg-Crate
Support Bracing

Refractory Lining

Old Method

Upper Tubesheet

New Method

157048-1
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Page 62

Tie Rod / Eggcrate Connection


Several recent catalyst cooler inspections have revealed tie rod deformation,
usually more severe in the upper section between the eggcrate supports. While this
by itself had not caused any operational problems, it suggests that the fit between
the eggcrates and the outer tubes is extremely tight. Thermal expansion of the
eggcrates causes binding on the outer carbon steel tubes which are water cooled.
The hot stainless steel tie rods expand a greater amount and do not have adequate
strength to move the eggcrates as they are intended. Their thermal growth being
restricted, the tie rods buckle. As a result, the eggcrates are no longer welded
directly to the tie rods which allow them to expand independently of each other (see
Figure 36). The eggcrates are supported by minimal friction on the tubes
themselves. The hot tie rods are free to expand within the eggcrates. As a
precaution, large washers are welded to the tie rods a few inches above and below
the eggcrates to limit any unexpected movement of the eggcrates either during
operation or bundle handling.
Flat Tube Caps
The fluffing air headers and lances are supported by arms that are welded near the
top of the air lances (see Figure 37). Originally, each arm was welded to a stainless
steel pipe support stool that was welded to the outer tube hemispherical tube cap.
Later, the arm to support stool weld was removed in order to allow for a greater
degree of flexibility for the fluffing air headers and lances. In the current design, the
support stools have been replaced with flat tube caps (see Figures 37 and 38).
These new tube caps are machined bar stock that are rounded on the inside and
flat on the top. The removal of the pipe support stools has several advantages :

A weld to a pressurized tube cap is no longer necessary.


A postweld heat treatment step has been eliminated.
Tube alignment is easier.
A more uniform surface on which the air lances can rest has been created.

The small additional cost of the flat tube caps is recovered in assembly time.

157048-1
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Figure 37
Modifications to Outer Tube Caps
Aeration Pipe Header
Aeration Lance
Lance Support
Arms
Pipe Support
Plate
Pipe Support
Stool

Old Method

Flat Tube Cap

Outer Tubes

New Method

157048-1
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Figure 38
Flat Tube Cap

Inner Tube Wall Thickness


The wall thickness of the inner tube has been increased on most recent catalyst
cooler designs. The resulting smaller diameter increases the inlet water pressure
drop which ensures a uniform distribution of water to all of the tubes and guarantees
the tube cap and inside wall of the outer tube are fully wet.
Eight-Foot Cooler
As FCC and RFCC units become larger and are required to process very heavier
resid, the heat removal demand increases. In anticipation of this, UOP now offers
an eight foot diameter cooler (96" ID of shell). This cooler can provide about 40%
more duty than the typical seven-foot design. This is particularly beneficial when the

157048-1
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required duty is slightly higher than the duty of a seven foot catalyst cooler, making
a single eight foot cooler a less expensive alternative to two smaller coolers.
Update: Debris Screens
Since 1991, debris screens have been installed in all existing units. Debris screens,
which are installed at the entrance to the cooler, have become standard supply for
all coolers mounted on the lower regenerator cone or head. The screens prevent
large refractory pieces or other loose debris from accumulating at the bottom of the
tube bundle where the debris can restrict or divert the flow of air from the air lance,
potentially causing catalyst impingement on a tube and an eventual tube leak. Aside
from some minor improvements in the anchoring method, the screens have held up
well in operation and have performed their function. There have not been any tube
leaks caused by accumulated debris in coolers with debris screens.
Update: Air Lance Pressure Testing
Because the internal air piping and lances are not subject to code requirements,
UOP implemented a required shop pressure test of the completed aeration
assembly in 1991. Since that time, there have been no reported air leaks or weld
failures in any operating coolers that have received this testing. Prior to the shop
testing, air leaks had occurred in at least five units, three of which lead to tube
leaks.

157048-1
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CYCLONES
The flue gas leaving the dense bed will entrain some of the catalyst particles with it.
Some of these settle back to the bed; others are carried higher. Measurements of
the entrained particles taken at increasing heights above the bed show a gradual
decrease in the amount of fines entrained. At some point above the bed, the
concentration of particles entrained levels out. This is called the Transport
Disengaging Height, or TDH.
Early FCC units used a number of small tubes, called multi-clones to remove
particles. These were not particularly effective and were difficult to maintain. The
cyclone design shown in Figure 39 was the next step. The shaveoff was intended
to increase efficiency, but also proved difficult to maintain. The cyclones used in the
modern FCC unit use a fairly simple principle to remove most of the particles. See
Figure 40. The catalyst bearing gas enters a cylinder through a tangential opening.
The catalyst is 500-1000 times as heavy as the gas, and is subjected to forces
several hundred times that of gravity as the gas swirls around the cylinder. The
larger particles are removed through centrifugal forces which force the particle
outward to collide with the wall. The collisions slow down the particle so that they
fall by gravity into the dust hopper and are returned to the vessel through the
diplegs. The viscous drag forces of the gas tend to carry some of the catalyst
particles with it. Generally only the smaller particles are light enough to stay with the
gas, because the inertial and centrifugal forces acting on them are small.
The catalyst separated from the gas stream swirls downward due to the force of
gravity. The chamber below the entrance of the cyclone tapers downward and tends
to keep the catalyst against the wall which is away from the cleaner area at the
center core (where the gas disengages and moves up). There is more disengaging
area in the hopper, which feeds catalyst to the dipleg; this disengaging area also
decreases the amount of erosion which could be created by the vortex of the
catalyst particles.

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Figure 39
Cyclone-Catalyst Fines Collector with Shaveoff
Catalyst-Free
Gas Outlet

Gas Out
Catalyst
Shave-Off

Bypass
Catalyst Shave-Off
Bypass
Catalyst-Laden
Gas Inlet
Re-Entry
Opening

Note:
Because of the High Maintenance
Required on the Catalyst Shave-Off
(Caused by Erosion) many Refiners are
Choosing to remove this Device

Catalyst-Laden
Gas Inlet
Stream PatternLower Portion
Stream PatternUpper Portion
(Principally Finer Particles)
Disengaging
Hopper
Catalyst
Outlet
Dip Pipe
UOP 2119-28

157048-1
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Figure 40
Cyclone-Catalyst Fines Collector

There is a pressure drop between the cyclone inlet and dipleg outlet. If the catalyst
is to be returned to the bed, the dipleg must hold a head of catalyst sufficient to
overcome this differential. If the catalyst in the dipleg stops flowing, the gas will
simply carry the catalyst out the top. If the dipleg is submerged in the bed, then the
pressure at the bottom will increase and catalyst will be forced out as the level in
the leg rises. The required head will determine the dipleg length.
There are two general types of dipleg termination devices the trickle valve and
counterweighted flapper valve. The trickle valve in Figure 41 is generally used on
submerged diplegs. The valve is simply a flat plate held closed by gravity and
external pressure until the catalyst head in the dipleg is sufficient to open it. The leg
dumps, and the trickle valve swings shut. The counterweighted flapper valve in

157048-1
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Figure 42 is another method, with a better seal than the trickle valve. The
counterweight holds the flapper closed until the catalyst head is sufficient to open
the flapper.
UOP has updated the design of the counterweighted flapper valve to improve its
mechanical reliability and maximize the unit onstream efficiency.
The major revisions to the design are:
1.

Addition of a stop bar to prevent the valve from opening more than 45 (see
Figure 42).

2.

Addition of a stiffener bar on the fixed portion of the pivot mechanism to


minimize warpage or movement over the course of repeated thermal cycles.

3.

Minimizing the tolerance between the concentric bushings to 3 mm plus 1.6


mm minus 0 mm (1/8" plus 0.0625" minus 0") to allow for thermal growth
(see Figure 43).

4.

Requirement that the hard surfacing used on the pin and bushings be crack
free. There is some concern that surface cracking may contribute to
roughness and thus restrict smooth motion of the hinge mechanism.
Alternative hard surfacing such as Waspalloy, Wallex 50 and Triten should
be considered as options for hard surfacing of the pin and bushings.

5.

Increasing the amount of counter weight used (Table 1).

157048-1
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Figure 41
Trickle Valve

Hinge

Flapper Plate

Stop

3-5 From Vertical

157048-1
Equipment
Page 71

Figure 42
Counterweighted Flapper Valve

STIFFENER

LUG
DETAIL

Closed Position

Open Position

157048-1
Equipment
Page 72

3mm

+0.0625"
-0.000"
+1.6mm
-000mm

1 1/2 " PLUS/MIN 1/32 "ID

1/8 "

(BOTH SIDES)
(BOTH SIDES)

38mm PLUS/MIN.8mmID

Figure 43
Bushing Detail

3/8 "(10mm)

7/8 "
(22mm)

OF BUSHING

(INCLUDES 1/8 "(3mm)


HARD SURFACING)

LUG ON DIPLEG

1/8 "

(3mm)

3"(75mm) DIA

HARD

1/8 "(3mm)

BUSHING

SURFACING

CONCENTRIC

DIA

2 9/32 "(58mm)

OF HOLE

OF BUSHING

7/8 "

3/8 "(10mm)
(INCLUDES 1/8 "(3mm)

OF BUSHING

HARD SURFACING)

3"(75mm) DIA

HARD

(22mm)

1/8 "(3mm)

DIA

2 9/32 "(58mm)

BUSHING

SURFACING

ECCENTRIC

38mm PLUS/MIN.8mmID

1 1/2 " PLUS/MIN1/32 "ID

ECCENTRIC BUSHING

CONCENTRIC BUSHING

OF BUSHING
AND HOLE

157048-1
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TABLE 1
FLAPPER VALVE COUNTERWEIGHT
Dipleg
Diameter
6 (150 mm)
8" (200mm)
10" (250mm)
12" (300mm)
14" (350mm)
16" (400mm)
18" (450mm)
20" (500mm)
22" (550mm)
24" (600mm)

Counterweight
Lbs / Kg
1.9
3.3
5.4
7.8
9.6
12.8
16.4
20.5
25.0
30.0

0.9
1.5
2.4
3.6
4.4
5.8
7.4
9.3
11.4
13.6

Two important factors in cyclone efficiency are the velocity of the gas and the size
distribution of the particles. In general, the higher the velocity, the higher the
efficiency. It should be remembered, however, that higher cyclone velocities may
mean higher vessel velocities, with more catalyst carried up to the cyclones. If these
are larger particles, most of them will be collected, but in extreme cases, the
cyclones could be overloaded and the larger particles lost. Higher velocities also
means higher rates of erosion and catalyst attrition. The solids distribution is not
under immediate control, except by minimizing attrition of the catalyst by avoiding
areas of high velocity. In general, the small fines, less than 20 microns, will be lost,
with most of the larger size particles collected. The reactor cyclones generally do a
better job because here the coke on the catalyst fines makes them larger and
easier to collect.
The design of the cyclone is the important factor in its efficiency as well as the
resistance to erosion; it is normally handled by the cyclone manufacturers.
However, in the early 1980's, erosion in the cyclones and cyclone diplegs increased
noticeably. Units were beginning to process larger quantities of heavier and more
contaminated feeds. These feeds produce more coke, which increases air demand
and regenerator temperatures. The net result is increased erosion as a result of an

157048-1
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increase in catalyst loading and cyclone velocities. Competition among vendors was
another factor leading to an increase in instances of erosion. In some cases,
vendors supplied cyclones with key geometric ratios, such as L/D, minimized for
cost reasons.
To address these problems, UOP began to specify cyclone geometric relationships
and velocity criteria. The purpose was to ensure that all cyclone vendors bid on the
same basis and that the cyclones supplied met the process and mechanical
requirements set by UOP.
The requirements set forth in the "Mechanical Considerations In FCC Design" paper
presented at the 1996 UOP FCC Symposium have significantly reduced erosion
problems. These requirements are as follows:

Single-Stage Reactor Cyclone Criteria

Inlet velocity shall not exceed 65 ft/sec (19.8 m/sec).


Outlet velocity shall not exceed 100 ft/sec (30.5 m/sec).
Ratio of barrel area to inlet area shall be 5.5 minimum.
Ratio of the main cone outlet diameter to the barrel diameter shall be 0.4
minimum.
Ratio of cyclone height, measured from the roof of the cyclone to the outlet of
the dust hopper cone, to its barrel diameter shall be 5.0.
Projected apex point of the main cone shall terminate at a minimum distance of
0.3 x barrel diameter above the outlet of the dust hopper cone (0.5 x barrel
diameter for eccentric diplegs).
Ratio of the dust hopper diameter to the main cone outlet diameter shall be 1.5
minimum.
Ratio of the dust hopper cone height to the barrel diameter shall be 0.45
minimum.

157048-1
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Regenerator Cyclone Criteria


First Stage

Inlet velocity shall not exceed 65 ft/sec (19.8 m/sec).


Outlet velocity shall not exceed 80 ft/sec (24.4 m/sec).
Ratio of barrel area to inlet area shall be 3.7 minimum.

Second Stage

Inlet velocity shall not exceed 75 ft/sec (22.9 m/sec).


Outlet velocity shall not exceed 120 ft/sec (39.6 m/sec).
Ratio of barrel area to inlet area shall be 4.3 minimum.

Both Stages

Ratio of the main cone outlet diameter to the barrel diameter shall be 0.4
minimum.
Ratio of cyclone height, measured from the roof of the cyclone to the outlet of
the dust hopper cone, to its barrel diameter shall be 5.0.
Projected apex point of the main cone shall terminate at a minimum distance of
0.3 x barrel diameter above the outlet of the dust hopper cone.
Ratio of the dust hopper diameter to the main cone outlet diameter shall be 1.5
minimum.
Ratio of the dust hopper cone height to the barrel diameter shall be 0.45
minimum.

The reactor cyclones are normally a low alloy steel, such as 1 Cr, Mo. Some
older partial CO combustion regenerator cyclones used 5 Cr or 12 Cr, with 1 Cr
diplegs sometimes. For the higher temperatures of modern, complete CO
combustion, Type 304 stainless steel (18 Cr, 8 Ni) is used. Abrasion resistant lining
is used on all cyclones to protect them from catalyst erosion. The inlet horn, the gas
outlet pipe, barrel, disengaging hopper, and part of the dipleg will be lined. The

157048-1
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extent of the dipleg lining will depend on accessibility and prior experience; erosion
in one area usually leads to a lining at the next turnaround. The exterior of the
diplegs must be protected with an abrasion lining where they are subject to catalyst
impingement, such as from the spent catalyst inlet or from another dipleg discharge.

ORIFICE CHAMBER
Orifice chambers (Figure 44) are used on FCC units when the regenerator pressure
is controlled by flue gas slide valves. The chamber is a cylindrical vessel with a
series of perforated grid plates (Figure 45). These plates hold a backpressure
downstream of the slide valves. By reducing the pressure drop across the valves,
their operating life is greatly extended because there is no sudden acceleration of
the catalyst bearing gas stream. The flow through the orifice chamber may be
upflow or downflow depending on downstream equipment. There are no moving
parts, so no adjustments can be made on stream. UOP designs the orifice chamber
as follows:

the flue gas slide valve is designed for approximately one-third of the pressure
drop and the orifice chamber is designed for the remaining two-thirds of the
pressure drop.
enough grids are installed to limit the pressure drop across each individual grid
while maintaining a specified velocity across each hole.
the distance between the top grid and the flue gas slide valve is kept at a
maximum. In revamp situations, this distance may be short and lining will be
required for the first grid only. Additionally, the installation of a shroud at the
inlet has proven to be beneficial in reducing erosion.

Given the UOP design philosophy of using cold wall construction whenever
possible, UOP has developed a cold wall orifice chamber. As a result, the chamber
walls are no longer prone to buckling, cracking, bulging and other phenomena
associated with high temperature stainless steel design.
Because of the high inlet temperature of the orifice chamber, the grids must be
designed for stainless steel metallurgy (if a waste heat boiler is installed upstream,
then carbon steel or low chrome can be used). The grids are supported by a

157048-1
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cylindrical skirt section; typically two grids are supported from one skirt section. The
cylindrical skirt is supported by a tapered skirt section which is then welded to the
chamber wall. The tapered skirt requires a certain length to accommodate the
thermal expansion of the stainless steel grid relative to the cold wall shell. A gap is
also provided between the skirt and the refractory lining to allow for this expansion.
Blanket insulation is provided behind the tapered skirt to allow for the thermal
deflection.
The cold wall orifice chamber significantly reduces the amount of thermal growth of
the flue gas line (as compared to the hot wall design). This reduction will reduce or
eliminate the amount of expansion joints required. Given the change in thermal
movements, as well as the additional weight (due to the refractory), the entire flue
gas system should be reviewed for both support and flexibility for revamps.
Inspection
UOP has developed two types of orifice chambers to accommodate various revamp
inspection requirements. The first option allows external manway access to each
pair of top skirt grids (due to the skirt support scheme, external access to all grids is
not possible). To accommodate the external manways, extra tangent length for the
orifice chamber is required.
In the event there are space limitations, a shorter version has been developed.
Inspection access for this design requires the use of internal manways on each grid.

157048-1
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Figure 44
Cold Wall Orifice Chamber
Inlet Shrould
FLOW
Internal
Manways

157048-1
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Page 79

Figure 45
Orifice Chamber Details
C GRID

RING NO 5

RING NO 4

RING NO 3

RING NO 2

RING NO 1

INTERNAL MANWAY

AIR SPACE

HIGH DENSITY
REFRACTORY
LINING
RING NO 5
RING NO 4
RING NO 3

STAGGER HOLES
WHERE POSSIBLE

CERAMIC FIBER
BLANKET
INSULATION
LINING TRANSITION

RING NO 2
RADIUS RING NO 1

C GRID

ABRASION
RESISTANT LINING
HIGH DENSITY
REFRACTORY LINING

+
- GAP
AIR

157048-1
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ELECTROSTATIC PRECIPITATORS
Electrostatic precipitators (Figure 46) are used to remove catalyst fines from the
flue gas. The equipment consists of a large rectangular steel shell which contains a
number of wires called discharge electrodes, and a number of flat collecting plates.
The wires and plates are hung vertically, in alternating rows. A high electrical
potential is put on the discharge electrode wires, and the plates are electrically
grounded. A corona discharge surrounds the discharge electrode because of the
high potential. Gas ions formed by this corona move rapidly towards the collecting
electrode. When an ion strikes a catalyst fine, it becomes charged. The electrical
field between the electrodes causes the particle to deposit on the collecting
electrode. As more particles collect, a layer of fines builds up on the plate. A
mechanical rapper periodically strikes the frame of the collecting plate, and the
particles are knocked off. The fines tend to agglomerate into larger particles which
fall into dust hoppers under the electrodes. There is no physical change in the
particles, simply an agglomeration which makes them large enough for gravitational
forces to exceed the carrying force exerted by the gas.
Precipitators usually operate at pressures slightly above atmospheric. Inlet
temperatures range from 400-800F (205-425C). The temperature is especially
important if the flue gas has acidic components such as SOx or NOx. These may
condense and combine with water to form corrosive agents. The precipitator shell
may be insulated to hold the metal temperature high enough to prevent
condensation.

157048-1
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Page 81

Figure 46

Electrostatic Precipitator
Insulator
Discharge
Electrode
Rapper

Collecting Surface Rapper


Transformer Rectifier

Gas Out

Collecting
Surface
Gas Flow In
Hopper

UOP 2119-34

Discharge
Electrode

Catalyst Fines Out

157048-1
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Page 82

Collection efficiencies range from 70-99%, with 90-95% more common. The factors
affecting the efficiency are:
1.
2.
3.
4.
5.
6.

Effective voltage and other electrical factors


Resistivity of fines
Size distribution
Gas flow rate
Collector plate area
Rapping cycles

As the effective voltage increases, the efficiency increases. Too high of a voltage
can lead to arcing, which will damage the electrodes. Arcing can also occur if the
weights holding the discharge electrode wires fall off and allow the wires to swing
over towards the collecting plate. The precipitator should be designed with the
proper number of power supplies and control equipment to prevent excess
sparking.
The resistivity of the fines is approximately constant. It may be decreased for better
collection efficiency by adding small (<20 ppm) amounts of ammonia, but this is
usually not required. Spray water is also used in some cases.
The size distribution will be determined by cyclone performance in the regenerator.
Large solids rates to the precipitator, even with high efficiencies, may still lead to
emission problems, so it is better to have lower loadings to the unit. Larger particles
are easier to collect, because the smaller ones are more easily carried with the gas.
Typical gas flow rates are 5-6 ft/sec (1.5-1.8 M/s). Lower flow rates will give greater
efficiency. A higher collecting area will also increase efficiency.
The final factor, the rapping cycle, is normally designed for one strike from each
rapper every 1-3 minutes. Greater power and frequency of rapping will increase
efficiency, but must be balanced against cost. Both collecting and discharge
electrodes are fitted with rappers, most of them positioned on the collectors.

157048-1
Equipment
Page 83

CATALYST STORAGE HOPPER


The FCC unit is normally built with two or three catalyst hoppers (Figure 47). One is
for fresh catalyst, the other is for equilibrium catalyst. RFCC units or FCC units with
high metals feed stocks may have a third hopper for storing low metals equilibrium
catalyst. The vessels are normally carbon steel, constructed to withstand a full
vacuum, although this should be checked before the first use. Many units are built
with automatic gauging devices, but these are not always accurate because the
float tends to sink in the catalyst. For accurate measurement of the catalyst level,
the hopper should be fluffed with air from the bottom and the catalyst allowed to
settle. A hand gauge can then be used to read the tons of catalyst from a chart of
inventory as a function of hopper ullage. Exact settled densities for a given type of
catalyst may be determined by measuring level change after a weighed amount of
catalyst has been loaded or unloaded by truck or cartons. A discussion of catalyst
loading and hopper operation is provided in the procedure section.
CATALYST LOADING AND UNLOADING LINES
The catalyst transfer line at the bottom of the regenerator is normally used to
remove catalyst from the regenerator when the unit is shut down. Most of the
catalyst will be loaded and unloaded through a connection (4-6 inch or 100-150
mm) in the dense bed area. For rapid transfer, a large line is used. For gradual
fresh catalyst addition, a smaller line is used which connects into the large line just
before the regenerator at an angle to minimize erosion. The catalyst lines are
usually carbon steel. The catalyst withdrawal lines from the regenerator should be
1 Cr, Mo (up to the second block valve). It may be cased in places for
personnel protection, but should be allowed to cool off to the atmosphere so that
the temperature limits of the metal are not exceeded when hot catalyst is unloaded.
Some units have finned pipe to help in cooling off the unloaded catalyst.

157048-1
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Page 84

Figure 47
Catalyst Storage Hopper

Auto Gauge
Instrument
Vacuum
Nozzle

Grate with
Wire Mesh

Outlet

Manual
Gauge Hatch

Relief Valve
Inlet

Manway
Catalyst Makeup
(Fresh Catalyst Only)

157048-1
Equipment
Page 85

CATALYST STANDPIPES AND EXPANSION JOINTS


Catalyst flows through refractory-lined standpipes from the regenerator to the base
of the riser, from reactor to the regenerator, and from the upper regenerator to the
combustor. Expansion joints (Figure 48) are placed in these large catalyst-transfer
lines to absorb thermal movement within the system and thereby minimize stresses
imposed on vessel nozzles. The expansion joint is lined to protect the bellows from
catalyst erosion. Pantographic linkages are used on the expansion joints to assure
equal movement of both expansion bellows during temperature changes.
Parameters affecting expansion joint design are movement to be absorbed, process
environment, mechanical construction, and specified cycle life. During the last 10
years, advances have been made in the engineering and metallurgy of expansion
joints. For a hot wall regenerator standpipe using 304H SS, the expansion joint had
Inconel 625 bellows that were annealed after forming [for combined resistance to
polythionic attack (PTA) and stress corrosion cracking (SCC), Inconel 625 is one of
the recommended alloys]. The maximum allowable bellows temperature for this
design was 1200F. Today we use cold wall design for the standpipe and expansion
joint. The expansion joint bellows use Inconel 625 LCF (low cycle fatigue) with a
maximum allowable temperature of 1000F and it is not annealed after forming.
Annealing reduces the strength of the bellows as well as the fatigue properties.
It is important that the bellows material not get too hot so age hardening does not
occur. It is also important to stay above the dew point of the process so the bellows
stay dry and corrosion is avoided. For example, the regenerator expansion joint
bellows temperature would be close to the dew point so UOP specifies external
insulation of 25 mm which is enough to raise the bellows metal temperature to 600800F and to stabilize it from external changes caused by the weather.

157048-1
Equipment
Page 86

Figure 48
Expansion Joint Location

Top of Support

Spring Hangers

Spent Catalyst
Expansion Joint
Recirculation Catalyst
Expansion Joint
Regenerated Catalyst
Expansion Joint

Top of Support

Structural Bumper

157048-1
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Page 87

The typical components of a UOP specified expansion joint are shown in Figure 49.

Figure 49
Expansion Joint Components

Convolution

Liner

Root
Ring

Cover

Purge
Connection

Bellows
Flow

Bellows Design UOP presently specifies single ply bellows. Dual Ply bellows are
acceptable provided each ply is designed for full temperatures and pressure. Dual
Ply bellows should include a method for pressure leak detection (preferably a
positive pressure gage) as shown in Figure 50. When adding a dual ply
replacement to an existing expansion joint, the piping system should be reviewed
for the additional loads induced by the higher spring rates of the dual ply.

157048-1
Equipment
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Figure 50
Two-Ply Bellows
WEEP HOLE

TWO-PLY TESTABLE

FOR LEAK

BELLOWS

DETECTION

SEAL BAND TO ISOLATE


BELLOWS ATTACHMENT
WELD

PROCESS PIPE

ATTACHMENT
WELD

Control Rod Design The control rods are intended for control and stability of the
expansion joint and are not intended to take the full bellows pressure thrust force.
The control rods should be used for reference when determining the installed
position of the expansion joint as well as a reference during operation and shutdown
(for future trouble shooting information).
Equalizing Rings UOP presently specifies a self equalizing expansion joint. Root
rings are an acceptable alternative to equalizing rings. (UOP specifies a minimum
area requirement for root rings). Equalizing rings and root rings are intended for
added protection in the event of over pressure.
Bellows Packing Details Several methods of packing the bellows are shown in
Figure 51. External insulation is required on packed bellows to minimize the
potential of condensation during operation. UOP currently uses packed bellows for
all expansion joints except for the spent catalyst expansion joint which is
continuously steam purged to remove hydrocarbon and minimize coking. Several
refiners have successfully used packed bellows for the spent catalyst expansion
joint. UOP is currently evaluating several FCC units before packed bellows for this
service is incorporated in the project specifications.

157048-1
Equipment
Page 89

Figure 49 illustrates a typical expansion joint with an aeration connection. The


purge prevents an accumulation of catalyst between the bellows and inner wall
which would restrict the movement of the expansion joint. The purge should be 5-10
psi (0.35-0.70 kg/cm2) above standpipe pressure; the purge is normally controlled
with a restriction orifice.

Figure 51
Packing Details of Expansion Joints

The expansion joint of the spent catalyst standpipe is of hot-wall construction to


match the spent-catalyst stripper. Based on the location of vessel supports, this

157048-1
Equipment
Page 90

expansion joint absorbs both axial compression and lateral offset. These forces are
due to the regenerator expanding upward, the spent catalyst stripper downward,
and the standpipe compressing during operation. This standpipe is relatively short
and therefore not subjected to out-of-plane movement that occurs on inlet and
outlet nozzles connected to large-diameter vessels. Early units used carbon steel
standpipes and slide valves for the spent catalyst to the regenerator. Most of the
newer units use 1 Cr, Mo; although a few have stayed with insulation lined
carbon steel.
On new units, the regenerated catalyst standpipe and the lower portion of the
reactor riser are of cold-wall construction. On this type of unit, the expansion joint
needs to absorb axial extension and lateral offset, mainly as a result of the large
thermal growth from the hot-wall stripper and upper reactor riser. On older units
having a hot-wall wye section and regenerated catalyst standpipe, the primary
movement during operation is still axial extension and lateral offset. However, on
shutdown of the unit, the expansion joint may need to absorb axial compression,
which occurs when the raw oil is cut from the unit, steam is added at the bottom of
the riser, and the regenerated catalyst slide valve is closed. The steam cools the
reactor riser while the regenerator standpipe remains at operating temperature
because of hot catalyst filling the standpipe above the closed slide valve. The
regenerated catalyst standpipe can also be subjected to additional movements
because of the long length of reactor riser and standpipe. Any bowing of the riser or
the stripper or sagging of the standpipe affects the amount of axial movement and
lateral offset the expansion joint has to absorb. The regenerated catalyst standpipes
and slide valves range from 5% Cr on conventional units to stainless steel (Type
304) in older higher temperature units and cold wall design in modern high
temperature units.
Thermal movement is absorbed within the expansion joints by means of a flexible
item referred to as bellows. The bellows are formed into a corrugated shape from
thin-gauge material of a metallurgy selected to perform in the process environment
encountered; the expansion joint bellows are normally Alloy 625. The geometry and
number of corrugations used relate to the total movement capacity of a bellows.
The bellows design is based on equations outlined in the Standards of the

157048-1
Equipment
Page 91

Expansion Joint Manufacturers Association (EJMA). These equations were


developed from engineering efforts with expansion joint manufacturers, extensive
testing programs, and operating history. See Figure 52. The expansion joint must
also conform to the ASME Code for Pressure Piping, B31.3.
The expansion joint bellows absorb movement by means of axial compression or
extension, angular rotation, and lateral deflection. See Figure 53. The expansion
joints used in the FCC unit standpipe are subjected to both axial movement and
lateral deflection. For this reason, two separate sets of bellows, called a dual
element expansion joint, are incorporated in the design. The lateral deflection
occurs in the vertical plane, parallel to the expansion joint pantographic linkage, and
is absorbed by means of angular rotation of the bellows.

157048-1
Equipment
Page 92

Figure 52
Bellows Movement

D
C

h
E

L
TAN =

=
2

h
L

If Ends are Parallel: = =

A
B

Ratios:
C A F
= =
D B E

C-A
Tan ( 2 ) = ( 2 )( F )
or

( 2 )( D E- B )

157048-1
Equipment
Page 93

Figure 53
How Motion is Absorbed by Bellows

157048-1
Equipment
Page 94

SLIDE VALVES
Slide valves are used to control catalyst flow. These are gate-type valves driven by
a hydraulic actuator. The primary problems encountered with slide valves were
associated with erosion and corrosion. The elimination of guide steam purges have
alleviated many of the corrosion problems. However, if guide steam purges are
present, then the steam purge can be used once or twice a shift to keep the guides
free of catalyst. In some cases, a continuous purge is used, but its flow should be
restricted to prevent erosion of the guides. To prevent erosion, the valve disc is
covered with an abrasion-resistant refractory anchored by stainless steel hexmesh.
Hard metal surfacing is used on other parts of the valve exposed to catalyst flow
(see Figures 54 and 55). The clearances between the support guides on the sides
of the valve and the disc are set by the manufacturer. The entire system will expand
when it gets hot, so these clearances should be checked to avoid binding or
sticking. The new slide valves are designed such that no guide purge is required.
Cold wall design which uses carbon steel (see Figure 54) has also eliminated some
corrosion problems as well as many of the cracking problems generally associated
with hot wall design (specifically polythionic attack on the stainless steel). By
working closely with many slide valve suppliers, UOP has also incorporated design
and geometry guidelines which minimize erosion during normal operation. These
changes include locating the orifice plate upstream of the valve and sloping the
bottom of the bonnet a minimum of 30 from the horizontal. The sloped bottom
prevents catalyst accumulation in the bonnet. The support guides for the disc are
recessed a minimum of 3" (75mm) from the sides of the inlet port. Other design
improvements recently developed are as follows:
1. Five second stroke time for normal operation.
2. Two second stroke time for emergency shutdown.
3. Emergency shutdown features are testable on stream.
4. Offset port to center flow during normal operation.
5. Development of cold wall valves for spent catalyst standpipe service.
6. In shop hot stroke test required to guarantee trouble free operation in the field.

157048-1
Equipment
Page 95

Figure 54

Cold Wall Slide Valve


Flow

CL Port
CL Port

CL Valve

CL Valve

Port Opening

Stem
Stuffing Box
Guide Bolting
Bonnet

Drain Slots
Guide

Bonnet
Carbon
Steel
Shell

Disc

Orifice
Plate

157048-1
Equipment
Page 96

Figure 55
Hot Wall Slide Valve

HYDRAULIC OIL SYSTEM


A hydraulic oil cylinder is used to drive the slide valve because of its size and the
required fast response. A low capacity, high head pump supplies the oil through the
controlling pilot valve. A manual control valve, the joystick, is also provided in case
the pilot valve plugs. Most slide valves are equipped with a handwheel for use
during total hydraulic oil failure. When the bypass valve between the two ends of
the hydraulic oil cylinder is opened to equalize pressures, the handwheel is
engaged. It is somewhat risky to attempt control on handwheel during normal
operation, because the handwheel is usually very slow. A typical response time for
a slide valve on a conventional hydraulic oil operation would be fully open to fully
closed in 30 seconds maximum. Many older systems unfortunately are slower than
this. Startup should never be attempted with handwheel control as valve closings
will be slower than required. The handwheel should never be engaged until the
hydraulic cylinder is bypassed. The equipment may be damaged if the hydraulic
cylinder exerts force against the hand wheel.

157048-1
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A typical FCC slide valve hydraulic oil system, used in earlier designs, is shown in
Figure 56. The hydraulic oil is pumped out of the low pressure tank through a filter
to the slide valve. It circulates back from the valve or from two flow by-passes. One
of these is a hand controlled valve at the end of the hydraulic header; the other is a
minimum flow bypass on automatic control. These keep the oil circulating and
prevent pump damage that might occur if the pump were to run against a closed
system, such as when the pilot valve is holding the valve in one position. A spare
pump with auto start is used to maintain flow if the first pump fails. The high
pressure oil tank will supply sufficient hydraulic oil to close the slide valves if both
pumps go down. This tank is not large enough to hold oil pressure for more than
one to two minutes. If both pumps are lost, the unit should be brought down until at
least one is running again. Modern plants are designed with a separate oil system
for each valve, but it is more common to have one hydraulic oil system for all slide
valves. Small multi-stage centrifugal pumps are gradually replacing the
reciprocating pumps on older plants.

157048-1
Equipment
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Figure 56
FCC Slide Valve Hydraulic Oil System
N2

From Control
Instrument

IA
Must Drain
F

FV
RO

SV

HC
FH

PI
D
HPR

HV

LPR
F

FIC
F

F&W

Legend
D = Drain
F = Filter
FH = Flexible Hose
FIC = Flow Indicating Controller
F & W = Filling & Withdrawal
HC = Hydraulic Cylinder
HPR = High Pressure Receiver
HV = Hand Valve
IA = Instrument Air
LPR = Low Pressure Receiver
PV = Piolet Valve
RO = Restriction Orifice
SV = Safety Valve
UOP 2119-44

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UOP currently specifies electrohydraulic actuator assemblies with an individual


hydraulic power source for each slide valve (see Figure 57). The individual
hydraulic power source has several advantages in that the valves act independently
and eliminate all interconnecting piping.
A continuous running variable displacement pump maintains the system's hydraulic
pressure. When no valve movement is required, the pump operates near its no-load
current level and reduces heat generated in the reservoir. Hydraulic oil flows from
the pump through a set of filters into the accumulators and actuator. The actuator is
electronically controlled and directs hydraulic oil pressure to either end of the
cylinder, positioning the slide valve in response to the process demand.
An accumulator makes the fast response of the valve possible. When necessary,
this accumulator will drive the valve two complete cylinder strokes at an
approximate speed of 5 seconds per stroke. If the accumulator becomes depleted,
the pump motor itself can supply power to move the slide valve 10% of its stroke
every 10 seconds.
There is an emergency accumulator, which normally is isolated from the hydraulic
system and can be used only if directed from the control room. This accumulator
will also generate two actuator cylinder strokes.
If the pump and spare motors are lost and the emergency accumulator is not used,
there are two means of manually positioning the actuator. One mode of manual
operation uses a hand pump to move the cylinder. During normal operations, the
hand pump is isolated from the system. The other mode uses a mechanical jack or
manual handwheel to move the cylinder. When the handwheel is put into operation,
the hydraulic cylinder is automatically bypassed to prevent damage should hydraulic
power be restored.
The hydraulic pilots are very sensitive mechanisms and it is imperative that the oil
supplied to them is absolutely clean. It is important that the hydraulic oil used has
the proper viscosity and meets all the specifications given by the valve
manufacturer.

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Figure 57
Slide Valve Actuator
Component Arrangement and Hydraulic Circuitry

REACTOR RISER DISENGAGER DESIGNS


The heart of any catalytic process is the reaction site. In the case of the modern
FCC unit, this is the riser. With the introduction of riser cracking, the reaction site
has changed from the reactor vessel to the riser. Today's reactor could be more
properly called a disengaging vessel. A historical progression of riser termination
devices (from the 70's to early 90's) is illustrated in Figure 58. These include: the
traditional T-type disengager, downturned arms, vented riser, and direct-connected
cyclones or suspended catalyst separation.

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Downturned arms had essentially replaced T-type disengagers in revamp situations


where the scope did not extend to a change in reactor cyclone design. The
downturned-arm separation device began to replace the traditional T-type
disengager in 1984. Currently, UOP has nine of these designs in operation.
The downturned-arm design offers an increase in separation efficiency compared to
the traditional T-type disengager. The T-type disengager has a separation efficiency
in the range of 70%. Modeling work performed by UOP indicates that the separation
efficiency of the downturned-arm separation device is about 80%. As a result of the
improvement in separation efficiency, a reduction in catalyst loss from the reactor is
observed if the existing cyclones are heavily loaded with catalyst. The reduction in
abrupt changes of catalyst direction has reduced erosion compared to the T-type
disengager.

Figure 58
Reactor Riser Disengaging Devices

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Vented-riser systems, which use the momentum of the catalyst exiting the riser for
ballistic separation, have been successfully operating for more than 10 years and
are well proven in commercial applications. UOP has 11 vented-riser designs in
operation. On later vented riser designs, no mechanical or erosion problems have
been observed. However, limited erosion has been noticed on units revamped to a
vented-riser when the catalyst flux is high. As a preventative measure, UOP now
recommends additional " (19 mm) abrasion-resistant refractory lining to be
installed in the following areas on vented-riser reactor systems (Figure 59):

The reactor head extending approximately 3 ft beyond the tangent line. The
refractory lining is used to cover a target area on the head of the reactor
where the catalyst impacts directly. The lining is a precaution since erosion
has not been observed in this area.

DA points. Half-pipe shields coated with refractory lining are installed over
the DA points to protect them against erosion.

Manways. Refractory lining is installed in the lower half of the manways in


active areas. The most important site for installation of the refractory is on
the large manway.

TI points. Half-pipe shields coated with refractory lining are installed over the
TI points to protect them against erosion. The thermowells are to be the hard
surfaced type. The control point is moved to the reactor plenum chamber.

The reactor shell above the cone section. A stainless steel taper bar should
be used to terminate the abrasion resistant lining being added. The angle of
this taper bar should be as small as possible. The abrasion resistant lining is
usually extended a minimum distance of 3' (0.9 M) above the reactor cone.

157048-1
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Figure 59
Extent of Reactor Cladding and Hex Lining
For Vented Riser Terminations

Direct-connected cyclones are now a well-proven technology. They represented a


continuing evolution toward minimizing counterproductive post-riser residence time
and maximizing separation efficiency.

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In this design, the combined catalyst and product vapor mixture exits the riser and
passes directly into the riser cyclones for separation. The product vapors exit the
riser cyclone gas tube and pass through a second stage of cyclones before exiting
the reactor. The catalyst flows down the cyclone diplegs into the catalyst stripper.
The vapors carried down the diplegs and the vapors from the catalyst stripper are
swept from the reactor system back into the cyclone system with steam into a vent
tube entering the cross over duct between the cyclone stages.
Because all of the catalyst flows into the cyclones, erosion was concern in the
design of a direct-connected cyclone system. Reports from the operating UOP
direct-connected cyclone systems that have undergone scheduled mechanical
turnarounds indicated only negligible erosion in the riser and cyclone areas.
Because of the transfer piping now incorporated between the primary and
secondary cyclones, the hydrocarbon vapor product and hot catalyst are no longer
in contact with the reactor shell. Consequently, a large thermal differential is
introduced between the reactor internals and the adjacent reactor shell at startup, at
shutdown, and during emergency situations. The mechanical design of the reactor
must accommodate this thermal gradient. UOP's standard design practice is to use
a thermal differential, which is based on the difference between the reactor design
temperature and the steam condensation temperature.
The thermal gradient is not limited to the reactor internals. The reactor riser, reactor
vapor manifold, and reactor vapor line are also subjected to the same thermal
differential. As a result, all guides, supports, and other attachments to the reactor
shell must be designed to accommodate this condition. UOP's experience has been
that all support guides, and sometimes the actual vapor line, require some type of
modification when the direct-connected cyclone system is incorporated into the
design. In summary, the addition of direct-connected cyclones affects the entire
reactor system and is not just limited to the internals.
During the 90's, UOP developed and put into commercial operation the suspended
catalyst separation system which combines the features of the vented riser
(allowing pressure upsets) and direct connect (high containment) systems (see
Figure 60). This system is a two cyclone vented riser which operates with a similar
flow pattern to the direct connect system, but the riser above the first stage is open.

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The riser fills with a dense zone of catalyst above the inlet to the first stage cyclone
during normal operation, but during a pressure upset the catalyst is free to
discharge harmlessly into the reactor. It was also proven that the suspended
catalyst separation system had the same advantage as the direct connect system;
post riser cracking is minimized because all of the vapor goes to the first stage
cyclone.

Figure 60
Suspended Solids Separation Riser Design

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The most recent commercially proven riser termination technology developed by


UOP is the Vortex Separation Technology. This includes the Vortex Separation
system (VSS) for internal risers and the Vortex Disengager Stripper (VDS) for
external risers. (see Figures 60 and 61).
The operating principle of the VSS riser termination system is quite simple. Catalyst
is discharged centrifugally in the horizontal plane, swirls downward along the wall of
the chamber, and contacts the prestripping vapors before entering the stripper
vessel. The vapor outlet from the VSS chamber is directly connected to a single
stage of conventional cyclones.
The base of the VSS is submerged in a fluidized dense phase of catalyst in the
reactor cone. The catalyst discharging from the cyclone diplegs easily
communicates with the catalyst level within the VSS chamber to maintain a
controlled catalyst level. Tray and baffle arrangements at the bottom of the VSS
chamber and top of the stripper direct stripped hydrocarbon vapors and stripping
steam rising from the stripper up through the VSS chamber for use as prestripping
media. Any vapors entrained down the cyclone diplegs, along with fluidization
steam, and purge steam flow out of the reactor vessel on pressure balance through
vent nozzles in the VSS outlet duct.
The top of the vessel, the lower section above the stripper and the reactor riser
above the stripper are lined with abrasion resistant lining for erosion protection.
Material of construction is normally 1 Cr Mo. The vessel normally operates at
510-530C (950-990F). External insulation is required not only for personnel
protection but to prevent excess coke formation. Formation of coke in the reactor
prevents the use of air for heat up during normal startup procedures.

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Figure 60
Vortex Separation System (VSS)

Vortex
Chamber
A
Prestripping
Section
Prestripping
Steam

Dipleg

Gas
Catalyst

Catalyst
Level
Internal
Riser
Spent Catalyst
Stripper

Vortex
Chamber
Section A-A

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Figure 61
Vortex Disengager Stripper (VDS)
To Main
Column
Plenum

Cyclones

Vortex
Disengager
Riser
Counter Weighted
Flapper Valves
Support
Brackets

Gas Flow To
Cyclones

Fluffing
Steam Ring

Reactor Shell

Prestripping
Section
Catalyst Return
Slots

Spent
Catalyst
Stripper
Catalyst Flow to
Stripper

Stripping
Steam Ring
Fluffing
Steam Ring

Spent Catalyst To
Regenerator

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REACTOR RISER
The reactor riser is a vertical pipe in which the desirable cracking reactions take
place. Hot catalyst enters the wye section at the bottom of the riser and is lifted up
to the feed injection point by the lift gas/steam mixture. Two wye designs, a hot wall
and a cold wall, have been used. The two wye sections differ in wall temperature
and resulting stresses. The modern cold wall wye with 5" (125 mm) of refractory
lining has a lower wall temperature and reduced stress, permitting the metallurgy to
be changed from 304H stainless steel to carbon steel. The cold wall wye and the
hot wall wye are illustrated in Figures 62 and 63. A mixture of lift gas and steam is
injected through the lift nozzle at the bottom of the wye section. Catalyst and lift
media travel up the riser to the feed distributors where the riser diameter increases.
This increase allows for the increased volume of hydrocarbon vapors as the oil is
injected and vaporized when it meets the catalyst. Because the riser volume is
small it limits the contact time between the catalyst and hydrocarbon. This prevents
overcracking of the products. Below the point where the riser enters the reactor
stripper, the riser is carbon steel with castable refractory lining. This lining is
abrasion resistant and insulates the carbon steel from the high catalyst
temperatures. Above the point at which the riser enters the reactor stripper, the riser
becomes hot wall so the metallurgy is upgraded to typically 1 Cr Mo.

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Figure 62
Cold Wall Wye

5 High Density Refractory

Carbon Steel

Reinforcing Rings

Bumper

Lift Gas Distributor

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Figure 63
Hot Wall Wye

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REACTOR RISER FEED DISTRIBUTION


The earliest feed distributors were simple open pipe bayonets located in the base of
the wye section. Figure 64 shows an example of this type. Efforts were then made
to generate some feed dispersion by using multiple nozzles at the exit point of the
distributor. This led to the design of the "showerhead" distributor shown in Figure
65. This change generated a substantial improvement in overall process
performance. Figure 66 shows the effect on cross-sectional temperature profiles in
the riser when changing from a single nozzle bayonet to the multi-nozzle
showerhead design.
In the late 1970's and throughout the 1980's, much emphasis was placed on
atomizing the oil into very fine droplets and evenly dispersing these droplets into the
flowing catalyst. UOP's efforts led to the development of the WYE premix distributor
shown in Figure 67. Steam is injected into the feed upstream of the distributor. The
combined stream is then "pre-mixed" inside the distributor to obtain a pseudo
emulsion phase before it exits the nozzles at the distributor tip. The expanding
steam at exit conditions helps to break up the oil into fine droplets to achieve rapid
vaporization and even mixing with the catalyst.
Further refinements to the wye feed distributor were made by utilizing an annular lift
around the base of the distributor. Either steam or gas can be used as the lift
media. The intent is to provide some pre-acceleration of catalyst around the
distributor before the catalyst is contacted with feed. This serves to reduce the
degree of backmixing in the wye and lower riser. Figure 68 shows a wye premix
distributor with annular lift.

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Figure 64
Reactor Riser Feed Distributor
Bayonet Type

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Figure 65
Reactor Riser Feed Distributor
Jet Nozzle Type

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Figure 66
Effect of Feed Distributor

UOP 3110-9

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Figure 67
Premix Feed Distributor (Wye)

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Figure 68
Premix Feed Distributor with Annular Lift (Wye)

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ELEVATED FEED SYSTEM


During the 1990's, the industry widely accepted that elevated radial injection system
on the riser is the preferred feed injection location. A typical elevated feed injection
system is shown in Figure 69. The wye section, acceleration zone, and mix zone
are the main elements. The term system must be emphasized because the best
result will not be realized without all the parts functioning in the proper manner. The
UOP system has evolved over many years from a combination of strong process
understanding, commercial testing, cold flow modeling, and mathematical modeling.
Acceleration Zone
The base of the wye section is quite turbulent because the huge mass of catalyst
changes direction here. Significant backmixing occurs as the catalyst begins to
move up the riser. Clearly, injecting the feed at this location cannot be desirable.
Restoring an even flow of catalyst is important before injecting the feed. Restoring
an even flow is the function of the acceleration zone.
A carrying gas, either steam, dry gas, or a combination of both, is injected at the
base of the wye. Proper acceleration of the catalyst results in a more even catalyst
flow distribution and a lower slip factor. The slip factor is the ratio of the gas-phase
velocity to the catalyst-particle velocity. The catalyst is always moving at a lower
velocity and slips relative to the gas phase. At higher gas-phase velocity, the slip
factor decreases. A riser flow with a high slip factor is a less uniform and more
unstable system. The goal is to minimize backmixing when the feed is injected.
Uneven catalyst flow and high slip in the riser can lead to localized areas of high
temperature and feed overcracking, which result in greater amounts of coke and dry
gas and reduce selectivity to desired products. In addition, lift gas has proven to
passivate metals which further reduces the dry gas yields.

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Figure 69
Elevated Feed Injection System

Mix Zone

Feed &
Steam
Acceleration
Zone

Catalyst

Steam or Gas
UOP 2569B-1

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Catalyst Velocity and Density


Computational fluid-solid dynamic modeling work has indicated that the catalyst flow
in the riser can be subject to undesirable slugging phenomena at low velocities.
Increasing the catalyst velocity helps to reduce such slugging and improves the
initial contact with feed. All evidence, both commercial testing and theoretical
principles, confirms that an accelerated, moderate-density catalyst phase is the
ideal environment for feed injection in a flowing riser.
Mix Zone
The last part of the feed distribution system is the mix zone, the point of contact
between the flowing catalyst and injected feed. At this location, the feed is
vaporized rapidly, and cracking reactions begin. This zone is a complex three-phase
system: flowing solids, liquid feed spray, and vaporized gas phase. Rapid and
intimate mixing at this point is critical to achieving the best yield performance. The
number of feed nozzles, location and angle of injection, spray pattern and riser
coverage, and droplet size and velocity are all important parameters that are
optimized to generate the best performance.
A final objective of the mix zone is to achieve a plug-flow environment as quickly as
possible once the catalyst and feed have been mixed. An even distribution of
catalyst and hydrocarbon vapor helps promote and complete the desired reactions
as the mixture flows up the riser. Backmixing of catalyst at the point of contact must
be minimized. Riser gamma scans at this location have helped identify and optimize
the desired flow patterns.
The first generation of elevated feed system used the elevated premix feed
distributor shown in Figure 70.

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Figure 70
Elevated Riser Premix Feed Distributor

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Optimix Feed Nozzle


After the elevated premix feed distributors were proven successful, UOP instituted a
program to further improve the atomization and dispersion characteristics of its feed
nozzles. The result of these efforts is the new Optimix feed nozzle (see Figure 71).
The important features of the Optimix nozzle are:

Small average droplet size


Narrow droplet size distribution
Flat fan spray pattern
Even liquid flux across spray
Moderate pressure drop
Three stages of atomization
Short residence time after internal droplet generation
High turndown efficiency

The Optmix nozzles have been commercially proven in more than twenty units and
major performance benefits with the Optimix nozzle system have been achieved in
dry gas reduction and gasoline yield improvement.
The feature most recently added to the Optimix distributor is the DUR O LOK
coupling. This coupling provides a means for replacing the tips for maximum
flexibility in both maintenance and modification for changes in design charge rate.

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Figure 71
UOP Optimix Feed Nozzle
Steam
DUR O LOCTM
Coupling

Oil

REACTOR PLENUM
The direct-connected cyclone reactor systems prompted the development of new
reactor plenum designs. In a direct-connected system, the area surrounding the
cyclones is relatively inactive. The traffic in this area is limited primarily to the
vapors being carried out of the reactor stripper. During startups and shutdowns, the
temperatures observed at the reactor shell and cyclones can therefore be
substantially different. To accommodate the large differences in thermal expansion,
new plenum designs were required. Different approaches to this problem are shown
in Figure 72. UOP typically uses an internal plenum design to minimize overall
vessel height and cost.

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Figure 72
UOP Plenum Chamber Designs

External Plenum

Internal Plenum

External Manifold

SPENT CATALYST STRIPPER


The spent catalyst stripper (Figure 73) surrounds the upper portion of the reactor
riser. Catalyst descending from the reactor passes into the stripper where it flows
over stripper baffles. The steam to the stripping section is distributed through a
number of small holes in two opposing semi-circular steam rings. A rate of 1.5-2
lb/1000 lb catalyst is typical. The stripping steam displaces oil vapors from the voids
between the catalyst particles and in the catalyst pores and returns this vapor to the
reactor. The catalyst flows out the spent catalyst standpipe with some entrained
steam. A small quantity of steam is injected into the base of the stripper cone
through an additional semi-circular steam ring which maintains catalyst fluidization
and assures an even temperature distribution at this section.
Improved stripping of hydrocarbon from the spent catalyst provides significant
advantages: catalytic coke from higher conversion replaces entrained hydrocarbon
due to the increased catalyst-to-oil ratio resulting from lower regenerator dense bed

157048-1
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temperatures. Alternatively, a lower coke yield for the same conversion can be used
to increase throughput on main air blower limited units.
In 1998 and 1999 UOP conducted an extensive research program to evaluate the
existing commercial stripper tray designs and develop a more efficient design. A
commercial scale Plexiglas model was built to allow visual observations of the
catalyst and gas flow patterns. Catalyst circulation rates greater than commercial
flux rates were possible in this model. Helium tracer gas injected to the catalyst
entering the top of the model was used to quantify the stripping efficiency for each
tray type.
The three stripper tray designs which were used commercially in the past by UOP
and tested in the model are shown in Figure 74.
The classic UOP tray, which had 2 rows or large holes on the top of the tray was
used up to the mid 1980s. The stripper tray style with three rows of holes in the
skirt was used from the mid 1908s to early 1990s. In the early 1990s the jets were
returned to the top of the trays with longer skirts which allowed more pressure drop
across the tray for better steam distribution. Each of these designs perform well at
low to moderate catalyst flux rates, up to ~60,000 lb/hr/ft2 (290 kg/hr/m2). Above
these rates the efficiency falls quickly and fluidization problems can occur which
limit the capacity of the stripper.
The modern tray design developed from the cold flow modeling is shown in Figure
75. This tray uses a larger number of smaller jets on the top of the tray spread out
over a larger percentage of the tray than in previous designs. This provides for
better steam/catalyst contacting resulting in improved stripping efficiency. Another
advantage resulting from this is that all areas of the bed are uniformly fluidized
resulting in smoother catalyst flows and uniform catalyst flux. This improved
fluidization has allowed the upper limits on catalyst flux to be pushed above 100,000
lb/hr/ft2 ( 490,000 kg/hr/m2) while maintaining very high stripping efficiency. The
catalyst flux is based on the annular area between the riser and stripper shell.

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The modern stripper is also designed for higher catalyst residence times than the
early models. This residence time is important to allow completion of bed cracking
reactions of the absorbed hydrocarbons which continue to generate strippable
vapors that can be removed before the catalyst enters the regenerator. The uniform
catalyst flux in the modern stripper also increases the effective catalyst residence
time by eliminating areas of stagnant catalyst and areas of high catalyst flux.

Figure 73
High Efficiency Spent Catalyst Stripper

Insulation

Riser
Stripper Shell

Stripping
Steam

Stripping
Steam

Abrasion Resistant
Lining
Fluffing Steam

FCC-E005

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Figure 74
Historical Stripper Tray Designs

Classic UOP Tray


Up to Mid 1980's
Short skirt
Holes on top near the edge

Mid 1980's to Early 1990's


Longer skirt
Holes on vertical skirt

Modified Classic UOP Tray


Early 1990's to 1999
Long Skirt
Jets on top near the edge
FCC-E006

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Figure 75
Modern Stripper Tray Design
C
L Spent Catalyst
Stripper
Abrasion
Resistant Lining

Detail

12-14 Gage
Tubing

Riser

Stripper
Shell
FCC-E007

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REFRACTORY LlNING
Refractory lining is used extensively in the reactor and regenerator. The types of
refractories generally fall into three categories: abrasion resistant, insulating, and
castable. Castable refractory lining exhibits both abrasion resistant and insulating
properties. In recent years, abrasion resistant plastic linings have entered the
market. Plastics have become popular for small repair jobs because of their ease of
application. The material is putty-like and comes ready for installation without
addition of water. A listing of the various applications is given in Table 2.
TABLE 2

REFRACTORY LlNING

Application
Reactor
Reactor Stripper
Upper Regenerator
Lower Regenerator
Standpipes
Upper Reactor Riser
Lower Reactor Riser
Cold Wall Wye
Hot Wall Wye
Feed Distributor
Expansion Joint
Slide Valve
Cyclones
External Mixer
Flue Gas Line
Catalyst Cooler

Abrasion
Resistant
X
X
X
X
X
X
X
X
X
X
X
X
X

Castable

Insulating

X
X
X
X
X

X
X
X
X

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UOP has made several modifications to the refractory specifications to ensure the
proper use of materials, installation procedures, and inspection and testing
methods. Some of the major revisions to the UOP Standard Specifications include
the following:

The anchor spacing has been reduced from 12 (300) for high density
vibrocast refractory and gunned refractory:
Anchor Location
Top head of Vertical Vessels
Plenum Areas
Overhead Areas
Horizontal Shells
Catalyst Transfer Lines
Overhead Vapor Lines
Vertical Shells
Bottom Head of Vertical Vessels
Downhand Areas

Anchor Spacing
1.0 x Lining Thickness

1.5 x Lining Thickness

2.0 x Lining Thickness

The straight-leg anchor design has been replaced with a "steerhorn"-style


anchor. The steerhorn-style anchor provides more positive anchorage and
minimizes slippage.

The coating on the anchor has been reduced to the tip of the leg. Coating on
just the top " (13mm) of the anchor leg allows a greater bond and allows
thermal expansion of the tips without spalling the lining on the surface.

Metal reinforcing fibers are incorporated in the refractory. The use of


stainless-steel metal fibers are required to improve the strength of the
refractory lining for cold crushing, modulus of rupture, and thermal shock and
to minimize cracking. The quantity of fibers is minimized (2 lb/ft3 or 32 kg/M3)
to ensure uniform mixing and to reduce handling problems.

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The heat drying procedure has been modified. The modified procedure is
required to ensure refractory quality by incorporating a controlled, slow heatdrying rate.

The installation temperatures are controlled to ensure that the lining is not
freezing or being subjected to incomplete hydration.

Mandatory testing of materials is now required to ensure the quality of the


materials and skill of the installers. Materials and installers must pass all
testing requirements prior to installation.

Figure 76
Steerhorn Anchors for Gunned and Vibrocast Refractory Lining

Cap

1-1/2 (38 mm)

1(25 mm)

60

5/16 (8mm)
Diameter Anchor

3/8
(9 mm)
Radius

Shell

Weld

1/2
(13mm)
Radius

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THERMOWELLS
Reactor thermowells are protected with a hard metal surfacing. The number will
depend upon the size of the unit. The most important temperatures are the riser
outlets for a modern unit, or the dense bed for an older unit. These can be checked
with the reactor over head and stripper bottom outlet thermowells. The catalyst in
the stripper usually is 5-10F (3-6C) hotter than the cyclone outlets, because heat
transfer from the catalyst to the oil is not perfect. Thermowells may inadvertently be
placed in a dead area, where false, usually low, readings are obtained. False
readings can be detected by comparing the different readings obtained around the
reactor.
The thermowells used in the regenerator are protected by a stellite hard surface
coating. Wear will vary, depending on location. During the inspection, each
thermowell should be carefully checked and replaced if necessary.

DRY STEAM, DRY AIR and DRY GAS SURGE POINTS


The instrument connections on the reactor and regenerator must be protected from
catalyst damage. The fluidized catalyst will behave like a liquid and "flow" into any
instrument opening. Once the catalyst is out of the fluidized area, it tends to settle
and pack. The instrument tap is blocked off and a false reading given. To avoid this
problem, a stream of dry air, gas or steam is injected into the line between the
vessel and the instrument to provide a buffer seal. This system is shown in Figure
76. It is important to point out that if air is used as the purge gas, its flow should be
minimal to prevent localized burning or harmful oxidation reactions. The amount of
steam injected is controlled by restriction orifices, 1/8" (3mm) for steam and 1/16"
(1.6mm) for air or gas. The pressure to the orifice should be 5 psi (0.35kg/cm2)
higher than the vessel pressure. For differential instruments, there is no error in
measurement because the isolating medium injected is the same for each tap. For
single instruments, any error introduced is negligible.

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Figure 76
DA, DG and DS Piping
1/2" Pipe to Instrument

Provide 6' (1800) or More


Clearance to Enable Use of
Reamer

3/4" SCH 160 Piping


Minimum Run Straight
Piping Between Fittings

1/16" Restriction
Orifice
Strainer
P

Nozzle on Vessle
Or Standpipe
3/4 '' Instrument Air for "DA" Points
3/4 '' Purge Gas for "DG" Points
3/4 '' Purge Steam for "DS" Points

FCC-E008

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During inspection, the pressure taps (and pressure taps used for level indication)
should be cleaned and the surrounding refractory should be checked. The reamer,
shown in Figure 77, can be used to clean out the taps when the unit is on stream,
or when it is down.

Figure 77
Pressure Tap Reamer
6'' (150) DIAMETER HANDWHEEL

1/4 '' (6) STEEL ROD


STEEL GLAND
STEEL STUFFING BOX

FLEXIBLE GRAPHITE
PACKING

3/4 '' FORGED STEEL


SCREWED TEE

3/4 '' SCHEDULE 80


SEAMLESS STEEL PIPE
NIPPLE 9'' (230) LONG

5'-0'' (1525)

ROUND HEAD
STEEL PLUG

3/4 '' NPT (NATIONAL


STANDARD PIPE
TAPER THREAD)
(NOTE 2)

1/4 '' (6) DRILL


(WELD TO ROD)

FCC-E009

157048-1
Equipment
Page 135

MAIN COLUMN
The FCC main column is shown in Figure 78. The column may be divided into two
sections: the regular fractionator and the lower disc and doughnut trays. The bottom
six trays are designed for high vapor and liquid flow rates. The trays are shown
schematically in Figure 79. A coke trap, shown in Figure 80, prevents large pieces
of coke or other debris from entering the bottom line.
The steam ring may be used on some units to steam strip the bottoms material of
any lighter hydrocarbons. The column is fitted with three sample lines which are
normally called try lines; the bottom try line is also used as a sample line. These are
used to check the bottoms level because the level glass and indicator are subject to
occasional plugging by fines or coke particles. Both level instruments are protected
with an LCO flush which flows into the level instrument from the top.
The FCC main column is mounted on a table top instead of the skirt mounting seen
on most columns. Table top mounting simplifies maintenance work on the bottoms
lines, which are subject to plugging from coke or catalyst fines. A separate suction
line to each pump allows operation to continue through one line while the other is
cleaned. As an additional note, every valve in the bottoms circuit should be installed
with the stem up to keep catalyst fines out of the bonnet. If plant layout does not
allow a stem to be straight up, it should be as close to the vertical position as
possible.
The upper part of the tower is similar to any other fractionator. Sidecut streams
must be stripped to remove absorbed light material. Stacked heavy cat naphtha and
light cycle oil strippers are shown in Figure 81. Steam is the most common
stripping method, although reboiler strippers are sometimes used. Reboiler
strippers decrease the amount of sour water that must be treated. The overhead
vent from each stripper returns to the main column in a vapor space.

157048-1
Equipment
Page 136

The overhead from the column is condensed by air or water coolers, normally a
combination of the two. Water from the gas concentration section washes the
ammonia and some other salts from the last bank of condensers. If it were injected
before this, much of the water could vaporize, decreasing its effect. The sour water
is separated in the overhead receiver (see Figure 82) and sent to a sour water
stripper. Gasoline and gas go to the gas concentration section, with some gasoline
returned to the tower for reflux.
The main column is made of regular or killed carbon steel, with a 1/8 inch (3 mm)
thick Type 405 or 410 (12 Cr) cladding from below the naphtha or LCO draw tray to
the bottom outlet. Any nozzles or manways in this clad section should also be alloy
lined. All the trays and caps in the column are Type 410 stainless. The inspector
should look for any evidence of pitting, cracks or bulging in the alloy lining. Metal
thickness should be checked and recorded for future reference. A general
inspection should be made for loose caps, clips and bolts, and for general metal
loss or tray distortion. The upper part of the column is usually not subject to severe
corrosion. The bottom of the column should be checked for integrity of the lining
and for any signs of coke buildup. Excess amounts of coke may indicate that the
bottoms temperature was too high during operation. The coke trap and steam ring
should be cleaned and checked for corrosion. The steam ring should have the
nozzles pointing upward, to avoid erosion to the bottom head lining.

157048-1
Equipment
Page 137

Figure 78
Main Column
Manway and
Vent
Reflux

Vapor Out

HCN Liquid
Return

4
5

HCN Stripper
Vapor Return

HCN Reflux
Draw
HCN Reflux
Return

HCN Pumparound
and Product Draw
7
18

LCO Pumparound
Return

19
20

LCO Stripper
Vapor Return
LCO Reflux
Draw
LCO Reflux
Return

21

LCO Pumparound
and Product Draw
410S or 405
cladding

17

26

HCO Pumparound
Return

27
28
29

Feed Surge Drum


Equalizing Line
HCO Pumparound
and Reflux Draw
HCO Reflux Return

30
31
32
33
34

MCB Pumparound
Return

35
36
37

38

Reactor Vapor Inlet

Try Lines
Quench

Steam Out
Coke Trap

Bottoms Pumaparound
and Product Draw

FCC-E400

157048-1
Equipment
Page 138

Figure 79
Typical Disc and Donut Pans
C VESSEL
1-3/8" DIAMETER HOLES
ON 5" EQUILATERAL
1-3/8" DIAMETER HOLES
ON 2-1/2" EQUILATERAL

TRIANGULAR PITCH

TRIANGULAR PITCH

OMIT HOLES FOR


TOP DONUT ONLY

SUPPORT
RING

C VESSEL

A
OPEN AREA
4" HIGH WEIR FOR
TOP DONUT ONLY

PLAN OF DONUT
C VESSEL
DOWNCOMER
OF TRAY

TRAY

SUPPORT
RING

DONUT TRAY
DISC TRAY

SECTION A-A
C VESSEL
1-3/8" DIAMETER HOLES
ON 2-1/2" EQUILATERAL
OPEN AREA

TRIANGULAR PITCH

C VESSEL
SYMMETRICAL
ABOUT CENTERLINE

1-3/8" DIAMETER HOLES


ON 5" EQUILATERAL
TRIANGULAR PITCH

PLAN OF DISC
NO HOLES AT FEED POINTS

FCC-E401

157048-1
Equipment
Page 139

Figure 80
Typical Coke Trap
120

40

150

SUPPORTS

OPENINGS

25 R
150

50 (TYPICAL)

OD OUTLET NOZZLE

100

PROVIDE 2 DRAIN
OPENINGS, LOCATED
180 DEG APART.

(BOTTOMS OUT)

FCC-E402

157048-1
Equipment
Page 140

Figure 81
Heavy Cat Naphtha Stripper (Top)
Light Cycle Oil Stripper (Bottom)
Manway and Vent

Vapor to Main Column


BAFFLE
HCN from Main Column
1

Stripping Steam

LC-LG

Vortex Breaker
Vent
Vapor to Main Column
Stripped HCN Product

1
LCO from Main Column

Stripping Steam

LC-LG

Vortex Breaker

Stripped LCO Product

FCC-E403

157048-1
Equipment
Page 141

Figure 82
Main Column Overhead Receiver
Vent and Ventilation
Vapor Outlet
Manway
PC

Steam Out
Inlet Distributor
(Detail)

LC & LG

LC & LG
Water
Water Boot
Water Outlet

Slots Must Face


Nearest Head
1/2" Drain Hole

Hydrocarbon
Outlet
Vortex Breakers

FCC-E404

157048-1
Equipment
Page 142

MAIN COLUMN BOTTOMS


The main column bottoms pumps are detailed in Figure 83. The minimum
distances shown are important to prevent catalyst fines from settling in a line that is
not in service and plugging it. The draw stream for heavy oil out of the unit (i.e. to
the slurry settler or storage) always comes off the bottom of the main column
bottoms header. Any catalyst or coke which has a tendency to settle will be drawn
off and removed from the circulating loop. Steam and LCO lines are provided for
flushing on shutdown and for cleaning. If the unit is shut down without flushing,
catalyst fines may settle, or the heavy oil may set up causing problems with
cleaning.
The suction and discharge lines of the main column bottoms pumps range from 5
Cr, Mo to 9 Cr, 1 Moly. The exchanger metallurgy ranges from carbon steel to 5
Cr, Mo. Carbon steel does not last long if it is exposed to hot main column
bottoms so the slurry service side of the tubes, tube sheets, and heads should be
clad with a chrome alloy, such as Type 410. After the first exchanger, most of the
piping is carbon steel. All piping and exchangers should be inspected for corrosion
and fouling at each turnaround, and the appropriate records kept.
The recommended main column bottoms velocities through the tubes are 3.75 to
7.0 ft/sec for straight tubes and 3.75 to 5.75 ft/sec for U-tubes. Deviations outside of
these ranges will show up as excessive amounts of settled catalyst fines or erosion
to the tubes.
The main column bottoms pumps normally have steam turbine drivers. Speed is
limited to 2000 rpm to minimize erosion. The shaft is tungsten carbide or stellite
coated, with a light cycle oil flush to the throat bushing and wear rings and HCO to
the mechanical seal. UOP recommends aluminum foil packing with light cycle oil
flush for cooling and lubrication. Graphite or asbestos have occasionally been used
in this service. Many refiners have installed mechanical seals with good success.

STEAM

LP

RETURN HEADER

MAIN COLUMN BOTTOMS

TO CIRCULATING

STEAM
CONDENSATE

3/4 ''

MP
STEAM

TI

PUMP WARMUP/COOLDOWN

HEAVY CYCLE OIL FOR

PUMP WARMUP/COOLDOWN

FLUSHING OIL FOR

PDI

PG

MIN

TO CIRCULATING
MCB HEADER

MIN

COKE
STRAINER

OIL

FLUSHING

STEAM

OIL

FLUSHING

MIN

BLANKOFF

STEAM

MP

COKE
STRAINER

MIN

MIN

PG

PDI

TI

PUMP WARMUP/COOLDOWN

HEAVY CYCLE OIL FOR

PUMP WARMUP/COOLDOWN

FLUSHING OIL FOR

3/4 ''
Try Lines

MP STEAM

Figure 83
Main Column Bottoms Circulating Pumps

MOV

MIN

FCC-E405

OIL

FLUSHING

MOV

157048-1
Equipment
Page 143

MIN

157048-1
Equipment
Page 144

Besides the turnaround, the bottoms pumps usually require some repair work
during the course of the run. The seal flush system should be checked for
cleanliness, and the packing replaced if necessary. The packing is especially
vulnerable to the hot, erosive conditions. There may also be wear to the pump case
and rotor. If this is severe, a hard surfacing material may be applied to the rotor.
The inspector should also check the pump suction strainer for corrosion and holes.

SEAL AND GLAND FLUSH


The main column bottoms pump is protected by gland and seal flushes to keep
catalyst fines out of the throat and to lubricate and cool the packing. HCO is used
as the flushing medium. LCO is not used as a flush to the main column bottoms
pumps because suction will be lost when vapors are formed in the pump casing.
For earlier units, all main column bottoms and slurry flow instruments and control
valves are flushed with LCO to keep out fines that could plug up or erode the
equipment. The total amount of LCO required will depend on the number of flushing
points. The flush to each instrument will not be exactly the same because of the
pressure drops through the system, although this can be partially balanced by the
globe valve provided at such point. The primary control is a 1/16 inch (1.6 mm)
restriction orifice after the globe valve. These orifices must be kept clean. A rough
number for total LCO required is 1000-2000 BPD (6.5-13 M3/hr). Smaller units
usually have fewer exchangers and, therefore, require fewer control valves and less
oil. The LCO which enters the main column bottoms stream will flash off when it is
returned to the column. Excessive flush will cause cooling problems in the bottoms,
and should be avoided.
Currently, UOP designs slurry flow instruments which do not use flushing as shown
in Figure 84.

157048-1
Equipment
Page 145

Figure 84
Slurry Service Orifice Meter Piping Assembly
Closed Coupled Above Orifice for ANSI Class 300/600
Screwed Cap
(do not seal
weld)

" Globe

"
minimum

2" Field Fabricated


Instrument Pipe
Support

Pipe

Transmitter

Mounting
Bracket

P
Capsule

Single
Valve
Equalizing
Manifold

minimum

Flange Adapters

" Gate
(Install on Vertical Tap)

" Pipe

Flow

Pipe Strap
" Solid Plug

FCC-E406

157048-1
Equipment
Page 146

SLURRY SETTLER
In earlier units when the cyclone efficiency was not as high, the main column
bottoms stream contained catalyst fines which had to be removed to meet certain
product specifications. Part of the bottoms stream was sent to the carbon steel
settler (sometimes called a clarifier) where the fines would settle out and were
returned to the reactor with a slurry recycle. Clarified oil came off the top of the
vessel. The settler operated liquid full, with a cross-sectional area designed for an
upward oil velocity of 30 BPD/ft2 (2.1 M3/hr/M2) or less at normal charge rates.
Heavy cycle oil or raw oil diluent could be used to flush the fines back to the reactor.

Figure 85
FCC Slurry Settler
Vent

Clarified Oil Outlet


Relief Valve

Manway
Main Column
Bottoms Inlet
Nozzle and
Wear Plate

Dilute Oil
Inlet and
Distributor

Flushing
Nozzle

Steamout
Slurry Outlet
UOP 2119-67

157048-1
Equipment
Page 147

SLURRY FILTRATION
Filtration of the slurry product to achieve product specifications of 100 wppm total
solids or lower is becoming increasingly common. Sales of the slurry product as
carbon black feedstock and desire to minimize the increasing cost of tank cleaning
are driving this trend.
The most common type of filters use pourous, sintered metal filter elements. A
typical filter system will have 2 or 3 vessels with a number of filter elements in each.
One vessel is typically in filtration mode while another is in backflush mode to
remove the filter cake from the elements. When enough catalyst fines have
deposited on the filter elements to increase the pressure drop across the filter to a
pre set limit the vessel is taken off line for back flushing. Once the filter vessel is off
line and drained the vessel is filled with backflush liquid, either HCO or LCO, and
allowed to soak to help dissolve any heavy aromatic compounds on the elements.
The top of the vessel is then pressured up with either fuel gas or nitrogen to provide
the driving force for a high velocity back flush. The back flush material is collected in
receiver vessel and pumped back to the reactor riser or to the spent catalyst
stripper. A typical arrangement for the filtration equipment is shown in Figure 86.

157048-1
Equipment
Page 148

Figure 86
FCC Slurry Filter
BACKFLUSH
GAS
BACKFLUSH GAS
ACCUMULATOR

CLEAN
PRODUCT
OUT

FILTER
VESSEL
#1

FILTER
VESSEL
#2

FILTER
VESSEL
#3

VENT

SLURRY
IN

BACKFLUSH
RECEIVER

HCO or
LCO
SOAK IN
BACKFLUSH
TO
REACTOR

FCC-E407

157048-1
Equipment
Page 149

GAS CONCENTRATION SECTION


The gas concentration unit is relatively easy to operate and usually trouble free. It
may be forgotten in the planning for the turnaround. This can prove to be a serious
mistake because the vessels and lines are sometimes subject to severe corrosion.
The amount and type of corrosion will depend on the feedstock, vessel metallurgy,
and the methods used to combat this corrosion
Corrosion in this unit can be broken down into three classifications:
1.

Hydrogen blistering and/or embrittlement.

2.

Corrosion of steel by hydrogen sulfide, cyanides, and other acids.

3.

Ammonia attack on Admiralty tubes.

The first of these, hydrogen blistering, is the most common problem with general
metal attack by the various acids a close second. Hydrogen blistering occurs in
steel where surface corrosion is active. Blisters are formed by the diffusion of
atomic hydrogen into steel and then accumulate at slag or inclusions within dirty
steel. The atomic hydrogen then converts into molecular hydrogen, and the
resultant pressure forms the blister. Blisters may rupture to the thin side of the
defect. The presence of cyanides (Prussian blue) greatly increases susceptibility of
H2 blistering in steel. The inspector should look for a bluish color when the plant is
first opened, because this is a good indication of areas where corrosion and/or H2
blistering may be found. Hydrogen sulfide (H2S) also contributes to blistering and
corrosion; it is present in most gas concentration units. The inspector should look
for H2S pitting, blisters, and general metal loss. Inspection of the equipment should
be thorough, and when corrosion is found, the type and extent of the corroded
areas should be determined. It is not unusual to find one head or one particular
plate in a vessel full of blisters, with the remaining portion of the vessel in good
condition. Repairs can be made by replacing the damaged areas and still maintain
the equipment in service.

157048-1
Equipment
Page 150

Ammonia attack on Admiralty tubes in the condensers or coolers is not severe if


there is sufficient wash water during operation. Stress corrosion of brass tubes may
be seen in exchangers where the pH is high. Galvanic corrosion and dezincification
of brass tubes may be found where dissimilar metals are used in the condensers or
coolers. Water side erosion or corrosion of the tubes may occur if dirty or
contaminated water is used. This could be caused by suspended solids, or if there
were salts or other chemical species, for which the exchanger was not designed.
The type and amount of problems will vary between refineries. It may even change
over a period of time for one unit, as feed or cooling water quality changes. Every
turnaround a good inspection should be made with precise records on each piece of
equipment. Previous records should be available, and corrosion rates determined
each time. Changes of materials in bundles or shells, should be considered if
exchanger life is too short.
Gas plants are usually easy to gas free and open for inspection. Some units that
have been coated with an epoxy type paint cannot be subjected to steam for gas
purging. These items must use water or inert gas to clean for entry, which makes
the job more difficult. Knowledge of protective coatings and locations is a must for
the refinery safety and inspection departments. Operations supervisors should have
written orders for each piece of equipment which detail the correct procedures to
follow in flushing and opening these items.
Admiralty tube bundles should be handled in special slings to eliminate overstressing and potential stress cracking of the tubes at the lifting areas. Good
supervision of opening and removing of equipment is critical in this unit.
The inspector should follow the flow from the low and high pressure receivers to the
final condensers. Corrosion found in any item should be followed to the next item in
the flow pattern to determine the extent and area the corrosion has covered.
Because there is a certain amount of crossover flow, such as wash water from the
HPS to the MC overhead, there may be some backtracking. The corrosion
products, such as iron sulfide scale, will not necessarily be in the same area as the
most severe corrosion. Should hydrogen blistering be found, the blisters should be
measured, drilled if necessary with air drills, and the ruptured metal should be
measured to determine if the corrosion allowance has been exceeded. If blisters are
small, " (13mm) or less, they can be covered with a protective lining to eliminate

157048-1
Equipment
Page 151

future growth. Corrosion allowance in the blistered areas should be maintained if


possible. General corrosion, such as H2S pitting, may require replacement of all or
part of a vessel or line. Scabbing is usually not effective, but can be used if time is
short and if the scabbing is done well.
If repairs are not made, the item should be programmed for the next turnaround as
necessary work. Various metal corrosion test samples can be installed in the
corroded area to determine the best material to be used to resist the corrosion.
Hydrogen probes, electrical resistance corrosion probes, and corrosion coupons
can be used to indicate the rate and severity of corrosion activity during the run. Onstream inspection of piping can also be used to monitor present problems and to
find areas that should be checked carefully or shutdown.
If corrosion or blistering is found, there is usually a question concerning
replacement with a higher quality material. All equipment eventually wears out; it is
a matter of comparing cost with possible benefits. Replacement of trays and other
tower internals is easier than replacing the vessel shell. If the refiner feels that the
equipment is wearing out too quickly, then a higher alloy may be justified. Before
the decision is made, a careful investigation should be conducted to determine
other ways of resisting corrosion. For the FCC gas concentration section, the best
method to resist corrosion is to maintain the wash water injection at a rate of 6.5-7.0
vol.% of the feed. This has greatly limited or eliminated corrosion in most cases.
Inhibitors have been used in some cases, but they are usually not necessary.
Most of the material used in the gas concentration section is carbon steel. Killed
steel is common for towers and the upper trays in the absorbers. The debutanizer
reboiler is very often 5% chrome, % moly steel. A lower alloy steel, such as
1% chrome, % moly, may be used in areas that have had corrosion problems.
In severe cases, the affected area may be lined with a 12% chrome, such as Type
405 or 410. The compressor rotor is usually a specially tempered 1% chrome,
% moly steel.

157048-1
Equipment
Page 152

WET GAS COMPRESSOR


The compressor of an FCC unit separates the relatively low pressure of the main
column from the higher pressure gas concentration and recovery section. Positive
displacement reciprocating or centrifugal machines can be used; the latter have
become more common because of better performance at lower cost.
During the turnaround, thickness measurements of piping headers and manifolds
should be made each down period and compared to previous readings. Severe
corrosion may be found in the discharge manifolds and piping to the receivers. The
manufacturer's instructions should be followed for the gas compressor inspection.
This machine normally requires maintenance work on the seals or packing.

CENTRIFUGAL MACHINES
Centrifugal compressors (Figure 87) are multi-stage machines, contained within the
two external stages. Each of the two stages is protected by an anti-surge device
which will over-ride normal controls to protect the machine. Gas leakage out of the
casing is prevented by suction and discharge end labyrinth seals. These seals are
backed by either buffer gas or seal oil, normally oil. The seal oil system runs 5 psi
above suction gas pressure, using a seal oil head tank or differential pressure
controller to hold this differential pressure even if suction pressure varies
somewhat. A balancing drum is used to offset axial thrust, so suction pressure is
maintained at both ends of the compressor. The seal oil system must be kept in
operation while the casing is under pressure or gas will leak out.

157048-1
Equipment
Page 153

Figure 87
Centrifugal Compressor

FCC/DS-R00-45

157048-1
Equipment
Page 154

RECIPROCATING MACHINES
Reciprocating compressors can be driven by gas engines, turbines, or electric
motors. They are usually constant speed machines. Suction valve unloaders and
clearance pockets are provided on some machines for greater operating flexibility.
A reciprocating machine should never be run with discharge valves blocked in.
Liquid slugging is also very dangerous, as the liquid is incompressible and will lead
to broken piston rods or a cracked head. Suction knockout drums should be
checked frequently for any liquid.
The reciprocating machine uses packing to prevent gas leakage from the
compressor. This simple system should work quite well as long as the packing is
tightened correctly. Over tightening will lead to excess wear and then leakage.

157048-1
Equipment
Page 155

FIRST AND INTERSTAGE SUCTION DRUMS


These vessels are designed to remove any liquid from the gas streams to the
compressor. They are normally carbon or killed steel, with a stainless steel mesh
blanket to remove any entrained droplets. The first stage liquid is drained to a
blowcase, and pressured back to the overhead receiver. The liquid from the
interstage drum is pumped to the HPS. A typical drum is shown in Figure 88. Pitting
corrosion has been found in the lower portion of the shell and bottom head.
Hydrogen blistering and embrittlement has also been found.

Figure 88
Compressor Suction Drum
Ventilation and
Vent Nozzles

Gas Out

Mesh Blanket
(Demister Pad)

Gas Inlet with


Distributor

LC-LG

Manway

Steamout
Vortex breaker

Liquid Out

FCC-E700

157048-1
Equipment
Page 156

WASH WATER
The overhead stream from the main column contains various contaminants which
may cause corrosion, plugging, or fouling. These would include ammonia, sulfides,
cyanides, chlorides, and phenols. A wash water stream is used to remove them,
because most of them are ionic or polar species, readily soluble in water. Flow rates
are usually maintained at 6-7 vol% of the fresh feed rate.
The water should be clean, preferably steam condensate, to prevent adding more
problems such as salts or dissolved oxygen to the system. The water is injected
after the compressor first stage and is pumped out of the interstage suction drum to
the HPS. Here it collects in a water boot and is pressured back to the main column
overhead condensers. It collects in the overhead receiver water boot and is pumped
out to the sour water stripper for disposal.
There is always water present in the main column and gas concentration section
from stripping steam and other sources. If the wash water is not used to flush out
the sulfides, ammonia, cyanides, and other species, the water present can become
highly corrosive from absorption of these contaminants. Sulfide levels of greater
than 20,000 ppm have been reported in the overhead receiver water. Hydrogen
blistering and general corrosive attack may become quite severe, especially if feed
sulfur is greater than 1%, or nitrogen greater than 1000 ppm. Also, while the
overhead receiver water may be basic, pH >7, most of the ammonia that is
responsible for this will drop out in the main column receiver.
The water in the gas concentration section may become acidic from H2S and CN-. If
there is any oxygen present, elemental sulfur may be formed from oxidation of the
sulfides. This will cause problems in meeting gasoline product specifications. Wash
water will solve many of these problems by diluting the corrosives, and keeping the
water pH at 8-9, where sulfide oxidation is greatly reduced.

157048-1
Equipment
Page 157

HIGH PRESSURE SEPARATOR


The HPS Figure 89 receives the liquid streams from the interstage suction drum
and primary absorber bottoms, and the gas streams from the second stage
compressor discharge and the stripper overhead. The vessel is carbon or killed
steel; it looks very similar to the main column overhead receiver shown in Figure
82, with a slotted pipe distributor instead of a baffled inlet. Sour water is pressured
from the boot to the main column overhead, while gasoline is pumped to the
stripper. The gas goes to the primary absorber. Pitting corrosion has been found in
the lower section. Hydrogen blistering and embrittlement has also been found.

Figure 89
High Pressure Separator
Inlet Pressure Relief

PI & PC

LI & LC

Ventilation
and Vent

Vapor Out

Slotted Pipe
Distributor
Manway

Steam Out

Vortex
Breaker

LI & LC
Liquid Out
Water Boot
Water Out

FCC-E701

157048-1
Equipment
Page 158

PRIMARY ABSORBER
The primary absorber (Figure 90)is a killed steel column with about 30-40 trays.
The trays are normally carbon steel with Type 410 stainless steel fittings. Valuable
light products such as LPG are absorbed from the gas as it travels from the bottom
to the top outlet. The most common tower design uses two intercoolers to remove
the heat of gas absorption from the gasoline as it fails down the tower. This
temperature rise is roughly 20-25F (11-14C). These intercoolers are located
roughly one-third and two-thirds of the way down the tower. The gasoline circulation
through the water coolers may be pumped or gravity driven. Water drain pots are
required on the gravity circulation systems to prevent accumulation of water as the
gasoline cools; a water head would stop gasoline circulation. Pumped systems are
better from a velocity, and thus heat transfer, viewpoint.
Another design that has become popular recently uses debutanized FCC gasoline
as a final wash before the gas leaves the tower. A cooled slipstream from the
bottom of the debutanizer is introduced at the top of the column, with the gasoline
from the main column overhead receiver entering the tower 5 to 7 trays lower. This
system allows the use of only one intercooler with the same or better C3 recovery
efficiency, i.e., the amount of C3 recovered in the debutanizer overhead compared
to the total amount produced. The gasoline from the bottom of the primary absorber
is pumped to the HPS; the gas flows to the sponge absorber.
Serious corrosion can occur in this column from H2 attack. Hydrogen blistering can
be severe in the upper section and top head, and is also seen occasionally in the
middle of the tower and in the intercoolers. The shell and heads should be
inspected at each turnaround. The inspection of the internals should pay particular
attention to stagnant areas around weirs, downcomers, and nozzle extensions.
Bolts and trays should be inspected for tightness and embrittlement of materials.

157048-1
Equipment
Page 159

Figure 90
Primary Absorber
Vent and Ventilation
Vapor Outlet
Distributor

Recycle Gasoline Inlet


1

Distributor
Unstabilized
Gasoline Inlet

Manway

12

Upper Inter Cooler Return

13
14

26

Upper Inter Cooler Draw


Lower Inter Cooler Return

27
28

Lower Inter Cooler Draw

40

LC & LG

Vapor Inlet

Liquid Outlet

FCC-E702

157048-1
Equipment
Page 160

SPONGE ABSORBER
The sponge absorber (Figure 91) is a "guard" tower which uses LCO to absorb any
remaining liquid from the gas. If any significant quantities of C5 or C6 remain in the
gas stream, these will cause problems with treating. If the gas is sent directly to the
fuel system, condensation of heavy material is dangerous.
The sponge absorber is fabricated with killed steel. It used to be designed with 25
carbon steel trays; the tray fittings were Type 410 stainless. Currently, UOP designs
all sponge absorbers with packing towers which minimizes the risk of foaming. A
mesh blanket, Type 304 stainless, is installed at the top of the absorber to trap any
entrained liquid.
The gas leaves the tower on pressure control. Absorption LCO is flow controlled,
with a lean oil/rich oil exchanger to heat the rich sponge oil as it leaves the
absorber. This decreases the temperature effects when the LCO is returned to the
main column. The lean oil is water cooled after it leaves the rich oil exchanger, to
100F (38C) maximum.
The inspector of the tower should follow the same pattern of inspection as the
primary absorber. The sponge absorber is subject to corrosion and hydrogen
blistering, but usually somewhat less than the primary.

157048-1
Equipment
Page 161

Figure 91
Sponge Absorber
Vent and Ventilation

Vapor Outlet
Mesh Blanket

Pre-Distributor

Re-Distributor
Hold Down Grid

Manway
Bed Support
Vapor Inlet

LC-LG

Steam Out

Liquid Out
FCC-E703

157048-1
Equipment
Page 162

STRIPPER
The stripper (Figure 92) removes light hydrocarbons and H2S from the gasoline. A
LCO reboiler is used to heat the tower and to preheat the gasoline feed. The off-gas
goes to the HPS; an FRC in the gas line controls the LCO to the reboiler.
The stripper is made of killed carbon steel with about 30-40 carbon steel trays. Tray
fittings are Type 410 stainless. Some units have experienced high corrosion rates in
the stripper. The reboiler is usually carbon steel, but may be 5% Cr % Mo in
cases where severe corrosion has occurred. This corrosion is not common and can
usually be corrected without the additional expense of a chrome reboiler. Inhibitor
has been used in some cases, but this protection can be lost with unstable
operating conditions. The inspector should check metal thickness and the reboiler
should be checked for unusual wear during the turnaround.

157048-1
Equipment
Page 163

Figure 92
Stripper
Vapor Outlet
Vent and Ventilation

Distributor
Liquid Inlet
1

18

Manway
19

36

Reboiler Return
Reboiler Draw Off Well
LC & LG

Liquid Out to Reboiler

Steam Out
Liquid Out
Vortex Breaker

FCC-E704

157048-1
Equipment
Page 164

DEBUTANIZER
The stripped gasoline is pressured to the debutanizer for vapor pressure
adjustment. The LPG product after treating can be used for fuel or further
processed for petrochemicals. The gasoline product usually requires treatment for
sulfur, and the addition of inhibitors for better stability.
The most common method of pressure control is a hot vapor bypass around the
overhead condenser. The reflux back to the tower is temperature controlled by a
TRC device located on the fourth tray from the top. This scheme gives a better split
than overhead temperature control. Heat is supplied by a HCO reboiler,
occasionally supplemented by a main column bottoms reboiler. Hot fluid to the
reboiler tubes is FRC controlled. Insufficient heat will not give good fractionation,
too much heat will flood the tower.
The debutanizer (Figure 93) is killed steel with 35-40 carbon steel trays. Tray
fittings are Type 410 stainless. The overhead system is usually carbon steel, with
inhibited Admiralty tubes in the water condenser. The shell of the reboiler is carbon
steel; the tubes, tube sheet and floating head cover are 5% Cr % Mo. Carbon
steel clad with Type 410 stainless may be used instead of 5% Cr. Hot fluid flow is
through the tubes. This vessel and associated piping are occasionally subject to
severe corrosion and hydrogen blistering. The best solution to this and to the
corrosion problems of the other vessels is water injection at the interstage receiver.
As mentioned above, some refiners have also used alloy steel or monel instead of
carbon steel for severe cases of corrosion in the debutanizer.

157048-1
Equipment
Page 165

Figure 93
Debutanizer
Vent and
Ventilation

Vapor Outlet
Reflux
1

TIC
8

Stripper
Bottoms
Inlet

19

Manway

20

35
36

40

LC & LG

Vortex Breaker

Reboiler
Return
Manway
Steam Out
Liquid Out to
Reboiler and
Product

FCC-E705

157048-1
Equipment
Page 166

CORROSION
Steel Corrosion
It has been established that steel corrosion, hydrogen blistering, and weld cracking
problems come from a water, hydrogen sulfide, ammonia, and/or cyanide
environment. The overall corrosion reaction for steel is:
Fe + 2HS- = FeS + S-2 + 2H

(1)

The amount of bisulfide ion (HS-) formed depends on the pH, temperature, and
hydrogen sulfide (H2S) partial pressure and comes from the H2S dissociation:
H2S = H+ + HS-

(2)

The iron sulfide (FeS) scale provides some protection against corrosion if the
system pH is about 8. However, dissolved hydrogen cyanide (HCN) accelerates
corrosion by destroying the protective FeS film and converting it into soluble
ferrocyanide complexes:
FeS + 6CN- = Fe(CN)6-2 + S-2

(3)

The ferrocyanide (Fe(CN)6-4) is easily recognized by its blue color (Prussian blue)
when water samples are allowed to dry.
Hydrogen Blistering
Some portion of the hydrogen atoms formed in the corrosion process (Equation 1)
gradually penetrates the steel through surface imperfections and diffuse into the
steel as atomic hydrogen. This diffusing hydrogen reacts to form molecular
hydrogen:
2H = H2

157048-1
Equipment
Page 167

The hydrogen molecules are larger in size and are trapped in the steel cavities
causing local pressure to build up. The result is blistering and fissures in the metal.
High quality killed carbon steel usually has less inclusions today than in earlier
times, and blistering is usually less of a problem than before.
Water Wash
Most refiners feel that wash water is adequate for cyanide control. Hydrogen
blistering has not been a problem in most of the FCC Gas Concentration units.
Cyanide is effectively kept out of the Gas Concentration Unit through the use of an
adequate wash to the Main Column overhead receiver and to the wet gas
compressor Interstage suction drum. An effective water wash dilutes and scrubs the
corrosive species such as hydrogen sulfide, ammonia, chlorides, and cyanides from
the FCC light hydrocarbon streams.
As stated previously, the water wash rate should be at least 6-7 Vol% on fresh feed
to the FCC Unit. There should be no entrainment of water from the overhead
receiver to the primary absorber column. Recommended water wash sources
include oxygen free water, steam condensate, and boiler feed water before
alkalinity adjustment. If the wash water contains oxygen, gum formation will
increase and wet gas compressor fouling may occur. If the wash water contains
magnesium or calcium salts, these components will precipitate increasing the
fouling problems. Also, if oxygen is present, elemental sulfur may be formed
causing copper strip corrosion in the gasoline.
Condensate pH
Overhead streams in the fractionator and gas concentration section consist mainly
of hydrocarbon vapors, steam, and relatively small amounts of contaminants.
During condensation, the water phase absorbs some of the contaminants and can
become highly corrosive. The FCC Process condensate develops a pH of 7 to 9
because of the higher concentration of ammonia relative to the acid contaminants
and because ammonia is more soluble in water than hydrogen sulfide or hydrogen
cyanide.

157048-1
Equipment
Page 168

It is recommended to maintain the pH of the condensate in the range of 8.0 - 8.5 to


prevent elemental sulfur formation and reduce the corrosion rate. Polysulfide can
decompose at a pH below 7.8 forming H2S and free S. This will cause the gasoline
to be corrosive. The pH measurement of the high pressure separator and main
column overhead receiver water must be made at site with portable pH meters. The
pH of a water sample can change as much as 2 pH units if the sample is taken to
the laboratory.
Polysulfide Injection
Some Refiners who are processing feed with high nitrogen content and have high
cyanide concentrations in the Unit are using ammonium polysulfide to reduce the
overall corrosion rate. The ammonium polysulfide is an additive that converts
cyanides to thiocyanates by the reaction:
(NH4) 2S3 + HCN = NH4SCN + S2-2
The refiner should monitor the Gas Concentration Unit carefully when injecting
polysulfide, since these compounds could sometimes cause more problems than
benefits. The following are some disadvantages of the ammonium polysulfide:
1)

The pH of the system should be higher than 8.0. At lower pH values the
polysulfide decomposes into ammonia (NH3), hydrogen sulfide (H2S), and
elemental sulfur (S). The H2S will increase the corrosion rate and the
elemental sulfur (S) will give corrosive gasoline and equipment plugging
problems.

2)

The polysulfide will commence salting out at temperatures below 38F and
plug pump suction and discharge lines.

3)

The polysulfide will decompose at temperatures close to 250F producing H2S,


NH3, and S. As stated previously, the H2S will increase the corrosion rate and
the S will give corrosive gasoline and equipment plugging problems.

157048-1
Equipment
Page 169

4)

An excess of 10 to 15 ppm of polysulfide over the stoichiometric amount of


cyanide is desired. If over 30 ppm is present, there will be enough found in the
sour water stripper bottoms to give problems in the effluent treating. Upon
neutralization the (NH4)2S3 decomposes into NH3, H2S, and S. This can result
in bacterial kill in biotreating and equipment plugging.

5)

Wash water requirements are generally higher to assure that the polysulfide
stays in solution. If the polysulfide does not stay in solution equipment plugging
will increase. Also, processing the additional sour water can be costly.

157048
Fluidized Solids
Page 1

FLUIDIZED SOLIDS
Introduction
A fluidized bed is formed by passing a gas upwards through a bed of solid particles.
If the gas velocity (U) is above a minimum gas velocity, Umf, the solids become
fluidized and the mixture behaves like a liquid.

Figure 1
Fluidized Beds Behave Like a Liquid

No Flow

U Umf

Flow

U Umf

157048
Fluidized Solids
Page 2

A fluidized catalyst bed provides a number of key processing advantages.


Fluidization facilitates the transfer of catalyst, which permits the continuous
reaction/regeneration cycle of the FCC unit. Catalyst addition and removal is easy,
simplifying catalyst management. High mass and heat transfer in a fluidized bed
allow for efficient operation. For a given material and gas velocity, pressure drop is
lower in fluidized beds than in fixed catalyst beds. These characteristics make the
fluidized bed an attractive choice as a chemical or physical processing tool.
Fluidized Bed Theory
An unfluidized bed of catalyst is referred to as a fixed bed. The catalyst particles are
in close contact with each other and contain void spaces. The voids are due to the
spherical shape of the catalyst and the efficiency with which spheres can be
packed. By introducing a fluidization medium air, hydrocarbon vapor, or steam
the catalyst can be made to behave like a liquid. Once fluidized, the catalyst will
assume a level surface and exert a pressure profile similar to that of a liquid. In this
state, the catalyst can be made to flow through a pipe as in the case of the
standpipes and reactor riser. In essence, it is a liquid stream. It is this principle
which permits circulation of catalyst between the reactor and regenerator.
When a fluidization gas is initially introduced to a fixed bed of catalyst, there is no
change in the bed; the gas simply flows through the void spaces. As the velocity of
the gas increases, it begins to exert a force on the bed to lift the catalyst. The void
volume begins to increase as the bed expands. With a further increase in gas
velocity, there is a point at which the drag (friction) force exerted on the particle is
just equal to the force exerted by gravity on the catalyst. This gas velocity is referred
to as the incipient fluidization velocity or minimum fluidization velocity (Umf). Any
further increase in gas velocity allows the catalyst to freely move in the flowing gas,
constantly colliding with other catalyst particles. At this point the catalyst bed is
fluidized and behaves like a liquid.

157048
Fluidized Solids
Page 3

This behavior will change as more gas is pressured through the bed. Bubbles of gas
begin to appear in the bed. The point at which this occurs is defined as the
minimum bubbling velocity (Umb). The bubbles may be small ones which disappear
after a short rise, or larger ones that grow as they pass through the bed. As the
velocity is increased further, the bubbles begin to occupy more of the bed. The
bubbles bursting through the surface throw catalyst into the area above the bed.
The surface of the bed is violently disturbed by the slugs, yet remains fairly distinct.
As gas velocity is further increased, the bed enters a turbulent state, where the
upper surface of the bed is not well defined. Slugging by large gas bubbles
decreases. Bubbling bed regenerators typically operate in this region. Advantages
of this regime are high solids mixing and therefore high heat and mass transfer
rates, contributing to the combustion of coke off the catalyst. The mixing is primarily
in the vertical direction and is driven by catalyst particles being pushed upwards on
top of the bubbles then falling off and dropping down behind the bubbles as shown
in Figure 2.
Eventually, the gas velocity exceeds the terminal velocity of some of the particles in
the bed. This regime is known as fast fluidization. Combustors typically operate in
this regime. At this point, a fluidized bed is not maintained unless catalyst is
recycled to the bed. Further gas rate increase moves into the pneumatic conveying
regime. Without recirculation of catalyst, all catalyst will be blown out of the vessel.

157048
Fluidized Solids
Page 4

Figure 2
Bubble Driven Catalyst Mixing

Catalyst
Flow
Bubble
Wake
Drift

Gas
FCC-F001

157048
Fluidized Solids
Page 5

Figure 3 illustrates the pressure drop across a bed as a function of fluidization gas
superficial velocity. Initially, the pressure drop increases with velocity to the point of
initial fluidization, Umf. For typical FCC catalyst this value is around 0.01 ft/sec.
Once fluidized, the catalyst exerts a pressure profile similar to that of a liquid. The
pressure head exerted by the bed will be about equal the weight of catalyst and the
gas contained in it. As a result of frictional losses, the pressure drop across the bed
is slightly greater than its weight. Between the point of initial fluidization and the
point at which entrainment begins, the behavior of the catalyst may be described by
the following equation:
P = (cat + gas) * h where gas 0
P = Pressure Drop, psi
= Density, lbs/ft3
h=
Bed Height, ft/144
At higher velocities, we approach the pneumatic conveying regime in which the
entire bed is eventually entrained; hence a sharp pressure drop.

157048
Fluidized Solids
Page 6

Figure 3
Pressure Drop Across a Fluidized Bed
Bubbling
Bed
Regenerator

U-Umf < Umb

Increasing Pressure Drop Across the Bed

U>Umb
Combustor
U<Umf
Reactor
Riser

Particulate
Regime

Bubbling
Regime

Slug Flow
Regime

Turbulent
Regime
Fast
Fluidization

Fixed
Bed

Gas
Initiation of
Fluidization

Entrainment
Begins

Increasing Gas Velocity


P = (cat +gas) * h
P = Pressure Drop, psi

gas 0

U = Gas Velocity
Umf = Minimum fluidization Velocity
Umb = Minimum bubbling velocity

Density, lbs/ft3
hBed Height, ft/144

Pneumatic
Conveying

157048
Fluidized Solids
Page 7

FCC Catalyst Fluidization


FCC catalyst is a fine powder, generally smaller than most refinery catalysts. The
physical properties of the catalyst effecting the fluidization characteristics are
density, particle shape, and size distribution. In the Geldart powder classification
system, FCC catalyst is considered a Group A material. The A representing
aeratable. The classes of particles under the Geldhart classification system are
shown in Figure 4.
FCC catalyst bulk density (non-fluidized) is about 50-55 lb/ft3 (800-880 kg/m3) and is
a result of catalyst composition and the manufacturing process. FCC catalyst is
roughly spherical in shape. This shape is advantageous to fluidization as it tends to
pack less tightly when defluidized. Spheres also lack the sharp edges which can
contribute to plant erosion problems. FCC catalyst is a mixture of particle sizes
ranging from 10-130 microns. The presence of fines (particles < 40 microns) is
helpful for fluidization. Fines are introduced with the fresh catalyst and are produced
during operation of the unit by attrition. These smaller particles move more easily in
the gas and act as a lubricant between the larger particles to lower the minimum
velocity required for fluidization. Generally, the more fines in the catalyst inventory,
the easier the catalyst is to fluidize and the longer it takes to defluidize once the
aeration medium is stopped. The physical properties of the gas also have a strong
influence on fluidization. The primary factors are the gas viscosity and density.
FCC unit design takes into consideration all the fluidization parameters. Changing
temperatures, pressures, bed heights, and gas velocities are considered when
sizing and orienting process equipment.

157048
Fluidized Solids
Page 8

Figure 4
Geldarts Particle Classification

Pp, Pg, Kg/m3

10,000
5,000
3,000
2,000

D
B

1,000

500
300
200

100
10

20

50

100 200
500 1,000 2,000
dp, Microns

A: Aeratable (Umb> Umf) Have Significant Deaeration Time


B: Bubbles Above Umf (Umb= Umf)

C: Cohesive
D: Spoutable

157048
Fluidized Solids
Page 9

Fluidization in Regenerator
Superficial velocities in the FCC regenerator are considerably higher than minimum
fluidization. This is because the air rate is set by the coke make in the unit, not the
fluidization requirements. Less air would leave the unit behind in burning, with most
of the coke still on the catalyst. The regenerator diameter could be increased to
drop the superficial velocity but this would add considerable cost in construction.
Additionally, uniform distribution of air is more difficult in very large vessels. The
FCC design takes into account the need to regenerate catalyst, maintain
fluidization, retain catalyst inventory, and minimize capital expenditures.
The conventional or Bubbling Bed regenerator, shown in Figure 5, generally
operates with superficial air velocities of 2-3.5 ft/sec. This velocity is in the turbulent
fluidization regime. This regime exhibits violent bubbling and gas slugging which
causes catalyst to be thrown upward into the freeboard area above the bed. Most of
the catalyst settles back to the bed by gravity. However, some of the catalyst,
especially fines, is carried up above the freeboard area. The regenerator vessel can
thus be divided into two sections, the dense bed and the dilute phase.
The dense bed is all the catalyst contained below the established bed level. The
dilute phase is where larger catalyst particles separate from the gas and fall back to
the bed. Any catalyst particles that do not separate in the dilute phase, enter into
the regenerator cyclones. Catalyst entering the cyclones is separated by centrifugal
force with the larger particles being returned to the bed via the cyclone diplegs.
Catalyst fines too small to be separated by the cyclones are carried out of the
regenerator with the flue gas.
In a bubbling bed regenerator it is important that the coke and air are evenly
distributed. The air bubbles rising through the bed result in thorough mixing in the
vertical direction but little mixing horizontally. Therefore if the spent catalyst, and
therefore the coke, is not uniformly distributed the areas with more coke may be
short of air allowing CO to breakthrough the bed. The other areas with less coke
operate with excess oxygen. This combination results in afterburning and high

157048
Fluidized Solids
Page 10

temperatures in the dilute phase. For this reason a spent catalyst distributor or ski
jump is used on all spent catalyst standpipe outlets. In many cases the air grid jet
plugging pattern will be shifted to areas expected to have less coke present to
reduce the air in that area.
The design distance between the cyclone inlet and the surface of the dense bed is
determined by the Transport Disengaging Height, or TDH. The TDH is a function of
the superficial gas velocity, vessel diameter, and the particle size distribution. The
amount of catalyst entrained in the gas above a fluidized bed decreases with the
height above it. A given particle reaches a distance above the bed where
gravitational forces overcome the upward drag forces of the gas, and the particle
falls back to the bed. The smaller the particle, the greater the distance. A height is
reached where the amount of entrained solids becomes constant, no more particles
are overcome by gravitational forces. The particles here are to small to settle. This
height, the TDH, determines what minimum distance above the bed the cyclones
inlets must be placed. Other considerations for setting the cyclone design inlet level
include dense bed level variations and minimum required dipleg length. To account
for these considerations, the cyclone inlet height will be greater than the actual
TDH.
As illustrated in Figure 6, if a regenerator is operated in such a manner that the
distance between the catalyst bed and the cyclone inlet is less than the TDH, the
catalyst density at the cyclone inlet will be higher. This will increase the catalyst
loading to the cyclone and potentially increase catalyst losses from the cyclone.
In a bubbling bed regenerator the discharge of the primary cyclone diplegs which
are returning hot catalyst to the bed can be directed to heat colder areas of the bed,
typically near the spent catalyst inlet.

157048
Fluidized Solids
Page 11

Figure 5
Conventional FCC Regenerator
Flue
Gas

Transport
Disengaging
Height

Freeboard

Catalyst
Movement

Dense
Bed

Gas
Bubbles

Air

157048
Fluidized Solids
Page 12

TDH

Height

Figure 6
Schematic Depiction of TDH

Density of Solids

157048
Fluidized Solids
Page 13

The combustor section of aHigh Efficiency regenerator operates at much higher


velocities than the conventional regenerator. The lower part of the regenerator, the
combustor, operates at the low end of the fast fluidization regime at a velocity on
the order of 5-6 ft/sec. At this velocity catalyst is carried upward. The catalyst
travels up the combustor riser in pseudo plug flow. Much of the catalyst slips behind
and backmixes as it moves upward. At the top of the combustor riser the
regeneration gas and catalyst undergo a primary separation. The upper regenerator
vessel is designed to operate with superficial gas velocities on the order of 2-3
ft/sec. Since the regeneration gas does not pass through the catalyst bed in the
upper regenerator, a small stream of fluffing air is directed into the dense bed to
keep it aerated. Since the combustor velocity is so high and the net catalyst flow is
up, external catalyst recycle is necessary to maintain density in the combustor. The
density in a high efficiency combustor is controlled with a slide valve on a recycle
standpipe. The amount of catalyst circulated from the dense bed in the upper
regenerator controls the density and temperature in the combustor.
Figure 7 represents fluidization data for a commercial combustor operation at
various catalyst loadings and superficial air velocities. The figure shows the
pressure gradient, or fluidized density in lb/ft3, measured across the combustor
section. The catalyst loading, W (lb/ft2/sec), is referred to as the flux and is the
summation of both the reactor-regenerator catalyst circulation and the combustors
external recirculation. Lines A through D represent lines of constant gas velocity.
The gas superficial velocity A lies well below the catalyst transport velocity;
however, at low solids flux (region X-Y) dilute phase flow exists. At condition Y, the
solids flux is sufficient to choke the system and any further increase in solids
loading (region Y-Z) results in a substantial density (inventory) increase. At the
higher gas velocities B & C, choking takes place at much higher solids flux and
results in a less abrupt change in combustor density with further increases in flux.
Such a region can be referred to as fast-fluidized. Eventually, at higher velocities
like D, true transport flow will be generated under which conditions no solid flux can
choke the system.

157048
Fluidized Solids
Page 14

This operating data demonstrates how flexible the system is in adjusting combustor
inventory/coke burning capacity for various operating conditions. Consider the
operating condition E at gas velocity B. If the superficial velocity is now increased to
C either by a change in regenerator pressure or air rate, the combustor density will
decrease to condition F at constant solids loading. However, if necessary, the
combustor density may be reestablished at condition G by means of increasing the
solids flux (opening the external recirculation slide valve). Note that an adjustment
in combustor density also changes the combustor inventory and a change in the
upper regenerator level (surge inventory).
The catalyst bed density in a regenerator is primarily a function of superficial
velocity. For typical bubbling bed regenerator velocities, bed densities would range
from 30 to 40 lb/ft3. By contrast, typical combustor densities range from 10 to 15
lb/ft3. Figure 8 gives a correlation between bed density and superficial velocity.
Figures 9, 10, & 11 show normal catalyst densities in various unit configurations.

157048
Fluidized Solids
Page 15

Figure 7
Combustor Operation
A

Gas Velocity, ft/sec

(Z)

3 3
Combustor Density, lb/ft

Combustor Catalyst
Inventory, I =
Density x Volume

D
(Y)
(Y)
(X)

Catalyst Loading (W) lb / sec/ft2

157048
Fluidized Solids
Page 16

Figure 8
Catalyst Bed Density

Bed Density, lb/ft 3

60
50
40
30
20
10
0
0

0.1

1.0

3.0

10.0

Superficial Velocity, ft/sec


*Adapted from a paper "Fluidization and the FCC Process" by W.S. Letzch of Katalistiks

157048
Fluidized Solids
Page 17

Figure 9
Catalyst Densities
Side by Side FCC with Bubbling Bed Regenerator/
Tee Disengager Riser Termination

2
(30)

40-45
(640-720)

3
(50)

35
(560)

Densities in lb/ft3 (kg/m3)

35
(560)

5
(80)

157048
Fluidized Solids
Page 18

Figure 10
Catalyst Densities
High Efficiency Regenerator/ Highly Contained
Riser Termination/ Elevated Feed

<1
(<15)

1
(20)

3
(50)

40
(640)

40-45
(640-720)

35
(560)
5
(80)

8-12
(130-200)

15-20
(240-320)

157048
Fluidized Solids
Page 19

Figure 11
Catalyst Densities
RFCC 2 Stage Regenerator

<1
(<15)

40-45
(640-720)

3
(50)
5
(80)

35
(560)

3
(50)

35
(560)

35
(560)
15-20
(240-320)

157048
Fluidized Solids
Page 20

Fluidization in Standpipes
Fluidized catalyst can be made to flow through pipe in the same manner as a liquid.
Standpipes generate static head which allows transport of catalyst between the
reactor and regenerator. The static head generated must be enough to overcome
any pressure differences between the reactor and regenerator. As catalyst travels
down the standpipe it carries gas with it which keeps the catalyst fluidized and
flowing smoothly. The pressure will increase as the catalyst progresses down the
standpipe because of the additional head. This increase in pressure causes the
entrained gas to compress and the void volume to decrease. If the gas is
compressed too much the catalyst in the standpipe becomes dearated, it will no
longer flow smoothly and can cause circulation problems. A condition know as slipstick flow can ensue where the catalyst breaks away from the dearated mass and
passes down the standpipe. Reactor temperature and reactor level swings can be a
symptom of this phenomenon. Standpipe design criteria are set to ensure that
pressure head build up, flux rate and velocity, and aeration levels are adequate to
ensure stable operation.
Figure 12 illustrates the pressure profile in a standpipe. Troubleshooting of low or
erratic standpipe flow should start with a single gauge pressure survey to ensure
that the right amount of head is generated in the standpipe. The head generation
should be the density in the standpipe, typically 35 lb/ft3 (560 kg/m3) times the
elevation change. Another useful troubleshooting exercise is to check the flow
through the slide valve versus the expected flow predicted by the slide valve
equation:

A x Cd x (DP x )1/2
W=
1.5
Where:

W = Catalyst Mass Flow (lb/sec)


A = Total Slide Valve Open Area, in2
Cd = Valve Coefficient (0.9 Typical)
DP = Slide Valve Pressure Drop (psi)
= Standpipe Density (35 lb/ft3 Typical)

157048
Fluidized Solids
Page 21

Flow problems in standpipes can have several causes including:

Too much gas entrained into the standpipe


Insufficient gas to keep the standpipe fluidized
Shallow standpipe angle
Elbows in standpipes
Poor catalyst fluidization properties (typically lack of fines <40 )

Figure 12
Standpipe Pressure Profile

Standpipe Entrance
Effects

Head Generation

Height
Slide Valve Entrance Effects
Slide Valve DP

Pressure

157048
Fluidized Solids
Page 22

Fluidization in Reactor Riser


Elevated feed systems use steam and/or lift gas to accelerate catalyst up the riser.
Typical velocities in the lift zone are 12-18 ft/sec (3.6-5.5 m/sec). This velocity is in
the conveying regime and transports the catalyst up the riser with minimum
slippage. This velocity region results in a moderate and uniform catalyst density
profile at the point of feed injection. The moderate density allows the feed droplets
to penetrate the catalyst more easily resulting in more uniform catalyst/oil
contacting. Feed is radially injected roughly 1/3 the distance up the riser where
rapid vaporization and reaction take place. The vapor expansion results in a
dramatic increase in velocity up the riser. Riser exit velocities of 60 ft/sec are
typical. Feed riser residence times are on the order of two to four seconds. This
would be considered dilute phase pneumatic conveying. During startup, shutdown,
or emergency situations, it is important to maintain lift media in the riser to ensure
that catalyst does not slump and plug the riser. Typically, lift steam is added to the
wye to ensure adequate velocity in the riser in such situations.
Because fluidized solids flow like a liquid they will flow into any stagnant area.
Therefore it is important to keep the feed nozzles purged with steam any time there
is catalyst in the riser without feed.
Fluidization in Reactor
Depending on the reactor riser termination, catalyst and oil exiting the riser are
separated in a ballistic manner or by centrifugal force in a vortex chamber or
cyclone system. The catalyst, once separated from the reaction products, falls down
into the reactor stripper. With modern, highly contained riser terminations, the
reactor is essentially a large disengaging device as the majority of the reaction
takes place in the riser.
As in standpipes, the catalyst flowing down the diplegs is kept fluidized by the
reactor vapors which are entrained with the catalyst. In direct connected cyclone
systems with almost all of the catalyst circulation flowing down the primary cyclone

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Fluidized Solids
Page 23

diplegs this gas volume can be very large, as much as 6 wt% of the total product.
Once the catalyst exits the dipleg the entrained gas is exposed to high temperatures
for an extended period of time in the large reactor shell volume resulting in higher
light ends and coke make. This is one of the reasons for development of the vortex
separation technology which provides a highly contained riser termination without
the entrainment of hydrocarbons back into the reactor through the diplegs.
Fluidization in Reactor Stripper
The reactor stripper is similar in principle to a dense bed in the regenerator. The key
difference is that the fluidization, or stripping, medium is steam and not air. Steam is
introduced through pipe distributors and flows up through the bed displacing
hydrocarbons from the interstitial and void spaces of the catalyst. Roughly 1.5 to 2.5
pounds of steam per thousand pounds of catalyst is required for a well designed
stripper. The stripping action helps to recover valuable reaction products and
maintains proper fluidization of the catalyst as it moves back to the regenerator.
Typical superficial velocities are in the range of one to three feet per second.
Poor stripper design can result in uneven distribution of the vapor flow. As a result
of this, some of the catalyst may become defluidized while the catalyst flux in other
areas of the stripper increases. This can reduce stripping efficiency due to poor
catalyst/steam contacting, excessive gas entrainment down the stripper and lower
residence times in the active portion of the stripper. As the catalyst flux in the active
area of the stripper increases more gas can be entrained down the stripper and into
the standpipe resulting in lower densities, less standpipe head generation and lower
slide valve pressure drop.

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Fluidized Solids
Page 24

Fluidization in Catalyst Coolers


As stated earlier, bubbles rising through a catalyst bed result in thorough mixing in
the vertical direction. In a catalyst cooler this phenomena is used to continually
replace cooled catalyst with hot catalyst from the regenerator vessel by bubbling air
injected near the bottom of the tubes. As the fluffing air rate is increased the rate of
hot catalyst entering the catalyst cooler increases. The heat transfer coefficient
between the catalyst particles and the tubes also increase with increasing fluffing air
as the bed becomes more turbulent.
Flow through type catalyst coolers also use a standpipe and slide valve to
continually circulate hot catalyst from the regenerator through the cooler. This
increases the temperature of the catalyst in the cooler further so that ~50% more
duty can be obtained from a flow through cooler than a back mixed cooler.

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Catalyst
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CATALYST
INTRODUCTION
The FCC catalysts in use today are a complex blend of technologies. The
workhorse catalyst in this complex system is, itself, a complex blend of
technologies. The main component in the workhorse catalyst is a crystalline silicaalumina material known as a zeolite, or alternatively known as a molecular sieve.
The quantity and the properties of the zeolite in the catalyst can be altered to fit the
individual activity and product yield requirements of the refinery. A second active
component in the workhorse catalyst is typically an active alumina, included in the
workhorse catalyst to provide conversion of the very large and heavy molecules in
the feed, which are difficult for the molecular sieve to process. This second
component also can protect the molecular sieve from contaminants in the FCCU
feed, which can damage the performance of the molecular sieve. A third component
is added to this catalyst cocktail to make the catalyst hard enough to meet the
stringent particulate emissions requirements of the FCCU.
In todays world, other catalytic components are frequently combined with the
workhorse catalyst, as catalyst additives. These additives can be included to
provide increased gasoline octane, increased yields of light olefins, principally
propylene, enhanced coke burning characteristics in the regenerator, and
decreased SOx and NOx emissions from the regenerator.

HISTORY
The first FCC catalysts were finely ground, naturally occurring clays. By today's
standards, these catalysts were inexpensive, but they suffered from poor stability,
activity, and integrity. Activity was less than half what it is today, and erosion caused

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by the jagged edges of natural catalyst created maintenance problems which


required high makeup rates to keep up unit inventory.
The first major improvement in FCC catalysts was the introduction of the allsynthetic catalysts in 1946. These new catalysts were amorphous silica-alumina
materials containing approximately 12% alumina and 88% silica. They were spray
dried as the final step in their manufacture, which resulted in a roughly spheroidal
particle. This improved particle shape provided improved fluidization characteristics
and decreased equipment erosion problems. These low alumina catalysts were
more active than the ground clays and produced higher octane gasoline.
The early 1950's saw the next major improvement in these amorphous FCC
catalysts. The catalyst alumina content was increased to 25%. Catalyst activity
increased with increased surface area.
Shortly after the development of the higher alumina catalyst, a silica-magnesia
catalyst was introduced. Though advertised to be selective for middle distillate (light
cycle oil) production, these catalysts did not regenerate sufficiently to be
commercially acceptable.
A breakthrough in FCC catalyst technology for maximizing gasoline selectivity
occurred during the early 1960's, when it was discovered that molecular sieves
could be excellent cracking catalysts. The silica - alumina chemical composition of
the catalyst remained basically the same, but the structure was radically different.
The crystalline zeolite has a well ordered, repeatable framework structure in
contrast to the amorphous, sponge-like structure of the previous low and high
alumina catalysts. The zeolite, when first synthesized, contains ion exchangeable
Na+ cations. In that form the zeolite is a poor cracking catalyst. The break through
discovery occurred when it was found that the replacement of Na+ with either H+ or
rare earth (principally lanthanum and/or cerium) cations by ion exchange converted
the zeolite into an outstanding cracking catalyst.

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There are over 30 different naturally occurring zeolites, but only 8 exist in sufficient
quantities to permit commercial exploitation. Over 100 have been synthesized in the
laboratory. The zeolite used in todays FCC catalyst is called a Type Y sieve and is
close to a rare natural mineral called faujasite. Large quantities of this material are
synthesized by the catalyst industry; roughly 50 million pounds per year are used for
FCC catalyst.
When zeolites were first tested as FCC catalysts, a pure zeolite was used. In the
pilot plants in operation at that time, this zeolite proved far too active, more than 100
times as active as amorphous catalysts. But when the zeolites were incorporated
into an amorphous base, the catalyst showed great promise. The first commercial
catalysts were made with 8-10% zeolites, and showed an activity 1.5 to 2 times that
of the amorphous types. To utilize this higher activity, UOP introduced the short
contact time, all riser cracking concept. The short contact time minimized
undesirable over cracking, while the high activity maintained good conversion.
Since virtually all the cracking could be done in one pass, it was no longer
necessary to recycle large quantities of heavy oil from the main column. Obviously,
the fresh feed rate was increased. However, for distillate operations, the low reactor
severity desired still required a high recycle rate.
The Y-zeolite is made up of regularly reoccurring cage-like structures. The cage has
openings into the cage of approximately 7 in diameter. The zeolite is, thus,
sometimes referred to as a molecular sieve, since the constrained entrance into the
zeolite cage acts as a sieve. Molecules up to a certain size can enter the cage while
larger molecules are kept out. Cracking occurs inside the cage at the locations of
the active sites, which are associated with the aluminum atoms inside the cage. The
cracked products must then exit the catalyst. At this time, the accepted theory is
that the reaction is not diffusion-controlled or limited, although the effect is present.
When exposed to the severe hydrothermal conditions that exist in the regenerator,
the crystalline structure of the zeolite is susceptible to significant destruction of its
structure, resulting in loss of catalytic activity. A major advancement in catalyst
technology occurred in the late 1960s, when it was discovered that a controlled

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hydrothermal pretreatment could improve the stability of the zeolite. The resulting
product was designated as ultra-stable Y-zeolite, commonly referred to as US-Y.
The 1970s ushered in the age of Environmental Sensitivity. Air pollution concerns
impacted the operations of the FCCU. This in turn ushered in the age of Catalyst
Additives. The first environmental concerns that effected FCC operations were in
the areas of CO pollution from the FCC regenerator and lead pollution from car
exhausts.
Prior to 1970, burning coke in the regenerator resulted in equal volumes of CO and
CO2 in the flue gas. It was impossible to convert the CO to CO2 in the FCCU without
creating unacceptable temperatures in the upper part of the regenerator.. A
modestly sized FCCU (20,000 BPD) without a CO boiler typically emitted over
20,000 lbs/hr of CO into the atmosphere. In the early 1970s it was discovered that a
small amount of platinum (~ 1ppm) in the FCC catalyst inventory allowed the CO to
be completely converted to CO2 without causing excessive temperatures in the
regenerator. In addition to eliminating CO, complete combustion had economic
advantages as well. Today, the 1 ppm of platinum is typically added as a catalyst
additive, which contains a high concentration of Pt (500 1000 ppm).
Prior to the 1970s, tetra ethyl lead (TEL) was used to increase gasoline octane but
concerns were raised that it also resulted in toxic lead emissions in automobile
exhaust. In the 1970s, legislation in the U.S. was passed that reduced, and
eventually eliminated, the amount of TEL that could be used in gasoline. Refiners
had to take steps to regain the lost octane. The use of US-Y zeolites in the FCCU
was found to help increase FCC gasoline octane. At the same time, a new zeolite
with a smaller pore than Y-zeolite, designated as ZSM-5, was developed which,
when added to the FCC catalyst inventory, was found to increase gasoline octane.
An additive containing ZSM-5 was frequently used for this purpose in the 1980s.
Sulfur oxide emissions (SOX) from the regenerator flue gas became an
environmental concern in the 1980s. This led to another catalyst additive which
refiners could blend with their FCC catalyst. The additive captured the SOX

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produced in the regenerator and carried it back to the reactor, where the sulfur was
released as H2S and left the FCCU with the product gases. The sulfur could then be
recovered as elemental sulfur in a Klaus plant.
In the late 1990s, concerns about nitric oxide (NOX) emissions from the regenerator
began to be raised. Catalyst suppliers began to provide additives that could be used
to reduce NOX. With the aid of the NOX additive NOX was converted to N2 and left
with the regenerator flue gas.
Also in the late 1990s, demand for propylene increased to the point where
propylene became an FCC product of considerably greater value than FCC
gasoline. Refiners who could produce a high quality propylene product began to run
their cat crackers to maximize propylene. The use of a ZSM-5 containing additive
became the variable that had the biggest impact upon increasing FCC propylene
yields. Whereas, in the 1980s, a ZSM-5 additive was used to increase gasoline
octane, at the start of the 21st century, ZSM-5 additives were primarily being used to
increase FCC propylene yields. The trend towards increasing value of propylene
continued during the period 2000 2005, during which time the price of propylene
increased from ~$500 / metric ton to ~$900/ metric ton. Refiners have increased
their use of ZSM-5 additives during this period and catalyst suppliers have
responded by increasing the content of ZSM-5 zeolite in their additives. In the
1980s, ZSM-5 additives typically contained 10% ZSM-5 zeolite. By 2005, additives
containing 40% ZSM-5 were common. Catalyst suppliers were also beginning to
supply a multi-functional catalyst which contained, within one catalyst particle, both
a Y-zeolite component and a ZSM-5 zeolite component.

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MODERN FCC CATALYSTS


PURPOSE OF THE CATALYST
Understanding some basic principles regarding fluid catalytic cracking (FCC)
catalyst performance is important to understanding catalyst technology. The modern
FCC catalyst carries out a variety of functions.
One important function is to provide all the process heat requirements This is
achieved by the burning of coke on the catalyst in the regenerator, which:

Heats the hydrocarbon feed up to the reaction temperature

Provides for the endothermic heat of cracking

Compensates for all the unit's heat losses

Heats the air from the air blower up to the temperature of the
regenerator

On the reactor side, the catalyst must have sufficient activity to carry out catalytic
conversion of the hydrocarbon feed before any significant amount of thermal
cracking occurs and must have the selectivity characteristics that provides the type
of products required by the refinery.
Thus, the catalyst must have the thermal stability to maintain particle and catalytic
integrity under severe regenerator conditions. It must have the physical strength to
maintain particle morphology under the severe impact and erosion forces so that it
remains in the unit, and it must have the proper flow characteristics to allow it to
readily flow between the regenerator and the reactor.
Thermal (free radical) cracking is the predominant cause for the removal of
hydrocarbon groups from the ends of a hydrocarbon chain, producing most of the
methane, and a large portion of the ethane and ethylene produced. Significant
quantities of the larger fragments (C3 and greater) are generally not produced by

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thermal cracking. Small amounts of C4 to C16 -olefins are produced. A high


percentage of the olefins that are formed condense directly to coke.
Catalytic cracking, by comparison, produces fewer C2 fragments and relatively few
C1 fragments. With catalytic cracking, cracking occurs at the strong acid sites in the
zeolite cage where the Brnsted acid sites occur. Cracking is by beta scission. The
fragments that are cracked off the large gas-oil molecule are mainly in the C3 to C6
range. A large number of olefins are produced. Because of the ability of the catalyst
to achieve rapid double-bond shifts, the linear olefins are generally in thermal
equilibrium with each other. However, since hydrogen transfer (H-transfer) is a
principal reaction and is selective for tertiary olefins, the isomeric olefins are present
in less than thermal equilibrium, since some of the isomeric olefins are converted to
the saturated isomer before desorbing from the catalyst surface.
Basically, the catalyst carries out two classes of reactions:

Primary reactions, which involve only a single molecule.


Secondary reactions, in which bimolecular reactions take place. These
reactions involve molecules formed from the primary reactions.

Cracking of the original large gas-oil molecule is a primary reaction. Such reactions
can be:

Paraffin smaller paraffin + olefin


Alkyl naphthene naphthene + olefin
Alkyl aromatic aromatic + olefin
Multiring naphthene alkylated lesser-ring naphthene

The secondary reactions are mainly associated with H-transfer reactions of one kind
or another and generally result in the saturation of an olefin:

Olefin + paraffin paraffin + olefin


Olefin + naphthene paraffin + aromatic
Olefin + olefin paraffin + diolefin (or coke)

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Olefin + olefin paraffin + aromatic

The isomerization of a straight-chain olefin, after the initial formation of the olefin, is
another important secondary reaction.
CATALYST COMPONENTS
To carry out its functions, the modern FCC catalyst is typically made up of four
separate but important components:

Zeolite (molecular sieve)


Active matrix component
Inactive matrix component
Binder

The inactive matrix component and the binder control the overall activity of the
catalyst by diluting the highly active components down to the proper activity level
and provide the proper particle strength and morphology. In the area of particle
strength, all catalyst suppliers have made major advances in catalyst attrition
resistance. In the 1990s, achieving good catalyst attrition resistance is generally not
a problem.
From a catalytic point of view, the zeolite and the active matrix components are the
items of principal interest.
The Zeolite
The zeolite provides controlled Brnsted (proton donor) acidity from its crystalline
structure and both Brnsted and Lewis (electron acceptor) acidity from the
nonframework alumina. Non-framework alumina exists as a result of the hydrothermal removal of alumina from the silica - alumina zeolite framework. Some basic
zeolite concepts help to understand how the zeolite functions.

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Zeolite Reaction Pathways


Zeolitic cracking is believed to begin with the transfer of a proton from the catalyst
surface to an olefinic double bond in the hydrocarbon molecule, thus forming a
carbenium ion. The double bond was initially created through a free radical thermal
cracking step or by a Lewis acid reaction initiated by an active alumina surface.
These steps are illustrated below.

Initiation: nC10H22

CH3(CH2)6CH=CHCH3+H2

Carbenium ion formation (Brnsted Acidity)


(Hydrocarbon)

C7H 15 C C CH3
+
H

C7 H15 CH = CH CH3

O
O
|
Si O AL O
|
|
O
O

H+ O
O
|
|
Si O AL O
|
|
O
O
(Protonated Catalyst Surface)

Hydrocarbon Adsorbed on Catalyst


Surface in Carbenium Ion Form

The carbenium ion migrates freely through the hydrocarbon molecule to


increasingly stable locations, and arrives at a position where the flexing of the CC
in the position sufficiently weakens the bond, cracking the bond to a smaller,
stable carbenium ion and an olefin. This mechanism is known as Beta scission.
H

C6 H13 C C CH2 CH3


H +

O
O
|
Si O AL O
|
|
O
O

C6H 13 + CH 2 = CH CH 2 CH 3

O AL O
|
O

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In this illustration, the -CH3 fragment at the other C-C position can not generate
enough vibration to crack the bond.
The carbenium ion also promotes rapid skeletal isomerization to the tertiary carbon
location, which is the most stable configuration, as:
CH 3

C 2 H 5 CH 2 CH 2 CH 2

C 2 H 5 C CH 3

O AL O
|
O

O AL O
|
O

It also promotes the bimolecular H-transfer reaction:

CH3

CH3

C2H5 C CH3 + C10H21


+

C2H5 CH CH3 + C10H20


+

O AL O

O AL O

O O AL O

O
O AL O
-

In this illustration, the hydrocarbon molecule receiving the H atom is no longer


attached to the zeolite particle and desorbs into the product stream. The molecule
which donated the H atom is now doubly attached to the zeolite particle, making it
more difficult to desorb. As the molecule continues to donate H atoms, it becomes
more and more strongly attached to the catalyst particle, to the point where it may
be impossible to desorb. It is then classified as coke.

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Zeolite Structure
The zeolite used in today's FCC catalyst is the Y-type faujasite. The tetrahedral
structure is the basis for the entire geometry of the Y-type faujasite. The tetrahedron
is present at the beginning when silicon and aluminum atoms are combined with
four oxygen atoms (Figure 1) in a tetrahedral arrangement. The silica and alumina
tetrahedra are then arranged at the vertices of a truncated octahedron known as the
sodalite cage. This cage has 8 hexagonal faces, 6 square faces (Figure 1), and 24
silica and alumina vertices.

Figure 1
Zeolite Molecular Structure

Tetrahedron

Sodalite

Silicon
or
Aluminum
Oxygen

The sodalite cages also combine tetrahedrally, through the hexagonal faces, with
other sodalite cages (Figure 2) to form the supercage, also known as the unit cell.
Eight sodalite cages make a unit cell. Some important dimensions of these
structures in a Y-type faujasite crystal are:

Sodalite cage
Entrance diameter 2.2

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Supercage
Entrance diameter 7.4
Internal diameter 13
Unit cell (as synthesized)
External diameter 24.67

Figure 2
Zeolite Molecular Structure
Sodalite
Cages

Supercage

Hexagonal
Prisms
Zeolites are frequently referred to as either a large pore zeolite, with a 12 member
ring pore entrance; as a medium pore zeolite, with a 10 member ring opening; or as
a small pore zeolite, with an 8 member ring pore opening. The Y-zeolite is a large
pore zeolite with a 12 member ring.

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The key to the performance characteristics of this crystal is that aluminum is


trivalent and thus does not fit comfortably into a tetrahedral arrangement with four
oxygen atoms, whereas silicon, being tetravalent, does. In such an arrangement,
the silicon atom is electrically neutral, but each aluminum atom takes on a negativeone charge. This charge is counterbalanced by a cation, such as Na+, NH4+, Ce+2
or La+3. The presence of these charged particles directly or indirectly produces the
protons on the catalyst surface that create the catalytic properties of the zeolite.
Zeolite Ion Exchange
When the catalyst is first manufactured, the charged particle on the catalyst surface
is not a proton. Rather it is a sodium cation that comes from the sodium aluminate
and sodium silicate used to produce the zeolite. Each supercage thus initially has
the formula:
Na54 (AlO2)54 (SiO2)138 (H2O)250
Each aluminum atom has a corresponding sodium atom. Also, when manufactured,
approximately seven aluminum atoms are in each of the eight sodalite cages, for a
total of 54 aluminum atoms per super cage.
In the sodium form, the crystal has poor hydrothermal stability because sodium
promotes dealumination of the crystal lattice. The sodium cation is therefore
removed by ion exchange during catalyst manufacturing and is replaced with either
ammonium cations, which form the Brnsted acidity protons directly upon heating in
the FCC unit, or with rare earth cations (principally lanthanum or cerium). The rare
earth cations hydrolyze water molecules on the catalyst surface and thereby create
the necessary protons. The rare earth cations are the most successful in preventing
crystal dealumination. Consequently, the early zeolitic catalysts used in the 1960s
and 1970s were fully rare earth exchanged.

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Zeolite Dealumination
Under the conditions of steam and high temperature that exist in an FCC
regenerator, all Y-type faujasite zeolites dealuminate to some degree, even if fully
rare earth exchanged. The crystal structure is attacked by water molecules, which
extract the aluminum and deposit it within the supercage as Al(OH)3:
O
|
O Al- O
|
O

OH
+ 4 H+OH-

OH

OH
OH

+ Al(OH)3 + Cation OH

The non-framework alumina (NFA) that is deposited has catalytic activity (Lewis
acidity). It tends to catalyze the formation of C2 and lighter gases, olefins, and coke.
The hydroxyl nest, which is formed when aluminum is removed from the framework,
represents a point of framework weakness that can lead to crystal collapse. In some
cases, silicon atoms migrate from the crystal surface into the crystal lattice in an
annealing type of operation and fill the vacancies left by the departing aluminum
atoms. Also, in other cases, silicon atoms from a collapsed framework react with the
NFA to form silica-alumina compounds.
A further effect of dealumination is that the crystalline structure shrinks in size, the
O-Si-O bond being smaller than the O-Al-O bond. The greater the degree of
dealumination, the smaller the crystalline unit cell size. Also, as aluminum is
removed from the crystal structure, the ratio of SiO2 to Al2O3 in the remaining
framework increases. The measurement of unit cell size by X-ray diffraction
techniques then becomes a convenient way to determine the SiO2/Al2O3 ratio of
the zeolite in a catalyst. Such a relationship is shown in Figure 3.

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Figure 3
Effect of Dealumination on Unit Cell Size

24.70

Unit Cell Size (ao)


of NA-Y Zeolite,

24.66
24.60
24.50

24.52 (US-Y)

24.40
24.30
24.20

5 8
10

20

30

40

50

60

SiO2/Al2O3 mol Ratio in Unit Cell

0 30 50 60

70

80

85

90

% Dealumination (Starting with 5.0 SiO2/Al2O3)

Because rare earth exchange prevents dealumination, the degree of dealumination


can be controlled by controlling the amount of rare earth exchange. Thus,
decreasing the degree of rare earth exchange decreases the number of aluminum
atoms in the unit cell and results in a smaller unit cell size (Figure 4).

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Figure 4
Effect of Rare Earth Exchange on

Equilibrated Unit Cell Size

Zeolite Unit Cell Size,


(After 5 hr 815oC Steaming)

24.45
24.40
24.35
24.30
24.25
24.20
0

10

12

14

16

% RE2O3 on 100% Y-Zeolite


One of the important catalyst developments in recent years was the realization that
important selectivity benefits can be achieved by reducing the amount of alumina in
the crystal structure. Because only the presence of aluminum atoms causes the
protons to exist on the catalyst surface, decreasing the aluminum atoms causes the
catalyst activity to decrease. Reducing the number of aluminum atoms also spreads
the active sites further and further apart, making bimolecular secondary reactions
(H-transfer) more difficult. This site reduction results in less olefin saturation (more
olefin production) and less coke formation and also increases the strength of the
individual acid sites by decreasing the interaction between sites. The net result is an
increase in C3 and C4 production and an increase in aromatic hydrocarbons in the
gasoline fraction. An important benefit is an increase in gasoline octane. These
trends are seen in Figures 5 to 9.

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Figure 5
Delta Coke at 65 wt% Conversion

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Figure 6
Gasoline Olefin Content at 65 wt% Conversion

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Figure 7
C6-C8 Aromatics at 65 wt% Conversion

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Figure 8
Gasoline RONC at 65 wt% Conversion

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Figure 9
Gasoline MONC at 65 wt% Conversion

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Changing the degree of zeolite dealumination has some other subtle effects on the
cracking reaction and on FCC operating conditions. Increased dealumination (lower
unit cell size) increases the endothermic heat of cracking and also increases
cracking activation energy. The multiple effects of changing unit cell size are
illustrated in Figure 10. Although the higher heat of reaction and lower delta coke
resulting from lower unit cell size increases the catalyst circulation rate and lowers
regenerator temperature, it also increases coke yield because of the effect of
increased heat of reaction on the FCC heat balance.

Figure 10
Effect of Equilibrium Zeolite Unit Cell Size

Specific Catalyst Activity


Coke

Heat of Reaction
Octane
Activation Energy

24.25

24.30

24.35

24.40

Equilibrium Zeolite Unit Cell Size ,

24.45

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The ZSM-5 Zeolite for Octane and Olefin Production


The ZSM-5 zeolite cage, with a 10 member ring pore entrance, has a smaller pore
mouth (~ 5.5 ) than the Y zeolite, with a 12 member ring and a 7.4 pore mouth.
ZSM-5 is designated as a shape selective zeolite, meaning that the hydrocarbons
that can enter the Zeolite cage are limited to the smaller molecules, such as the
linear and singly branched molecules in the gasoline boiling range. Large
molecules, such as found in VGOs, can not enter the ZSM-5 cage. ZSM-5 is
considered to be a medium pore zeolite, compared to the Y-zeolite, which is known
as a large pore zeolite.
ZSM-5 also has significantly fewer aluminum atoms in the cage structure than the
Y-zeolite, hence it has higher SiO2/ Al2O3 ratios. Depending on the zeolite synthesis
procedure, ZSM-5 type zeolites, as produced, can have SiO2/ Al2O3 ratios in the 30
-50 range (the most common range) up to a 300 500 ratio. The latter are
commonly designated as Silicalites, since they are nearly 100% silica. Despite the
fact that these zeolites have very few aluminum atoms in the cage structure, and
hence, very few active sites, they still have surprisingly good activity.
ZSM-5 mainly cracks the larger olefinic molecules (C7= to C12=) in the gasoline
range, reducing them to smaller olefins, mainly C3= and C4=, with C3=/ C4= ratios
typically > 1. Some ethylene is also produced from the cracking of the large
gasoline molecules. At typical FCC riser temperatures, ZSM-5 does not crack the
saturated paraffins nor the aromatics in the gasoline boiling range.
Since the high molecular weight , paraffinic molecules in gasoline are low octane
components, removing them via ZSM-5 cracking, with the corresponding
concentration of aromatics, results in an increase in gasoline octane, both RON and
MON. Consequently, in the 1980s, ZSM-5 containing additives were used to
enhance gasoline octane. They did, however, have the disadvantage of reducing
the yield of gasoline.

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As the demand for propylene increased in the 1990s, ZSM-5 additives began to be
used to increase the yield of FCC derived C3=. That trend has continued to
accelerate in the 21st century. Placing a high concentration of ZSM-5 crystalline
zeolite into the FCC catalyst blend can produce high C3= yields. Yields of up to 20
wt% C3= can be achieved with the proper feed and operating conditions, compared
to a C3= yield of 3-4% at conventional FCC conditions.
Catalyst suppliers are actively working to produce more effective ZSM-5 additives.
The additives produced in the 1980s typically contained 10% ZSM-5 crystalline
zeolite. As the demand for C3= increased, the need arose for FCC catalyst blends
containing higher amounts of ZSM-5. However, using large quantities of the 10%
additive resulted in a dilution of the base Y-zeolite catalyst. Since only the Y-zeolite
could crack VGO, the dilution resulted in an unacceptable loss of VGO cracking
activity. Additives containing higher contents of ZSM-5 were developed. A second
generation of additives containing 25% ZSM-5 was provided to the industry. Going
higher in sieve content and maintaining adequate attrition resistance proved to be
difficult, but eventually that problem was resolved. Additives containing 40% ZSM-5
with good attrition resistance are now available. Catalyst suppliers are now working
on developing a single particle catalyst which contains both a Y-zeolite and a
ZSM-5 zeolite.
Todays ZSM-5 additives are modified by the addition of phosphorous to the zeolite.
Phosphorous combines with aluminum atoms in the zeolite crystal structure,
through an oxygen bond, and enhances the stability and acidity of that alumina site.
Catalyst suppliers now routinely include the equilibrium catalyst phosphorous
content on their equilibrium catalyst report. Knowing the phosphorous content of the
fresh additive allows the refiner to tract the amount of ZSM-5 additive in their
equilibrium catalyst blend.
A typical set of results for increasing amounts of ZSM-5 additive is shown in
Figures 11 and 12.

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Figure 11

20

50

18

48

16

46

14

44

Gasoline

12

42

10

40
Butylenes

8
6

38
36

Propylene

34
Ethylene

32

30
0

0.5

1.5

2.5

ZSM-5 Crystal Content in FCC Catalyst - wt%

3.5

Gasoline Yield - wt%

C2=, C3=, & C4= Yields - wt%

Effect of ZSM-5 on Product Yields

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Figure 12
Effect of ZSM-5 On Gasoline Octane

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The Matrix
The matrix is defined as the entire catalyst particle except the zeolite. Its function is
to provide catalyst hardness, as well as to adjust the catalyst activity to the proper
level by diluting the zeolite, and to provide some special properties, such as
bottoms cracking activity and metals traps.
Zeolites have one major drawback: their porosity. The pore opening is too small
(7 to 8 ) to allow the large molecules with high molecular weight to enter the
zeolite cage. For this reason, some precracking must occur before the zeolite can
play a major role.
To some extent, the zeolite itself can provide this precracking function. The zeolite
has some external, active surface area that can be reached through the large inert
pores provided by the kaolin-silica binder matrix. Some mesopores in the 20 to 50
region are also created within the zeolite as a result of sieve collapse. These
mesopores can then provide some access to the zeolite interior. Consequently, the
zeolite itself can precrack a large percentage of the paraffinic molecules in the feed.
The large, multi-ring aromatic molecules create a more-difficult problem.
Active Alumina Matrix
The active alumina matrix component provides the catalyst with the ability to crack
these large molecules. As seen in Figure 13, the active alumina matrix provides
significant surface area and hence active sites in the 50 to 200 region. These
pores are sufficiently large to provide easy access to the large molecules and thus
allow precracking to occur.

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Figure 13
Effect of Matrix on Pore Size Distribution

When precracking is insufficient, as it usually is when no active alumina matrix is


present, too few intermediate products are fed to the zeolite, and the zeolite tends
to overcrack these intermediates. The net result is a loss in LCO yield (poor LCO
selectivity). Thus, the addition of an active alumina matrix benefits LCO selectivity,
and the benefit is greater for an aromatic feed than for a paraffinic feed (Figure 14).

Figure 14

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Effect of Matrix on LCO Yield

27
Aromatic Feed
@ 60% Conversion

LCO, wt-%

25
23
21

Paraffinic Feed
@ 75% Conversion

19
17
15
20

40

60

20

100

120

140

160

Matrix Area, m2/g

The typical active alumina matrix achieves its activity to a large degree through
Lewis acid sites. These sites are well known to cause coke and H2 formation. Thus,
the selectivity achieved via active alumina cracking is expected to be substantially
poorer than with zeolitic cracking. This reaction occurs for both paraffinic feeds and
aromatic feeds (Figures 15 and 16).

Figure 15

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Effect of Matrix on Coke Yields

5.2

Coke, wt-% FF

4.4
Aromatic Feed

3.6
2.8

Paraffinic Feed

2.0
1.2
20

40

60

20

100

Matrix Area, m2/g

120

140

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Figure 16
Effect of Matrix on Dry Gas Yields

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Catalyst Contaminants and Poisons


Contaminant Metals (Coke and H2 Production)
A number of metals typically found in FCC feed are deposited on the catalyst.
These metals, including nickel, vanadium, copper and iron can catalyze unwanted
dehydrogenation reactions to produce large quantities of coke and H2. Nickel is
typically the strongest dehydrogenation catalyst of these metals. Vanadium
generally considered to be as strong. Iron, which originates as organically bound
iron in the hydrocarbon molecules of the feed, deposits on the catalyst and is an
active dehydrogenation agent. However, most of the iron deposited on the catalyst
originates from equipment scale and is inactive. The combined iron content, which
is thus relatively inactive, is typically considered to be approximately 1/10 as strong
a dehydrogenation agent as nickel. Copper has as much dehydrogenation activity
as nickel but is usually present in much smaller amounts.
A frequent method for expressing the combined contaminant potential of these
metals is through the use of an equivalent nickel value, where: EqNi = Ni + Cu + V/4
+ Fe/10. Since Copper is usually present in very low quantities and iron is such a
weak dehydrogenation catalyst the equivalent nickel is often expressed simply as Ni
+ V/4.
The ratio of hydrogen to methane is an indication of metals catalyzed
dehydrogenation reactions. A sponge absorber off gas H2/C1 ratio for
uncontaminated catalyst should be 0.1 to 0.3. A figure of 1.0 or greater would
indicate metals contamination.
One method of evaluating the effect of contaminant metals on catalyst selectivity is
to monitor the equilibrium catalyst performance in a standardized laboratory test
(see page 61) as the metals content changes. Some typical catalyst coke and H2
responses to increasing equilibrium catalyst (E-cat) metal contamination are shown
in Figures 17 and 18. As seen in these figures, the response varies significantly
from catalyst to catalyst.

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Figure 17
Effect of Metals on Coke Factor
Coke Factor of Equil. Catalyst

3.0
C atalyst
F
A
B

C atalyst F

2.5

V /N i
3.3
2.4
0.5

2.0
C atalyst A & B

1.5
1.0
0.5
1,000

2,000

3,000

4,000

5,000

E q u ivalen t N ick el (N i + V /4), w t-p p m

Figure 18
Effect of Metals on H2 Factor
H2 Factor of Equil. Catalyst

8 .0
7 .0

C a ta ly st
F
A
B

C a ta ly st F

6 .0

V /N i
3 .3
2 .4
0 .5

C a ta ly st A

5 .0
4 .0
C a ta ly st B
3 .0
2 .0
1 ,0 0 0

2 ,0 0 0

3 ,0 0 0

4 ,0 0 0

E q u iv a le n t N ic k el (N i + V /4 ), w t-p p m

5 ,0 0 0

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Extrapolation of Figures 17 & 18 would indicate that nickel levels above 10,000
ppmw would result in totally unacceptable H2 and Coke Factors. Recent experience
has shown that these factors do not continue to increase linearly with increasing
nickel content. Rather, as seen in Figure 19, they reach an upper limit, which
depends upon catalyst design. It is believed that there is a limiting catalyst surface
area for supporting the deposited nickel. Once the metal has covered the available
area, additional metal deposits on top of already deposited metal and does not
generate any additional catalytic metal surface area.

Figure 19
Effect of Nickel Upon E-Cat H2 & Coke
0.9

4.5

0.8

4
Coke

0.6

3.5
3

Hydrogen

0.5

2.5

0.4

0.3

1.5

0.2

0.1

0.5

0
0

5000

10000

15000

20000

E-Cat Coke Yield - wt%

E-Cat H2 Yield - wt%

0.7

0
25000

Nickel on E-Cat - ppmw

Metals Passivation
The FCC feed additives that form chemical complexes with nickel have been
successful in reducing the dehydrogenation activity of nickel. Antimony compounds,
which have been in use for more than 30 years, are effective chemical additives.

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Data showing the reduction in H2 yield as a result of using antimony are shown in
Table 1.
Bismuth-containing additives have also been found to reduce the dehydrogenation
activity of nickel. Although somewhat less effective than antimony, the bismuth
additives have the advantage of being less of a concern from an environmental
point of view.

TABLE 1
HYDROGEN YIELD DECREASE EXPERIENCED BY
PHILLIPS LICENSES USING METALS PASSIVATION
Hydrogen Yield, SCFB FF

License

Catalyst
4 Ni + V,
Ppm

Unpassivated

Passivated

% Charge

3,600

92

58

37

16,200

202

104

49

6,540

64

21

67

10,820

126

62

51

8,800

87

55

37

6,140

161

103

36

8,300

105

85

19

10,800

71

19

73

9,300

159

109

31

Average

44

Reference: W.C. McCarthy, et al. Paper No. 13, Katalistiks 3rd FCC Symposium, 1982.

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Perhaps the most-active area in catalyst development in recent years has been the
development of active matrices that minimize the adverse effect of metals. One
advancement has been achieved through pore-structure adjustments and alteration
of the surface chemistry of the aluminas, using a large-pore boehmite alumina.
Such a matrix alumina is believed to encapsulate the nickel, so that the nickel
surface is no longer exposed and cannot make contact with the hydrocarbons to
catalyze dehydrogenation. With this technology, antimony additives provide only a
small additional benefit. Equilibrium catalyst material data illustrating the
performance of such a nickel trap are seen in Figure 20.

Figure 20
Catalyst Performance with Nickel Trap and
Antimony
0.25
V=1,000-2,000
wt-ppm

Without Nickel Trap & with Sb

H2 Yield, wt-%

0.20

0.15

Without Sb
With Nickel Trap

0.10

With Sb

0.05
0

Nickel, ppm (thousands)

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Contaminant Metals (Catalyst Deactivation)


Vanadium destroys the zeolite. In the presence of steam and high temperature
(regenerator conditions), vanadium forms vanadic acid, a highly mobile compound
that moves freely across the catalyst surface. It reacts with the aluminum in the
zeolite structure to form a low melting point eutectic compound that causes the
crystal structure to collapse. This collapse destroys activity. A typical example of the
effect of vanadium on equilibrium catalyst activity is shown in Figure 21.

Equilibrium Catalyst MAT Activity

Figure 21
Effect of Vanadium on Catalyst Activity
70
68
66
64
62
60
58
56
54

Catalyst Addition Rate


~ Constant at 1.7%
of Inventory/Day

52
3,000 3,500

4,000

4,500

5,000 5,500

6,000

6,500 7,000

Vanadium Content of Equilibrium Catalyst, wt-ppm


Vanadium traps have also been an area of considerable R&D activity. One family of
vanadium traps that appeared to have great promise was the titanate family,
particularly barium titanate. Laboratory testing in 1984-1985 indicated that catalysts
containing a barium titanate metals trap could sustain high levels of vanadium with

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little loss in activity and with little increase in H2 and coke production. Unfortunately,
when placed in actual commercial use, the titanates appeared to be sensitive to
sulfur poisoning and have not lived up to their laboratory performance. As yet, they
have shown little trapping capability in refinery use.
Rare-earth-based vanadium traps, which are much less susceptible to permanent
sulfur poisoning, have been considerably more successful in commercial refinery
use. This technology, which was originally commercialized by Katalistiks in the late
1980s, is now being used by Grace, designated as their RV technology. Grace
catalysts that incorporate the RV trap are called Residcats. The RV trap can be
used either as a separate additive or incorporated into the cracking catalyst particle.
Because of its high mobility, vanadium readily jumps from particle to particle,
seeking those particle locations where it has a high affinity. Separate particle
vanadium traps thus work nearly as well as in-catalyst traps. An illustration of the
effectiveness of the rare earth vanadium trap is given in Figure 22.

Equilibrium Catalyst MAT Activity

Figure 22
Effect of Vanadium Trap
72
70
68
Vanadium
Trap

66
64
Base Case

62
60
58
1,000

2,000

3,000

Vanadium on Equilibrium Catalyst, wt-ppm

4,000

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Sodium and other alkalis or alkaline earths such as calcium, potassium and lithium
are strong catalyst poisons which can have an immediate and significant impact on
catalyst activity. Sodium is usually present in the feed as salt resulting from
operational problems in the crude unit desalter or from purchased feeds from
tankers. Poor steam quality can also be a source of these contaminants. An
increase in sodium of just 0.1 wt% can cause a drop of up to 3 numbers in catalyst
activity.
Iron is another potential catalyst poison in high concentrations. If enough iron
accumulates on the surface of the catalyst the access to the active catalyst sites
may be blocked resulting in lower effective catalyst activity. Several units have
reported significant loss in catalyst activity when the iron on the equilibrium catalyst
exceeds ~3000 5000 wt ppm above the fresh catalyst iron level.
Basic nitrogen compounds in the FCC feed are temporary poisons that bond with
the active acid sites making them inaccessible for cracking reactions. The nitrogen
is oxidized off the catalyst during regeneration and leaves as NOx compounds in
the regenerator flue gas. The deactivation effect, thus, lasts only as long as the
basic nitrogen compounds are present in the feed. Typically, basic nitrogen
compounds make up about 1/3 of the total nitrogen compounds in the feed.
Coke can also be considered as a temporary catalyst poison, which sits on the
catalyst active sites and is removed during regeneration. If coke is not completely
removed during regeneration, a loss in actual catalyst activity will result. Typically a
loss of 1.0 1.5 activity numbers occurs for every 0.1wt% coke left on the catalyst.
Note that the activity numbers reported on a catalyst vendors equilibrium catalyst
report are determined after any remaining carbon is burned off. If the catalyst
leaving the regenerator does have a significant amount of unremoved coke, the
reported activity on the equilibrium catalyst sheet will thus not reflect the actual
lower, working activity in the reactor.

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CATALYST ADDITIVES
CO Combustion Promoters
In the early 1970s, researchers discovered that certain Group VIII metals,
particularly platinum, can be incorporated into an FCC catalyst system at low
concentrations (13 wt ppm) to catalyze the combustion of CO to CO 2 effectively.
Of even greater importance was their discovery that at this low incorporation, the
Group VIII metals did not catalyze undesirable dehydrogenation reactions during
the cracking reaction. The cracking-selectivity characteristics achieved by the
cracking catalyst in use in the FCCU are thus not altered when such a CO
combustion promoter is added to the catalyst inventory.
The use of 12 ppm platinum in FCCU circulating catalyst inventories is now widely
practiced throughout the world to catalyze the combustion of CO to CO2 in the
FCCU regenerator. The promoter is added to the FCC catalyst inventory either as
an integral part of the fresh FCC catalyst, where it is included in the fresh catalyst at
12 wt ppm, or as a separate additive. The additive, which typically contains
5001000 wt ppm of platinum, is added to the FCCU by a small metering system
that is independent of the fresh cracking-catalyst addition system. In the United
States, the separate additive approach is generally used; in Europe, the additive is
most commonly incorporated with the fresh cracking catalyst.
Through the use of a combustion promoter, CO combustion occurs readily in the
dense phase at temperatures well below 700C (1292F). It has been reported that
promoted CO combustion occurred as low as 650C (1202F) in a commercial
FCCU operation.
Promoted combustion has a number of important benefits. First, the afterburn
problem, i.e., burning in the dilute phase, is greatly reduced. By consuming CO in
the dense phase, the potential heat release from burning in the dilute phase is
significantly decreased. A commercial example of a 90F reduction in regenerator
afterburn by using a CO combustion promoter is as follows:

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Without promoter

With promoter

Typical flue gas temperature, F

1290

1220

Typical dense phase temperature, F


Afterburn T, F

1225
+ 65

1245
- 25

The increased flexibility of FCCU operations resulting from using a CO combustion


promoter is an even greater advantage. When using a promoter, the air rate to the
regenerator can be varied to achieve any degree of CO combustion that is desired.
By this mechanism, heat can readily be added to or removed from the regenerator
to produce changes in regenerator temperature, catalyst circulation rate, coke yield,
and reactor feed conversion.
In actual practice, the regenerator temperature is normally controlled at the
maximum temperature allowed by the regenerator metallurgy. Variations in feed
quality in the FCCU can result in significant regenerator temperature excursions if
the degree of CO combustion is unchanged (constant heat of combustion). With a
CO combustion promoter present, the degree of CO combustion can be varied to
hold the regenerator temperature constant at the desired maximum value even
though significant changes in feed quality have occurred. This flexibility is achieved
mainly through regenerator air rate control. To a lesser degree, additional flexibility
is achieved by controlling the addition rate of fresh CO combustion catalyst to the
catalytic cracker. When a CO combustion promoter is used, changes in the air rate
affect the amount of CO converted to CO 2 both in the dilute and in the dense
phase. Changing the amount of CO burned in turn affects both the dense- and
dilute-phase temperatures. Increasing the amount of excess O2 in the regenerator
causes an increase in CO burning in the regenerator dense phase as indicated by
an increase in dense-phase temperature. Additional burning in the dilute phase also
occurs, causing an increase in T (afterburning) between dense and dilute phases.
As a typical example, a decrease in CO content in the regenerator flue gas from 5
to 3 vol % would result in a dilute-phase temperature increase of 55F, a densephase temperature increase of 29F, and an increase in dilute-dense T of 26F.

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The amount of promoter used can also be a variable in influencing the degree of
CO combustion. A promoted catalyst system can be classified as fully or partially
promoted. A partially promoted system is one in which an increase in promoter
content results in a decrease in the dilute-dense T. Conversely, a fully promoted
system sees no effect on afterburn T when the promoter level is changed. An
increase in the promoter content increases the proportion of CO that is burned in
the regenerator dense phase, and decreases the dilute-dense T, as seen in
Figure 23 . The change in dilute-dense T is mainly because of changes in the
dilute-phase temperature. Changes in promoter concentration have only a small
effect on dense-phase temperature but greatly affect dilute-phase temperatures.

Figure 23

Additives to Reduce Sox in Regenerator Flue Gas


Recently, governmental regulations, particularly in the United States, have
significantly reduced the allowable FCCU emissions for sulfur oxides. A new 50
MBPD unit or an existing 50 MBPD unit being significantly revamped in 2002 would
be required to meet <0.7 t/d of sulfur oxides in the regenerator flue gas.

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Currently, many refiners find that the use of a SOx adsorbing additive is the most
effective way to comply with the EPA regulations.. With such an additive, the
following steps occur:
SO 2 is oxidized to SO3 in the regenerator:
2 SO2 + O2 2 SO3
SO3 is adsorbed in the regenerator by the SOx additive
SO3 + MO MSO4
MO = metal oxide and M is most commonly magnesium:
The metal sulfate is reduced in the reactor
MSO4 + CH4 MS + CO2 + 2 H2O
Release of H2S is released in the stripper
The metal oxide adsorbent is regenerated
MS + H2O MO + H2S
The H2S is carried out with the reactor products, goes through the product-recovery
system of the FCCU, and eventually to further processing for sulfur recovery. The
metal oxide adsorbent recirculates with the spent cracking catalyst back to the
regenerator for the next SOx adsorption cycle.
The first commercially effective metal oxide adsorbent consisted of a solid solution
of a pure magnesium aluminate spinel (MgAl2O4) with MgO. Such a solid solution (
Mg2AlO5) does not destroy the spinel framework. The adsorption activity of the
dispersed MgO in the spinel is much greater than that of pure MgO itself.
Cerium is effective in oxidizing SO2 to SO 3. Consequently, a cerium-impregnated
Mg2Al2O 5 actively converts the SO 2 to SO3, which is then strongly adsorbed by the
dispersed MgO as MgSO4. A completely cyclic SOx removal catalyst contains, in
addition to the above component, a fourth metal component such as vanadium to
catalyze the conversion of MgSO4 to MgO.
Multifunctional SOx removal catalyst systems have been in commercial use since
1985 in the United States. Such systems have successfully reduced SOx

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emissions in the FCCU regenerator by typically 20-60%, with reductions up to 90%


reported. Additive levels in the circulating catalyst inventory range from 1-10%. The
additive level and the amount of SOx reduction depend on conditions, such as feed
quality, the presence or absence of a CO combustion promoter, regenerator
temperature, regenerator mixing efficency, and excess O2 content.
Hydrotalcite, a MgO/Al2O3 containing compound, has also been found to have SOX
adsorbent capability and is now being used in some SOX adsorbent additives.
Recently, both spinel and hydrotalcite types of SOx reduction technology have been
upgraded to higher performance standards, frequently by the addition of more
magnesium oxide component.
Because O2 is necessary to convert SO2 to SO3, decreasing O2 in the regenerator
has been found to reduce the effectiveness of the SOx removal additive. The SOx
additives used in regenerators operating in a partial CO combustion mode, where
excess O2 is frequently limited to 0.2vol in the flue gas, are less successful in
reducing SOx. In such cases, SOx removal is typically 2030% less than for a full
CO combustion ( 1+ excess O2) case.
Additives to Reduce NOx in Regenerator Flue Gas
NOx (nitrous oxides ) emissions are now recognized as a significant contributor to
photochemical smog and acid rain, and therefore have come under greater
regulatory scrutiny than in the past. In terms of tons emitted per year, the FCCU
regenerator is one of the largest point source of NOx emissions. Only a small
portion of the NOx present in the flue gas is produced through the oxidation of N2 in
the regenerator air stream. The main source of the NOx comes from the
combustion of organic nitrogen, originating in the FCC feed of which approximately
50% ultimately reaches the regenerator section in the coke. However, only 5% to
20% of the organic nitrogen compounds entering the regenerator end up as NOx,
predominantly NO. The remainder is converted to N2. Since most of the organic
nitrogen ends up as N2, there is likely a secondary reaction with CO or coke to
reduce NO to N2. Although feed nitrogen is the source of NOx, researchers have
found that final NOx concentrations are due more to the type of N in the feed and to

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the regenerator conditions, than they are to the absolute content of N in the feed.
The amount of excess oxygen may have a more direct correlation with the final NOx
concentration leaving the regenerator. Increasing the O2 in the regenerator flue gas
from 0.1 to 1.6% has been reported to double NOx emissions when no CO
combustion promoter is present. Adding a platinum-based combustion promoter,
which increases the available atomic oxygen, can increase the NOx content much
more.
An emerging picture of the complex NOx chemistry in the FCCU regenerator
includes the following reaction networks:
Pyrolysis

Oxidation

N (Coke) HCN

N2, NO, N2O

N (Coke) NH3

N2, NO, N2O

NO Reduction
2NO + 2 CO coke N2 + 2 CO2
NO + CFAS* 1/2N2 + CO

* FAS = Free Active Surface

The use of platinum based CO combustion promoters, which decrease the CO


concentration in the regenerator, have been found to result in increased NOx
emissions. It is also believed that platinum promotes the combustion of HCN, further
increasing NOx.
Catalyst additives have had mixed results in reducing flue gas NOx emissions.
Recent research in NOx additives has taken two approaches: the development of
CO combustion promoters that do not catalyze NOx formation and additives that
directly reduce NOx emissions. Non-platinum combustion promoters such as
palladium and cerium on alumina have had some success. Copper on alumina has
had some success in converting NOx to N2.
Additives to Reduce Sulfur in Gasoline

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The latest additive development has been directed at reducing the sulfur content in
gasoline, which is believed to be largely due to the presence of thiophene and
alkylated thiophenes in the FCC gasoline. The additives are intended to
dehydrogenate the thiophenes which then can crack, releasing H2S. Zinc based
catalysts on an alumina support have had mixed results.
CATALYST SELECTION
An enormous amount of flexibility is available in the design of FCC catalysts. The
catalyst designer can choose from a large variety of zeolites. Depending on the
zeolite chosen, the designer can vary the amount of zeolite, the type of ion
exchange, and the type of active matrix and can include metals traps or additives.
This complexity is illustrated in Figure 24. Each unique combination of these factors
provides a uniquely different result, and each has some specific positive and some
negative benefits. Catalyst suppliers are continuously working to improve the
catalyst to provide more flexibility to meet the specific needs of each individual
refiner.
The catalyst advancements are mainly related to improved coke and gas selectivity
in the presence of contaminant metals and in the presence of increased matrix
activity for better bottoms cracking and LCO selectivity.
Because of the wide variability in catalyst options and the individuality of each
refinery's situation, generalizing as to which catalyst is best should be avoided. The
choice is best arrived at when the refiner and catalyst supplier work closely together
to take advantage of the catalyst flexibility available. UOP can also assist in this
selection process by providing an assessment of the various catalyst options based
on commercial experience in other UOP units and on standardized testing in UOP
pilot plants.

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Figure 24
Catalyst Formulation

ReHY

USY

Other Zeolite
Treatments

ZSM-5

Low-Activity Matrix

Active Alumina
Matrix

Nickel Trap

Vanadium Traps

Plus

Rare Earth Variations


Variations in Total Sieve Content
Combustion Promoter
Bottoms Cracking Additives
Environmental Additives

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TIME AND TEMPERATURE EFFECTS


High temperatures in the presence of steam will result in loss in catalyst activity.
This condition exists in the regenerator where steam is formed as a result of
burning the hydrogen in the coke and in the lift zone of the reactor. The rate of
hydrothermal deactivation is relatively slow at temperatures below 1300 F (700 C)
and increases rapidly at temperatures greater than ~1350 1400 F (730 760 C)
although thermal stability varies from catalyst type to catalyst type. Generally,
hydrothermal deactivation in the FCC unit is minimal because the temperatures are
typically lower than 1350 F (730 C). Steam used in the reactor for feed
atomization and spent catalyst stripping does not contribute significantly to
hydrothermal deactivation because of the relatively low temperatures in the riser
and stripper. For a given catalyst over a set period of time (say one hour), a
graphical representation of the resultant catalyst activities at various temperature
levels is shown in Figure 25.

Figure 25
Catalyst Hydrothermal Deactivation

M.A.T. Conversion, wt%

80
75

Catalyst A
Catalyst B
Catalyst C

70
65
60
1350

1400

1450

1500

Deactivation Temperature, F
5 hours - 100% Steam

1550

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Use of torch oil can also result in thermal deactivation if the oil is not properly
atomized.
CATALYST MANAGEMENT
The type of catalyst used in a particular FCC unit depends on feedstock properties,
the desired product make, and unit bottlenecks. The choice of catalyst should be
made after careful study of all factors, including cost. Any catalyst changeover will
take significant time to be effective. Varying feedstocks and operating conditions
may also change yields and cloud the results of catalyst changes.
Fresh catalyst is typically added to the unit for two reasons:
1.
2.

To maintain catalyst quality.


To replace physical losses.

If the unit holds catalyst well, it may be necessary to withdraw equilibrium catalyst
and add fresh to maintain a desired activity. If the catalyst has been damaged by
excessive use of steam or torch oil, or contaminated by metals, it may be necessary
to increase the catalyst makeup rate.
The desired catalyst activity is based on several factors, the first of which is
economics. The refiner should examine.
1.

Relationship between yield and activity.

2.

Value of any extra conversion.

3.

Rate of catalyst degradation at higher yields.

4.

Ability of downstream units to handle extra conversion.

5.

Cost of catalyst.

The addition of fresh catalyst should be done as evenly as possible. There are a
variety of continuous loaders on the market which make this quite easy.

157048
Catalyst
Page 50

If a large batch of fresh catalyst is added too quickly, the relative activity increase
may cause overcracking with lower gasoline and higher dry gas yields.
The unit should be monitored with plots to follow:
1.
2.
3.
4.
5.

Catalyst activity. This is normally done weekly by the catalyst supplier.


Makeup and withdrawal rates.
Reactor and regenerator temperature.
Conversion levels and product yields.
H2/C1 ratio This will indicate possible metals poisoning.

These procedures are required for routine monitoring of the unit. Moreover, without
them, it is impossible to make intelligent decisions on catalyst management.
It may be necessary to add catalyst to make up physical losses. These can be due
to excessive or improper steam usage, equipment damage such as a bypassed
cyclone If catalyst losses are severe, or fresh catalyst addition is not desirable,
equilibrium catalyst can be added, either from a newly purchased stock or from onhand stock.
In some units, low metals equilibrium catalyst is added to replace higher metals
catalyst from the inventory. This is an effective way to reduce the levels metals and
therefore minimize the negative effects of the metals without the high cost of adding
large amounts of fresh catalyst. This is especially true in units with resid feed stocks
which are typically higher in metals than VGO.
Catalyst loading and use should be reviewed periodically to ensure proper unit
operation. This review should normally be done about every two months. If there
are special problems such as metals, the policy will have to be reviewed more
often. Care should be taken, however, that other factors such as different
feedstocks do not lead to hasty, inappropriate decisions.

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Catalyst
Page 51

CALCULATION OF FRESH CATALYST ADDITION RATE


The fresh catalyst addition rate is a critical factor in the operation of an FCC unit
and in maintaining a desired catalyst activity. The following sample calculation
illustrates a method of approximating the addition rate to achieve a desired activity.
Basis of calculation:
1.

Fresh catalyst activity is 79.

2.

Equilibrium catalyst activity is 69.

3.

Desired catalyst activity is 73.

4.

Present addition rate is 2.5 short tons/day.

5.

Unit inventory is 200 short tons.

6.

Catalyst retention factor is 0.80.

The retention factor is an index attrition number which accounts for the weight
fraction of fresh catalyst that is not lost from the regenerator during loading.
Generally, the retention factor will vary from 0.70 to 0.80 depending on the specific
catalyst.
1.

Calculate average catalyst age


ACA = INV/CAR
where:

ACA
INV
CAR

=
=
=

Average catalyst age in days


Unit inventory in short tons
Present catalyst addition rate in short tons per day

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Catalyst
Page 52

In our sample calculation:


ACA = 200 tons/2.5 tons per day = 80 days
2.

Calculate the deactivation constant


DC = [LN ( FCA ) - LN (ECA)] /ACA
where:

DC

Deactivation Constant

FCA
ECA

=
=

Fresh Catalyst Activity


Equilibrium Catalyst Activity

ACA

Average Catalyst Age in Days

In our sample calculation:


DC = [LN (79) - LN (69)]/80
DC = 0.00169
3.

Calculate the new catalyst addition rate


NAR = [INV x DC x RF]/[LN (FCA) - LN (DCA)]
where:

NAR
INV
DC
RF
FCA
DCA

=
=
=
=
=
=

New Catalyst Addition Rate in short tons per day


Unit Inventory in Short Tons
Deactivation Constant
Retention Factor
Fresh Catalyst Activity
Desired Catalyst Activity

In our sample calculation:


NAR = 1200 x 0.00169 x 0.80]/lLN (79) - LN (73)
NAR = 3.43 short tons per day

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Catalyst
Page 53

4.

Calculate the time required for 75% turnover at the new addition rate.

PCT
Inventory Turnover = - LN 1 INV / NAR RF

100

where:

PCT
NAR
RF

=
=
=

Percent Turnover desired


New Catalyst Addition Rate in short tons per day
Retention Factor

In our sample calculation:


Time Required for 75% Inventory Turnover
75

= - LN 1 200 / 3.43 0.80

100

= 101 days

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Catalyst
Page 54

CALCULATION OF METALS ON EQUILIBRIUM CATALYST


Excessive metals concentration on equilibrium catalyst results in undesirable
dehydrogenation reactions and loss of catalyst activity. The following sample
calculation outlines a method of predicting the current metals concentration on
catalyst.
BASIS:
Feed Rate
Feed Specific Gravity
Metals in Feed
Catalyst Addition Rate
Metals on Catalyst Addition
Initial Metals on Equilibrium Catalyst
Equilibrium Catalyst Inventory

20,000 BPD
0.9042
3 ppm
2.5 Short Tons/day
ppm
1,000 ppm
200 Short Tons

Find metals concentration after 100 days of operation at the above conditions.

0.175 SG FFR FFM


CAR TS
-
EMI
FCM

EXP

EMF =

CAR
INV

0.175 SG FFR FFM


+
+ FCM

CAR
where:
EMF
EMI
FCM
SG
FFR

=
=
=
=
=

Final Equilibrium Catalyst Metals Concentration in ppm


Initial Equilibrium Catalyst Metals Concentration in ppm
Catalyst Addition Metals Concentration in ppm.
Feed Specific Gravity
Feed Rate in BPD

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Catalyst
Page 55

FFM
CAR
INV
TS

=
=
=
=

Metals Concentration on Feed in ppm


Catalyst Addition Rate in Short Tons per Day
Reactor/Regenerator Catalyst Inventory in short tons
Time Period in Days

0.175 0.9042 20000 3


2.5 100
1000
0

EXP

EMF =

2.5

200

0.175 0.9042 20000 3


+ 0
+

2.5

EMF

2996 ppm

CATALYST PROPERTIES AND TESTING


Catalyst manufacturers routinely test for their customers catalyst samples taken
from the FCCU circulating catalyst inventory. These are referred to as equilibrium
catalyst samples, or E-cat samples. Samples are taken generally on a weekly or biweekly basis, but, in special situations, can be taken more frequently. Samples are
also sometimes taken of the fines leaving the FCCU, when the FCCU appears to
have a catalyst loss problem. The evaluation report which a catalyst manufacturer
prepares contains valuable information that provides the refinery with a better
understanding of the unit operation and enables him to improve the operation of the
FCC unit. If the FCCU is having problems, the E-cat data can tell the refiner if the
problems are related to deteriorating catalyst performance or whether he should
look to mechanical problems in the unit.
At present, there are no standard catalyst testing procedures used by the various
catalyst manufacturers. Results for the same sample will most likely differ from one
laboratory to another. Catalyst reports are more useful as trend indicators than as
reliable guides based on their absolute values.

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Catalyst
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A catalyst test report will include information on the physical, chemical, and catalytic
properties of the equilibrium catalyst.
Under the category of physical properties, information will frequently be found on:
Catalyst surface area total area, zeolite area, and matrix area
Zeolite unit cell size
Catalyst bulk density
Catalyst pore volume
Catalyst particle size distribution
Catalyst fluidization properties
Following is a description of the various tests performed by laboratories:
PHYSICAL PROPERTIES
Surface Area
The body of catalyst particles is made up of pores which contain the active sites
where the cracking reactions occur. Nearly all (90 95%) of the catalyst's surface
area is internal. The total surface area, measured in square meters per gram of
catalyst, is made up of two components, the zeolite surface area and the area of the
material around the zeolite, known as the matrix surface area.
The zeolite surface area is the larger of the two and is a good indicator of the
catalyst activity. The zeolite surface area measures the area within the pores of
about 50 or less. The matrix surface area measures the surface area in the pores
> 50, which provide the channels through which the hydrocarbons can reach the
zeolite. The active alumina incorporated for bottoms cracking is found in this higher
pore range.
Surface area is measured by nitrogen adsorption at very low pressure. Total
surface area is typically determined by the BET method which measures adsorption
at a single pressure. Matrix surface area is determined by the t-plot method, which

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Catalyst
Page 57

measures adsorption over a wide range of pressures. Zeolite surface area is


typically obtained by difference.
Typical surface area values for Y-zeolite based catalysts range from 70-200 m2/gm
for equilibrium catalyst and up to 400 m2/gm for fresh catalyst. ZSM-5 has a much
lower surface area than does Y-zeolite. Unlike Y-zeolites, ZSM-5 loses little, if any,
surface area upon exposure to regenerator conditions. A ZSM-5 additive containing
25% crystalline ZSM-5 zeolite would be expected to have a surface area in the 70 90 m2/gm range, both in the fresh condition and in the deactivated condition.
Apparent Bulk Density (ABD)
The apparent bulk density of the catalyst is its density measured in grams / cc.
Fresh catalysts have ABD's ranging from 0.7-1.0 grams/cc, while equilibrium
catalysts vary from 0.75-1.0. The ABD depends upon the chemical composition,
pore volume, and particle size distribution.
Hydrothermal deactivation causes the fresh catalyst to both lose moisture content
and to shrink somewhat in size. With regard to bulk density, these are counteracting
influences. Bulk density, thus, does not change greatly due to hydrothermal
deactivation. Thermal deactivation, which can occur with an extreme regenerator
temperature excursion, does cause significant collapse of both the sieve and matrix
and hence causes a significant increase in bulk density. Monitoring the equilibrium
catalyst bulk density can provide an indication of such an event.
FLUIDIZATION CHARACTERISTICS
Some catalyst suppliers routinely test the catalyst in a fluidization test stand and
report the ratio of minimum bubbling velocity / minimum fluidization velocity
UMB /UMF. This ratio is a measure of the range of catalyst densities within which a
smooth standpipe operation is obtained. The larger the value, the better.
Particle Density

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Catalyst
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Particle density is the weight per unit volume of catalyst. Particle density is defined
as:
Skeletal Density
+ 1
(Skeletal Density Pore Volume)

Particle density is always less than skeletal density. A comparison of density would
be:
Particle Density 2 ABD 1.7 CPD
Compacted Particle Density (CPD) is similar to ABD, but the catalyst is tapped until
it settles to a minimum volume.
Skeletal Density
Skeletal density is the density of the solid portion of the catalyst, exclusive of the
volume of pores or voids. The values are obtained with a pycnometer after
determining pore volume. Typical skeletal density for low alumina catalyst is 2.35
g/ml; for high alumina the density is 2.5 g/ml. The zeolites fall somewhere in
between these two.

Pore Volume
Pore volume is another indicator of the zeolite content of the catalyst. Higher pore
volume would usually indicate higher zeolite content for two catalysts of the same
type, but would not necessarily indicate higher activity. Pore volume can be
determined by N2 adsorption, or by water titration. The values reported on the
equilibrium catalyst sheet are obtained from a water titration.

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Catalyst
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The pore volume of equilibrium catalyst generally ranges from 0.2-0.5 cc/gm. The
variation here is because of the many different types of catalyst, and because of
different manufacturing techniques. Hydrothermal deactivation causes a slight
decrease in pore volume, while thermal deactivation causes a greater decrease.
Pore Diameter
This is a convention used to describe the average pore size. The assumption is
made that the pores are in the form of minute cylinders of diameter, PD, and length,
L. By definition then, the following equations apply:
SA = (PD)L
Pore Volume (PV) =
Therefore:

(PD)2L
4

PV
(PD)2 1
PD
= L
=

SA
4
4 (PD) L

Therefore:
PD =

4 PV
SA

Using:
SA in m2/g
PV in cc/g
PD in Angstroms
The equation then becomes:
PORE DIAMETER (PD) =

4 PV 104
SA

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Catalyst
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Attrition Resistance
The attrition resistance of catalyst is an indication of its strength and hardness. A
more attrition-resistant catalyst will erode at a lower rate as it circulates through the
unit. Each catalyst supplier has their own technique for measuring attrition
resistance. Comparing one suppliers attrition value with another suppliers value is
not recommended.
Typical FCCU catalyst loss due to attrition is approximately 1 wt% of the catalyst
inventory per day.
Particle Size Distribution
The fluid properties of the catalyst are largely a function of the range of particle size.
Typical particle size distributions are:
% under 20 microns
% under 40 microns
% under 60 microns
% under 80 microns
% under 100 microns
Average Particle Size (APS)

1
10
33
55
73
75 microns

The average size, in microns, of the particles contained in a catalyst sample is


determined by the 50% point on a weight distribution plot. Equilibrium catalyst
usually has an APS of 65-85 microns.
The desirable particle size distribution is the coarsest one that still gives good
fluidization. This coarse distribution will also result in minimum catalyst entrainment
with the exiting gases. The catalyst will erode with time and provide its own supply
of fines, leading to a gradual catalyst loss.

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Catalyst
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Satisfactory fluidization demands a range of particle sizes. The percentages of


particles under 40 microns and over 100 microns are good indicators of the
performance to be expected from the catalyst. UOP FCC units are designed for
relatively coarse catalyst and normally operate quite satisfactorily with 5% or less of
particles smaller than 40 microns.
LOSS ON IGNITION
This is the amount of material which the catalyst loses after heating for a specified
period at temperatures in the range of 1000 to 1100F. Catalyst is usually sold on a
dry basis but shipped with some moisture present. Typical values are 10-15% by
weight. If the moisture content is too high, there may be problems with catalyst
packing in the hopper. If the value is too low, less than 5%, the catalyst has been
over dried. This could adversely affect activity and make smooth addition of fresh
catalyst difficult, due to static electricity.
CATALYTIC PROPERTIES
The catalyst's conversion ability is determined by testing in a small micro reactor
system at standard conditions. The test measures the equilibrium catalyst's activity
and selectivity. A decoked catalyst sample is used to crack a typical FCC feedstock
in a laboratory reactor. The resulting liquid and vapor products and the catalyst
coke content are analyzed and the results compared to a laboratory standard.
A catalyst activity number is reported, which is related to the conversion achieved in
the lab test, while the selectivity values relate to the catalyst's undesirable
characteristics of producing coke, light hydrocarbon gases, and hydrogen. These
data are found on each catalyst suppliers equilibrium catalyst sheet. Each
laboratory has its own unique feed and operating conditions for this test. Although
each catalyst suppliers reported values on the same sample will be different, their
values will not be greatly different, and changes reported from one sample to
another should be relatively the same.

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The test method does not duplicate commercial performance so the results are only
relative. By comparing the results to a standard, however, the performance of the
sample in a commercial unit can be predicted. It is important to remember that the
sample is tested after any remaining coke is burned off so in units with high carbon
on regenerated catalyst the reported activity will not correlate with the activity in the
commercial reactor.
SELECTIVITY
The selectivity values reported for an equilibrium catalyst relate its tendencies to
form coke, C1-C4 gases, and hydrogen to those of a standard reference catalyst
when corrected to the same conversion. Selectivity is affected by the catalyst type
as well as varying degrees of metals contamination.
The catalyst's coking characteristic is measured by the coke factor, CF, which is
dependent on the accumulated Ni + V level. This coke factor can be used to
separate the effect the catalyst type and its accumulated metals level has on coking
from the effects due to processing conditions such as the actual FCCU feedstock's
coking tendency and the FCCU reactor temperature.
Hydrogen (H2) production is also very sensitive to the catalyst metals
contamination. The H2 producing tendency is measured by the H2/CH4 factor which
usually varies from less than one up to two for metals levels up to 1500 ppm. Some
catalyst suppliers provide a H2 yield value from their standard test.
The other selectivity value which relates to the catalyst's gas yield is the gas factor,
GF. This, like the coke factor, varies with the fresh catalyst type, but it is not as
metals sensitive as is the coke factor or the H2 value . Generally, the gas factor will
not give an increasing trend until the metals accumulation exceeds 2000 ppm. This
factor is used to separate the effect the catalyst type and its contamination has on
light gas production from FCCU processing conditions such as reactor temperature,
regenerator temperature, or the feedstock quality.

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CO COMBUSTION TEST
Some catalyst suppliers test the equilibrium catalyst for its ability to combust CO to
CO2. The reported value is given as the performance of the catalyst relative to a
catalyst that is considered to be fully loaded with a CO combustion promoter.

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Process Variables
Page 1

PROCESS VARIABLES
INTRODUCTION
Proper control of an FCC unit requires careful balancing of many variables. Within
certain limits, the system can be controlled to provide optimum performance. The
limits, or restrictions, include feedstock quality, equipment limitations, and environmental constraints.
Of primary interest is the unit enthalpy balance which results from the many unit
operating conditions. The amount of coke produced in the reactor is a direct result
of the operating conditions imposed on the unit by the operator and is relatively
independent of the feed quality. The unit yields are directly related to the quality of
the feed and the operating severity set by the enthalpy balance. As these topics are
developed in this chapter, it will become clear that many of the assumptions made
by FCC operators are incorrect and a better understanding of the relationships of
the process variables is necessary to properly predict unit operation.

REACTOR-REGENERATOR HEAT BALANCE


The most fundamental principle in the operation of the FCC unit is that in steady
state operation the reactor will produce just the amount of coke necessary for the
regenerator to burn to satisfy the reactor energy demand. This is called the heat
balance. The calculation of the heat balance is shown in the calculation section of
this book. In this section, the relationship of coke burning to coke production will be
discussed.

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Process Variables
Page 2

The amount of energy flowing in the unit operation can be summarized as:
Energy In + Energy Produced = Energy Out + Energy Consumed
Energy In

= Energy in the air to the Regenerator, raw oil, steam, and lift
gas

Energy Produced

= Heat of Combustion from Coke

Energy Out

= Energy in the Flue Gas, Reactor Vapor, Steam from the


Cat Cooler, Radiation Loss

Energy Consumed

= Heat of Reaction, Sensible Heat of the Feed, and the Feed


Latent Heat of Vaporization

At steady state the net heat of combustion must equal the heat consumed by the
reactor. Stated mathematically:
NET HEAT OF COMBUSTION

BTU
[Hcomb - Hair - Hloss]
LB COKE
MUST EQUAL
TOTAL REACTOR HEAT LOAD

BTU
[Hfeed + Hdiluent + Hrecycle + HRx]
LB FEED

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Process Variables
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The coke yield from the unit can then be written as:
BTU
100 Hfeed + Hdiluent + H recycle + HRx
LB FEED
WT% COKE YIELD ON FEED =
BTU
Hcomb - H air - Hloss
LB COKE

Note that the coke yield depends on the energy balance of the unit and the only
term that represents feed quality is the heat of reaction. Thus as feed quality
changes and the heat of reaction changes, there will be a change in coke yield.
Otherwise, the coke yield is set by the operating conditions imposed by the
operator.
THE ENTHALPY OPERATING WINDOW
Let us take as an example a unit operating in full CO combustion with a heavy gas
oil feed in once-through (no recycle) operation. As shown in the calculation section,
the enthalpy changes for diluents and normal vessel heat losses are negligible, so
the coke yield equation can be simplified to:

WT% COKE =

100 H feed + H Rx
H Comb Net

The unit control variables then become the feed temperature and the reactor
temperature. The usual range of feed temperature is 350-520F and 970-990F for
the reactor so a table showing the enthalpy changes for these ranges is:

CONTROL VARIABLE

DEPENDENT VARIABLE

REACTOR TEMP.

970 - 990F

H REACTION

FEED TEMP.

350 - 520F

REGEN CAT. TEMP.

409 - 530

BTU/LB FEED

H FEED

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Process Variables
Page 4

Thus, the maximum range in coke yield variability for these operating ranges is
4.8-5.8 wt%. The potential change in coke yield due to any variation in dependent
variable such as heat of reaction, flue gas temperature, feed enthalpy and heat of
reaction is extremely limited. The following table shows the range of coke yields for
various variable changes.

DEPENDENT
VARIABLE
HEAT REACTION
REGEN TEMP.
H2 IN COKE

RANGE

ENTHALPY

COKE YIELD

LOW/HIGH CONV.

100 - 200
BTU/Lb Fd

4.6 - 5.5

1250 - 1400F

3407 - 4010
BTU/Lb Coke

5.14 - 5.39

6.0 - 7.0

16547 - 17000
BTU/Lb Coke

5.5 - 5.3

The net coke yield is thus essentially independent of feed quality. The conversion
and the cat/oil ratio are the variables that change with varying feed quality. In
essence, conversion coke from the quality feed is replaced by contaminant coke
from the poor feed at a correspondingly lower conversion.
Another way to look at this balance is to look only at the components of the reactor
side heat balance.

Feed Enthalpy Requirement


Stripping Steam Enthalpy
Feed Steam Enthalpy Requirement
Heat of Reaction
Heat Loss
TOTAL

BTU/Lb Feed
530
5
13
180
2
730

%
72.6
0.68
1.78
24.67
0.27
100

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Process Variables
Page 5

Over 70% of the coke produced in the unit is used just to heat up and vaporize the
feed. Only about one fourth of the coke is used to provide the heat of reaction. As
we saw above, the heat of reaction does not vary very much from feed to feed, so
the range of coke production can be seen clearly to be limited to less than half of
25% or about 10% of its typical value. In most units this corresponds to 5.5 wt%
plus or minus 10% (5.0 to 6.05) even for wide swings in feed quality and conversion
level.
THE DELTA COKE OPERATING WINDOW
Now that the coke yield on feed is known to be set by the operating conditions in the
unit, the next important term in the heat balance is the 'delta coke'. Delta coke is the
difference in coke content between the regenerated catalyst and spent catalyst.
Another way to express this is the coke yield on feed divided by the catalyst/oil ratio.

DELTA COKE =

ENTHALPY COKE
(or COKE YIELD)
CAT/OIL

Since the coke yield is set by the operating conditions, the cat/oil and the delta coke
must vary proportionally opposite to each other. The delta coke term is strongly
related to the regenerator temperature and thus the product selectivities.

C
TRegen = TRx +
Hcomb - Hair - Hloss
Cp
where:

Cp = catalyst heat capacity


C = delta coke

Rearranging the equation, the cat/oil ratio can be calculated knowing the
regenerator and reactor temperatures, and the coke yield from the heat balance
calculation.
Cat /Oil =

Coke Yield wt%


100 Cp

H Comb Net

TRegen

- TReactor

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Process Variables
Page 6

At constant operating conditions if the delta coke is changed the regenerator


temperature and cat/oil ratio will vary as follows:

DELTA COKE

0.5

0.775

0.928

1.137

REGEN TEMP F

1250

1330

1390

1470

CAT/OIL

11.4

7.6

6.5

5.4

5.7

5.91

6.03

6.18

COKE YIELD WT%

BASIS: 980F Rx, 350F Feed, 190 BTU/Lb Feed HRx, FULL CO
COMBUSTION, 1.0 CFR

The delta coke function therefore impacts conversion and selectivity enormously
due to its influence on regenerator temperature and corresponding cat/oil. At the
same time, since the regenerator temperature has little influence on the enthalpy
coke, the coke yield changes very little for large variations in delta coke at constant
heat of reaction.
HEAT REMOVAL FROM THE REGENERATOR BY CATALYST COOLING
Since we have just seen that the coke yield is set by the operating conditions and
not the feed quality, what can be done when a poor quality feed must be processed
and the conversion is not sufficient at the current operating conditions? At the same
time, this poor quality feed usually will result in a higher regenerator temperature as
well, causing a decline in liquid product yield. If a constant coke yield is required
due to an air blower limitation, any heat input to the reactor side must be offset by a
similar heat removal on the regenerator side. With the installation of a catalyst
cooler, the feed preheat can be increased to reduce the coke make, and a
corresponding heat removal via catalyst cooling can be done in the regenerator to
increase the cat/oil ratio and increase conversion to maintain constant coke

157048
Process Variables
Page 7

production. The overall yields can be greatly improved through the increase in
catalyst circulation. The higher E-cat activity resulting from the lower temperature
also improves the yields.
COKE YIELD FLEXIBILITY FOR OPTIMUM PERFORMANCE
The prime objective of most FCC operations is the conversion of feedstock to
gasoline and other valuable products, while minimizing the production of less
valuable products such as clarified oil and coke. The unique feature of an FCC unit
is that it supplies its own fuel, not only for the conversion to the products it
produces, but also for the fractionation of the products as well. This fuel is the byproduct of the cracking reactions left on the catalyst, commonly referred to as coke.
It has been the quest of designers not only to minimize coke on catalyst from the
cracking reactions, but to minimize coke on catalyst from other sources as well. It
has been documented that coke on catalyst can come from feed contamination
such as metals, coke added by the high boiling fraction of the feed, and by
entrainment from the catalyst circulation through the reactor stripper. The objective
is to produce the most desirable yield pattern for a given feedstock with the least
amount of coke possible. Once a unit is designed, it has a certain coke burning
capability which the operator can utilize to increase cracking severity as much as
desired for each feedstock. With heavier feeds that contain less hydrogen and
inherently produce less liquid yield volume, high coke burning capabilities are
needed and a way to increase the coke yield to improve yields is needed. The key
is to produce enough coke to increase the conversion of the feed until the optimum
yield pattern is achieved.
QUALITY AND CONDITION OF CHARGESTOCK
The typical feed to an FCC unit is a heavy gas oil, such as heavy atmospheric, light
vacuum, and heavy vacuum gas oil. The unit can accommodate a range of different
rates and types of feed within its design limitations. Typically a unit may run at
design conditions, at a higher charge rate with moderate conversion, or at low
charge rates with very high conversion levels.

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Process Variables
Page 8

Some FCC units recycle heavy oil from the main column back to the riser. The
amount is defined by the combined feed ratio:

CFR =

BPD raw oil + BPD total recycle


BPD raw oil

Typical combined feed ratios for riser cracking units operating with a higher activity
catalyst would be 1.0-1.10. Older units running on low activity catalyst could range
from 1.2 to 1.8. If the oil can be cracked on one pass and not recycled, more fresh
feed can be processed. The recycle is generally heavy material which tends to be
more difficult to crack, and when it does crack, it makes more coke and light gas
than does the fresh feed. Many refiners run only enough recycle to return catalyst
fines to the reactor from the main column. This generally means a CFR of 1.05 or
less.
Proper control of upstream units, such as the vacuum column, is essential to good
feed quality. This control is mentioned only briefly in the following discussion
because it is beyond the scope of this work, but will affect all the variables listed
below.
There are several important characteristics which are used to describe the raw oil
charge. These relate to its ease of cracking and to most potential problems. The
major elements are:
RAW OIL CHARGE CHARACTERISTICS
1.
2.
3.
4.
5.
6.

API GRAVITY AND UOP K (HYDROGEN CONTENT)


BOILING RANGE
AVERAGE BOILING POINT
CARBON RESIDUE
METALS
SULFUR, NITROGEN, AND OXYGEN

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Process Variables
Page 9

API GRAVITY
API gravity is a specific gravity relating the density of oil to the density of water.
Feed to an FCC can range from 15 to 45 API, with 20-25 API the most common.
Any change in this number is due to a change in boiling range, crude type, or both.
If the API gravity increases because the feedstock is more saturated (paraffinic and
less aromatic), the following changes can be expected:
1.

The charge will crack more readily for the same reactor temperature and there
will be greater conversion.

2.

At a constant conversion level, there will be a greater gasoline yield, with a


slightly lower octane.

3.

Products will be less olefinic.

A rough indication of the quantities of paraffins present is a characterization factor


which relates boiling point to specific gravity. This is the UOP K factor, which is
given by:

(CABP)
UOP K =
SG60

1/3

where:
CABP = Cubic average boiling point, R
SG60 = Specific Gravity at 60F
A detailed example of this calculation is given earlier. A UOP K factor of 11.2 would
show a more aromatic stock, while a K factor of 12.5 would indicate a more highly
paraffinic stock. One key feature of the FCC unit is that the hydrogen in the product
streams must come from the hydrogen in the feed. There is no added hydrogen in
this process. One good way to check the quality of FCC data and yield estimates is

157048
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to do a hydrogen balance across the unit as shown in the calculation section.


Gasoline yield is a very strong function of the H2 in feed as shown:

Gasoline Yield, Vol-%

GASOLINE YIELD vs. HYDROGEN CONTENT

70

60

50
11

12

13

Hydrogen in FCC Feed, Wt-%


BOILING RANGE
The boiling point range of FCC feed usually varies from an initial point of 500F
(260C) to an endpoint of about 1050F (565C). The distillation must be conducted
under vacuum and corrected to atmospheric pressure, because thermal cracking
will occur above 700F (371C).
There are two boiling point ranges which are used to describe the lighter material in
the feed. These are "percent over 430F" (221C), and "percent at 650F" (343C).
The first quantifies the amount of gasoline in the feed. This material may be
cracked, but only at a very slow rate. Most of it merely passes through the unit, with
perhaps some small octane improvement. The octane improvement is somewhat

157048
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higher for cracked gasoline, as compared to straight run material. Gasoline in the
FCC feed is not considered desirable because it occupies space which could be
used to process gas oil, and because it usually has a low octane number. It would
be better to remove this material in the crude unit and send it to a reformer.
The "percent at 650F" (343C) is a measure of the light fuel oil in the charge. The
boiling point of 650F is chosen because it corresponds to the normal LCO
endpoint. This material will crack, but not to the same extent as the heavier
molecules. It will produce more coke than will the gasoline, but again, less than the
heavier material.
The endpoint of FCC charge stock may vary, depending to some extent on the
suitability of the material for cracking operation. The presence of coke precursors,
such as polynuclear aromatics, organometallic compounds, and high sulfur material,
are, in many cases, good reasons for avoiding the inclusion of high boiling point
compounds in FCC feed. This depends very much on the individual stock.
AVERAGE BOILING POINT
The average boiling point of the FCC feed depends on the average molecular
weight. An increase in API and the molecular weight will typically cause the
following:
1.

3.

The charge will crack more readily, so at constant reactor temperature


the conversion will increase.
At constant conversion, the gasoline yield will increase about 1% for an
increase in the molecular weight of 20. This would correspond to an
increase of 2 API.
At constant conversion, the yield of C4 and lighter will decrease.

4.
5.

The olefinic content of the products will decrease.


The regenerator temperature will tend to rise.

2.

157048
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There are upper limits to these increases. An exceptionally heavy feed might prove
to be undesirable because of high Carbon Residue, Sulfur, and similar factors. The
exact changes will depend on the individual feedstock.
CARBON RESIDUE
The carbon residue of a feedstock is an indirect measure of its coke producing
nature. The value may be determined by either the Conradson or Ramsbottom
methods. An increase in residue of a feed from one crude source will generally
result in an increase in regenerator temperature. The exact nature of coke laydown
is somewhat complicated so this characteristic is not always reliable for comparing
feeds from different crudes.
The carbon residue can be a useful number for determining possible contamination
in storage, or of problems in the upstream feed preparation units. Because
entrainment in the vacuum tower is a common cause of increased carbon residue, a
higher metals level may be observed at the same time. Gas oil having a carbon
residue over 0.5% should be considered suspect.

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COLOR
Color may be used as a possible indication of problems. Darker stocks tend to have
higher carbon residues, sulfur, and metal problems. This method is especially
valuable because it is a relatively quick and easy test.
METALS
Organometallic compounds in the FCC feed can cause serious overcracking if the
metals deposit on the catalyst. The cleanliness of a chargestock is given by a
metals factor:

Fm = V + 10 (Ni + Cu)
where:
Fm
V
Ni
Cu

=
=
=
=

Metals factor
Vanadium concentration, wppm
Nickel concentration, wppm
Copper concentration, wppm

All metal concentrations are ppm by weight in the feed. A factor of 1.0 is considered
safe, over 3.0 indicates a danger of poisoning.
Normal dry gas make at 60-70% conversion is 50-100 SCF/bbl. A heavily
contaminated stock would produce 200 SCF/bbl or more. The ratio H2/C1 will
increase as dehydrogenation reactions are catalyzed by the metals, especially Ni.
An H2/C1 ratio of 1.0, as compared to the normal 0.3-0.5, would again indicate
metals poisoning. A third indication of metals would be an increase of 10-15% in the
olefin content of the C3 stream, to as high as 85%.
Sodium and vanadium pose a different threat to the catalyst than nickel. These
metals are mobile at high temperatures and can destroy the zeolite in the catalyst
causing low activity and conversion. Even with metal traps in the catalyst, high

157048
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catalyst usage will be required to flush these metals from the unit to maintain
reasonable activity, conversion and selectivity.
Proper control of the feed preparation units is necessary to prevent these metals
from contaminating the feed. Most of the metals are concentrated in the heavier
fractions, although a few may be volatile at lower temperatures. Keeping
entrainment in the feed towers to a minimum will keep metals level down to a safe
value.
SULFUR
Sulfur is as undesirable in cat cracker charge as it is in the feed to most refining
units, causing corrosion of the equipment and increased difficulty in treating
products. At 50% conversion, about 35% of the sulfur charged is converted to H2S,
and at 70%, this figure will rise to about 50%. The sulfur content of a 400F
endpoint cat gasoline will be about 10% of that of the raw oil charge, but this
fraction increases rapidly as the endpoint is raised above 400F. As would be
expected, the higher the sulfur content of the gasoline, the lower will be its lead
response, although lead response is no longer important in many parts of the world.
Hydrotreating will significantly improve FCC feedstock. The effect is twofold: the
removal of impurities and the hydrogen addition to saturate molecules. The first of
these is important when the charge is contaminated with sulfur, nitrogen or metals.
These poisons may cause both process and environmental problems. Hydrogen
addition to the feed, especially to the large polynuclear aromatics, will give higher
conversion and a decreased coke yield by making these heavy compounds easier
to crack.
The FCC product sulfur distribution is not even; it tends to concentrate in the heavy
products and as H2S. Table 1 is a typical product sulfur distribution for a nonhydrotreated feed.

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TABLE 1
COMMERCIAL SULFUR BALANCE
(80.7 LV-% CONVERSION)
STREAM
COMPOSITION
WT-% SULFUR

PERCENTAGE
OF FEED
SULFUR

FEED:

VIRGIN GAS OILS

1.04

100.0

PRODUCTS:

SPONGE ABS. OH
DEBUT. OH
H2S

44.4

RSH
GASOLINE
LIGHT CYCLE OIL
CLARIFIED OIL
FLUE GAS
SOUR WATER

0.15
1.35
2.08

3.8
6.5
16.7
17.1
9.1
1.9
99.5

Much of the feed sulfur comes off as H2S because H2S, once formed, is fairly stable
under the conditions encountered in the reactor. This desulfurization is beneficial
because concentrating the feed sulfur in one product stream decreases the
difficulties in treating other products.
Higher sulfur feedstocks that are mildly hydrotreated will tend to produce a lesser
percentage of H2S, and leave a larger portion of the feed sulfur in the heavy
products. The effects are shown in Table 2 for cycle oil sulfur content.

157048
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The results of this sulfur concentration in heavy products will vary with the refinery's
needs. Product specifications and uses must be balanced against changes in
corrosion rates and required metallurgy, and should be examined on a case by case
basis.
TABLE 2
SULFUR DISTRIBUTION
EQUIVALENT PROCESSING CONDITIONS

SULFUR,
WT-%

TOTAL
CYCLE OIL
SULFUR
CONTENT,
WT-%

PERCENTAGE
OF FEED
SULFUR
IN CYCLE
OILS

RAW

2.68

4.31

43.7

HYDROTREATED

0.56

1.40

55.8

HYDROTREATED

0.26

0.76

67.6

FEEDSTOCK TYPE

Metals
The reduction of metals by hydrotreating follows the same pattern as nitrogen and
oxygen removal. It is possible to reduce the feed metals factor, Fm, by 50-90% in a
moderate severity hydrotreater.
Hydrogen Addition
Hydrotreating an FCC feedstock to improve quality is generally more attractive if
gasoline or LPG is the desired product. Moderate severity LCO production may not
justify hydrotreating unless there is a high concentration of feed sulfur or other
contaminants. Table 3 shows the yield changes for a charge stock under equivalent
cracking conditions at three levels of hydrotreating.

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The increase in conversion in Table 3 is accompanied by an increase in gasoline


efficiency, except for the severe hydrotreating case where potential alkylate (C3 and
C4) is significantly higher. The decrease in sulfur content would be accompanied by
a decrease in nitrogen and metals, while the decreasing carbon deposition will
indicate a slightly higher product yield, with less feed being converted to coke.

TABLE 3
EFFECT OF FEEDSTOCK
HYDROTREATING: EQUIVALENT CRACKING CONDITIONS
FEED

RAW

HYDROTREATED

GRAVITY, API
SULFUR, WT-%
CONVERSION (LV-%)
C5+ GASOLINE (LV-%)

21.7
2.68
78.1
55.5

25.5
0.53
80.7
60.1

26.4
0.28
81.7
61.0

33.3
0.01
92.0
68.2

POTENTIAL ALKYLATE (LV-%)


RELATIVE CARBON DEPOSITION

33.6
1.0

37.2
0.78

37.1
0.76

41.8
0.43

FCC GASOLINE RESEARCH


CLEAR OCTANE NUMBER

93.8

93.9

94.0

92.0

RATIO ISOBUTANE/BUTYLENES
IN C4 FRACTION (MOL-%)

0.68

0.72

0.79

0.81

GASOLINE EFFICIENCY
VOL-%, GASOLINE/CONVERSION

0.71

0.74

0.75

0.74

A detailed analysis for two different feedstocks is given in Table 4. Two obvious
changes are the increase in API gravity and UOP K, indicating a greater degree of
hydrogen saturation. There is some small degree of hydrocracking, as shown by the
decrease in average molecular weight and boiling point.

157048
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TABLE 4
FCC FEEDSTOCK PROPERTIES
GACH SARAN
(HEAVY IRANIAN)

L. A. BASIN
SEVERELY
HYDROHYDROTREATED TREATED

RAW

HYDROTREATED

RAW

22.9

26.3

22.2

26.3

35.0

11.78
385
1.83

11.98
380
0.14

11.45
316
1.30

11.7
298
0.1

11.99
266
0.001

CON. CARBON, WT-%

0.34

0.06

0.1

0.1

0.0

N2, PPM

1880

1570

3380

2190

AROMATICS, WT-%

48.5

42.1

53

51

30.5

ASTM D 1160
IBP
10
30
50
70
so
95
% RECOVERED

504
661
760
822
877
958
983
98

458
632
739
799
856
933
990
98

382
548
653
724
795
880
965
98

360
530
628
707
779
868
954
98

360
440
518
594
682
810
920
98

FM FACTOR

2.3

2.9

0.0

0.0

PILOT PLANT
CONVERSION VOL-%

77

83

68

76

89

API
K
MW
S, WT-%

157048
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Feed hydrotreating is becoming more common as the quality of FCC feedstocks


decreases. Table 5 summarizes the advantages of hydrotreating. The economic
question of increased cost for hydrotreating versus increased yields and other
benefits must be solved for each plant.
TABLE 5
ADVANTAGES OF HYDROTREATING
1.

HIGHER CONVERSION

2.

HIGHER GASOLINE YIELD

3.

HIGHER C3-C4 YIELD

4.

LOWER SULFUR AND METALS

5.

LOWER CLARIFIED OIL YIELD

6.

LOWER COKE MAKE

J Cracking
A modification of feed hydrotreating is J cracking. This process treats the light cycle
oil stream, which is then recycled back to the riser with the raw feedstock. The
hydrotreated LCO can be cracked, increasing the yield of all the lighter products. J
cracking partially saturates the di-, tri-, and tetra-aromatics present in LCO. These
components then crack instead of forming coke when the stream is recycled. Table 6
compares the product yields for J cracking and normal operation for a hydrotreated
feed.

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TABLE 6
FCC YIELD COMPARISON FOR J CRACKING
FEED: HYDROTREATED 25 API MIDDLE EAST GAS OIL
OPERATION
NORMAL
+ J CRACKING
CONVERSION, VOL-%

85

95

H2S, WT-%

0.15

0.25

C2 MINUS WT-%

2.77

3.06

C3, VOL-%

12.5

13.7

C4, VOL-%

18.0

19.6

C5- 380F 90% GASOLINE, VOL-%

67.1

74.3

LCO, VOL-%

10.0

0.0

CLARIFIED OIL, VOL-%

5.0

5.0

COKE, WT-%

5.0

6.1

POTENTIAL C3-C4 ALKYLATE, VOL-%

32.8

34.5

TOTAL 10 PSI RVP GASOLINE, VOL-%

110.2

120.1

RESEARCH OCTANEFCC GASOLINE

92.5

92.6

RESEARCH OCTANETOTAL GASOLINE

93.2

93.3

MOTOR OCTANETOTAL GASOLINE

85.3

85.2

YIELDS

NOTE: RVP IS REID VAPOR PRESSURE

157048
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OXYGEN AND NITROGEN


Oxygen and nitrogen pose different problems than sulfur. Oxygen may be present in
the feedstock chemically bonded to a hydrocarbon, or it may simply be absorbed by
the oil as it sits in storage. Dissolved oxygen, if not stripped, may cause fouling of
heat exchangers when the temperature approaches 400F (200C). Another source
of oxygen is the instrument purges or the entrained oxygen carried into the reactor
with the regenerated catalyst. This is more of a problem with the complete CO
combustion units than with the traditional plants, because regenerator oxygen levels
are high. Most of the oxygen in the reactor will be quickly converted to water, carbon
oxides, phenols, cresols, or acids. Other reactions, including the problems of free
oxygen, are discussed later under Product Treating.
A severely contaminated feedstock may contain 4000 ppm nitrogen, a good feed
less than 500-600 ppm. Much of the nitrogen will be converted to ammonia, which
can cause plugging problems in the main column overhead. Cyanides are also
formed, these contribute to blistering and corrosion in the gas concentration section.
Wash water to the main column overhead and gas plant is used to minimize these
problems.
Some of the nitrogen will stay with the catalyst as a constituent of coke. It burns off
in the regenerator to give nitrogen oxides and small amounts of ammonia. These
problems are discussed in Section XIII, Environmental. High nitrogen levels are
detrimental to catalyst activity, since the basic nature of the ammonia formed tends
to deactivate the acid sites on the catalyst. This deactivation is reversible and
catalyst activity will be restored with low nitrogen feed.
Difficulties with nitrogen and oxygen are normally not severe enough to justify
hydrotreating for only these poisons. But they rarely occur alone; a bad feedstock
will usually have high concentrations of sulfur or metals in addition to the oxygen and
nitrogen.

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The amount of poisons removed again depends on what species are present, and
the severity of treatment. Moderate hydrotreating will remove 10-50% of the total
nitrogen. A high severity operation may run close to 100% removal. Treatment for
oxygen gives similar results.
PROCESSING OF RESIDUAL FEEDSTOCKS
There are several problems and penalties associated with processing residual
feedstocks. There is a loss of selectivity in liquid product yield since the feed
generally contains less hydrogen than the gas oil fraction. The increased boiling
range brings more contaminants into the unit, both as coke precursors and as
metals. The coke precursors will cause a higher delta coke on catalyst and will
result in a hotter regenerator and less conversion for the coke yield generated. The
higher metals will cause more light gas production as will the higher regenerator
temperatures. Catalyst activity will be effected by the high metals and by the
additional deactivation from the high regenerator temperature. The higher coke yield
will mean thruput will have to be reduced to stay within the coke burning capacity of
the unit.

157048
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The following table from a commercial unit illustrates what happens as the feed is
changed from VGO to Resid.

Commercial Operations
Changing from Gas Oil to Residue Processing
Feed

Composition, vol Ratio


VGO / Atm. Residue

100 / 0

38 / 62

25 / 75

0 / 100

Conradson Carbon, wt-%

0.16

2.25

2.96

3.95

Metals (Ni+V), wt-ppm

1.0

9.6

9.0

6.3

Conversion, lv-%

86.2

82.2

79.7

76.5

Gasoline Yield, lv-%

62.6

60.3

59.5

57.4

Coke, wt-%

5.6

7.2

7.1

7.5

Commercial Performance

As the contamination in the feed increased as a reflection of the poorer feed quality,
the coke make required to maintain conversion increased. However, by careful
selection of the crudes purchased, the metal content of the resid was controlled so
that their effect on the operation was limited and the additional coke burning
requirement was the major change. Note that the gasoline yield was reduced by
almost 5 LV% due to the change in feed.

157048
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This same dependency on feed quality is evident in the RCC unit as well. The
following tables show the performance of the unit on three different quality feeds:

RFCC Unit Feedstock Variation

API
Sulfur, wt-%
Nitrogen, wt-%
Conradson Carbon, wt-%
Metals
Nickel, wt-ppm
Vanadium, wt-ppm

Low
Carbon
Residue
22.8
0.9
0.12
4.8
8
17

Intermediate
Carbon
Residue
21.3
1.1
0.14
6.0
13
31

High
Carbon
Residue
19.2
1.2
0.19
7.9
17
52

Commercial RFCC Performance on Different Residues

Dry Gas, wt-%


C3s + C4s, lv-%
Gasoline
(430F EP), lv-%
Light Cycle Oil
(630F EP), lv-%
Clarified Oil, lv-%
Coke, wt-%
Total C5+ Liquid, lv-%
RON Gasoline

Low
Carbon
Residue
3.4
25.2
59.1

Intermediate
Carbon
Residue
3.2
24.7
56.6

High
Carbon
Residue
4.0
23.9
55.6

15.0

14.2

15.0

7.5
8.4
106.4
91.9

10.2
9.1
105.7
93.2

10.9
10.8
105.4
93.3

157048
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Figure 1 illustrates the relative loss in conversion as a result of an increase of


contaminants in the FCC feed, as expressed in terms of the Ramsbottom carbon. It
is assumed that the proper catalyst makeup policies have been followed, so as not
to operate with heavily contaminated catalyst (for example, total metals on catalyst
of less than 5000 ppm). The loss in conversion is, in part, attributable to the
deterioration of the feed quality, but the main cause is the decrease in catalyst
circulation resulting from the higher regenerator temperature experienced by the
unit.

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Figure 2 summarizes the effect that contaminated feed has on the unit's regenerator
temperature.

157048
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These plots also summarize the experiences of most refiners, who found that the
units designed for VGO could not accommodate more than about 3.5 to 4.0 wt-%
Conradson carbon in the feedstock due to excessively high regenerator temperatures. The high temperatures also resulted in severe catalyst deactivation and poor
unit performance. This fact, i.e., that residual stocks deposit more carbonaceous
material during the cracking cycle than can be effectively used to fuel the
conversions reactions, led to the development of alternative technologies directed
at:

Limiting the heat release during regeneration


Seeking external removal of heat

The first approach led to the development of the two-stage regeneration system that
is currently practiced in the Ashland RCC unit and the second to the development of
the catalyst cooler, also incorporated in the design of this unit.
Table 5 summarizes the relevant properties of an atmospheric resid that will be
used to illustrate the benefits that can be obtained by varying the heat removal in a
commercial unit. Case 1 found in Table 6 represents a very low coke make
operation where the regenerator temperature has been allowed to equilibrate at a
very high level, in the order of 1480F. The yield structure is poor and the gas make
extremely high. The subsequent cases illustrate the benefits that can be derived by
manipulating the heat balance forcing the unit to produce more coke. Even though
the unit is producing an additional amount of coke, the yield pattern improves. The
data in Table 6 is plotted graphically in Figure 3.

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TABLE 5
RCC FEEDSTOCK FOR COKE YIELD VS. CONVERSION STUDY
API
Conradson Carbon
Metals, wt-ppm
UOP K
Source

20.8
4.8
20.0
12.1
Atmospheric Resid

TABLE 6
RCC ESTIMATED YIELDS VS. UNIT COKE YIELD
Case
Coke Yield, wt-%
Conversion, LV-%
Dry Gas, wt-%
Gasoline, LV-%
LCO, LV-%
Slurry, LV-%
Total Liquid, LV-%
Heat Removal

1
7.3
68.3
7.2
46.0
16.9
14.8
101.6
No

2
8.57
77.2
4.2
56.3
13.4
9.4
106.6
No

9.73
80.9
3.4
58.5
11.4
7.7
107.6
Yes

11.10
83.0
3.3
59.1
9.7
6.4
107.5
Yes

Feed: Table 5
Gasoline, 380F at 90% Pt.
LCO, 600F at 90% Pt.
Installing a variable heat removal catalyst cooler enables the refiner to adjust the
heat removal required for a given feedstock to produce the optimum yield pattern.
Even though the coke yield has increased, the resulting yield pattern at the higher
coke make is more favorable than that which can be achieved at the lower coke
makes. These benefits are achieved at relatively low regenerator temperatures, of
less than 1350F, for good catalyst activity maintenance.

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Commercial experience indicates that operations at regenerated catalyst


temperatures greater than 1350-1400F offer very little advantage, and, in fact,
result in poor yields and very high gas production. Units currently processing some
resid which are forced to operate at high regenerator temperatures are ideally
suited for the installation of a UOP catalyst cooler. In addition to the conversion and
selectivity benefits obtained by operating at the lower catalyst temperatures,
considerable savings can be obtained by the reduction in catalyst makeup. This is
due to the reduction in the hydrothermal deactivation of the catalyst as a result of
the lower regenerator temperature. If it is desired to keep the unit coke make
constant, another interesting application of this technology is illustrated in the
following case.
Table 7 shows the savings possible in a unit processing resid. As can be seen in
the table, the heat balance has been adjusted to keep the coke make constant to
satisfy the unit constraints. The reduction in regenerator temperature results in a
lower catalyst addition rate, since the hydrothermal deactivation of the unit's catalyst
has been reduced. For a 20,000 BPD unit, this catalyst savings amounts to
approximately 1.6 million dollars per annum.
TABLE 7
CATALYST COOLER ADDITION FOR
MORE PROFITABLE OPERATION AT CONSTANT COKE MAKE
Feed
API
Conradson Carbon, wt-%
Feed Temperature, F
Reactor Temperature, F
Regenerator Temperature, F
Conversion, LV-%
Coke Yield, wt-%
Catalyst Addition
Heat Removal
Catalyst/Oil Ratio

No Cat Cooler

With Cat Cooler


27.0
3.0

Base
Base
1410
85
Base
Base
No
Base

Base + 160
Base
1350
85
Base
0.5 Base
2500 Btu/lb coke
Base

157048
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The preceding discussions have illustrated the benefits that can be derived with the
installation of a catalyst cooler. This flexible technology permits:

Adjustments in the unit conversion to achieve the optimal yield pattern for a
given feedstock

Enhancement of the unit's capability to process more contaminated feedstocks

A more profitable unit operation while keeping the unit coke production
constant.

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REGENERATION SECTION
The main purpose of the regeneration zone is to oxidize the coke on spent catalyst
and reestablish the catalyst activity of the fluidized particles prior to being returned
to the reactor riser. The heat from this combustion of coke in turn provides the
energy to satisfy the process requirements. Thus, the regeneration section has a
very fundamental significance.
Over the years this section has undergone fundamental design and mechanical
improvements. One of the first big movements occurred during the 1970's, with the
advent of total combustion. UOP moved away from the conventional bubbling or
turbulent-bed regenerator to a fast-fluidized, high-efficiency style combustor. Since
then this design has become well established as shown in Figure 8, and more than
45 units in commercial operation. Contrasting a modern high efficiency combustor
design with a typical bed style configuration of the past, as in Figure 6, the major
regenerator improvements are aimed towards:

Enhanced and controlled coke burning kinetics

Reduced catalyst inventory

Narrow catalyst residence time distributions

Ease of start-up and routine operability

Uniform radial carbon and temperature profiles

Limited afterburn and uniform temperature distribution at cyclones

Additional heat balance flexibility from


Total CO combustion
Dense phase catalyst cooling

Particulate, power and waste heat recovery

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These benefits are principally derived from the combination of a more


homogeneous gas and solids contacting regime and reduced yet controlled particle
residence time distributions.
The following sections will discuss in detail the fundamental regenerator fluidization
regimes, mixing characteristics, combustor hydraulics and coke burning kinetics,
and how they relate to commercial performance and unit optimization.

FCC REGENERATOR FLUIDIZATION REGIMES


In commercial FCC regenerator designs, various fluidization regimes exist. The
schematics shown in Figure 4 serve to illustrate these various regimes pictorially.

FIGURE 4
FLUIDIZATION REGIMES
A) Bubbling
Fluidized Bed

(B)

Turbulent
Fluidized Bed
(C)

Fast
Fluidized Bed

Transport
Riser Reactor

Bed Density

(D)

Catalyst Flux

Gas Velocity

UOP 3106-6

157048
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Bubbling Bed (Umb - 1.0 ft/s Superficial Velocity)


The bubbling bed regime ranges from the minimum bubble velocity Umb (which
typically for FCC type A particles is from 0.02-0.1 ft/s), up to about 1.0 ft/sec
superficial velocity. Here three distinct yet interchanging gas phases exist: the
bubble phase, the emulsion phase, and the gas phase inside the catalyst pores.
These three phases all flow at various relative velocities. Discrete bubbles of gas
flowing through the bed produce abrupt pressure fluctuations at the bed surface.
The relative fluctuations are determined by the bubble frequency or superficial gas
velocity Ug, as shown in Figure 5.

FIGURE 5
BUBBLING TO TURBULENT BED TRANSITION

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Figure 6 represents a typical bubbling bed regenerator in which there is limited


solids entrainment and transport through the freeboard region. Most of the larger
particles that are entrained are returned to the bed through the two stage cyclone
diplegs. There exists a sharp, distinct catalyst bed level. The distance between the
primary cyclone inlet horn and the surface of the bed should be greater than the
transport disengaging height (TDH).

FIGURE 6
BUBBLING BED REGENERATOR

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Turbulent Bed (1.0-3.5 ft/sec Superficial Velocity)


With higher gas velocities, the distinct bubble phase disappears and the bulk of the
gas flows as described by Yerushalmi "in voids which continually coalesce and split
tracing tortuous passages as they rise through the bed"1. The upper bed surface is
considerably more diffuse with reduced pressure fluctuations and substantially
higher entrainment of solids into the freeboard region (Figure 5 in Fluidization).
Because of the requirement for higher coke burning capacity and improved
contacting efficiency, the vast majority of commercial regenerators are operating in
the turbulent bed regime. In this regime the ultimate regeneration capacity is set by
the sharp increase in solids entrainment as velocity increases, see Figure 7, and by
the cyclone separation efficiency and dipleg hydraulics.

FIGURE 7
MAXIMUM DILUTE PHASE ENTRAINMENT
IN VERTICAL GAS-SOLIDS UPFLOW

1. Further Studies of the Regimes of Fluidization, Powder Technology.

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Fast Fluidized Bed (3 -10 ft/sec Superficial Velocity)


The regime now extends into a complex transport phase where there is a sharp
increase in the rate of solids carryover as the transport velocity is approached. In
the absence of any solid recycle, the bed would rapidly disappear. Beyond this
velocity, catalyst fed to the base of the regenerator traverses it in fully entrained
transport flow with the voidage or density of the resulting suspension being
dependent not only on velocity of the gas but also on the solids flow rate (flux =
lb/s/ft2). If the solids rate is low, dilute-phase flow will result. If on the other hand,
solids are fed to the regenerator at a sufficiently high rate, for example by
recirculating solids carried-over back to the combustor, then it is possible to
maintain a relatively large solids concentration referred to as the fast-fluidized bed.
The transport velocity may therefore be regarded as the boundary which divides
vertical gas-solids flow regimes into two groups. Below the boundary lies the
bubbling, turbulent fluidized bed. Above lies the transport regime which, depending
on the solids flux, encompasses a wide range of states from dilute-phase flow to the
fast fluidized bed. Due to cluster formation, for FCC catalyst the transport velocity is
approximately 20 times the terminal velocity of a single 50 FCC particle.

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COMBUSTOR HYDRAULICS AND MIXING CHARACTERISTICS


Figure 8 shows a typical high-efficiency style regenerator. The combustor section
can be operated either above or below the fluid cracking catalyst transport velocity.
The resulting catalyst/air suspension in the combustor depends not only on the gas
velocity but also on the solids flow rate (lb/sec/ft2). Adjustment in the quantity of
catalyst being externally recirculated (via slide valve control) can therefore be used
to control the catalyst inventory in the combustor for various air rates.

FIGURE 8
HIGH EFFICIENCY REGENERATOR

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Figure 9 represents typical combustor hydraulics for various catalyst loadings and
superficial gas velocities. The combustor density is measured across the entire
combustor height and the solids loading W (lb/sec/ft2) is the summation of both the
spent catalyst circulation and the combustor external recirculation. The gas
superficial velocity (A) lies well below the catalyst transport velocity, but at a low
solids flux (region X-Y), dilute phase flow exists. At condition (Y), the solids flux is
sufficient to choke the system and any further increase in solids loading (region Y-Z)
results in a substantial density (inventory/residence time) increase.

FIGURE 9
COMBUSTOR OPERATION
A

Combustor Density, lb/ft.3

Combustor
Catalyst
Inventory Is:
I = Density x V

Gas Velocity, ft/s

(Z)

Where V Is
The Combustor
Volume, ft.3

D
(Y)

(Y)

(X)

Catalyst Loading (W) lb / s/ft2

At the higher gas velocities (B) and (C), choking takes place at much higher solids
flux which results in a less abrupt change in combustor density with further

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increases in flux. Such a region is the fast-fluidized regime. Eventually at higher


velocities like (D), true transport flow will be achieved where there is no solids flux
that can choke the system.
This relationship shows how flexible the system is in adjusting the combustor
hydraulics (inventory/residence time) for various operating conditions such as
temperature, pressure, superficial gas velocity, catalyst circulation and carbon
concentration. Consider the operating condition 'E' at a superficial velocity (B). If the
superficial velocity is now increased to (C) either by a change in pressure or
combustor air flow rate, the combustor inventory will decrease to condition 'F' at
constant solids loading. However, if necessary, the combustor inventory may be reestablished at condition 'G' via an increased solids flux (external recirculation slide
valve). It is important to keep in mind that any adjustment in combustor inventory
results in a change to the upper regenerator level (surge inventory).
Since the externally recycled solids are at final regeneration temperature, this will
set the pre-combustion temperature of the combined spent catalyst, recirculated
catalyst and combustion air streams. Figure 10 shows a typical response of the precombustion temperature for various external catalyst recirculation rates. The control
of the quantity of solids being recycled to the combustor therefore sets both the precombustion temperature and inventory (residence time) required for complete
combustion with limited afterburn and low carbon on regenerated catalyst (<0.05
Wt-%).

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FIGURE 10
CATALYST PRE-COMBUSTION TEMPERATURE

Solids Mixing Characteristics


The bubble or gas induced solids mixing characteristics in the various fluidized bed
regimes have received considerable attention over the years. Although the bubble
induced vertical mixing rate of solids is extremely high, the radial mixing
characteristics are relatively poor (since bubbles flow vertically).
Since some commercial bubbling/turbulent bed regenerators exceed 50 feet in
diameter and have relatively low L/D bed ratios (<0.2), severe gas/solid
(carbon/oxygen) distribution problems can be encountered. This results in:

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1.
2.
3.

Thermal gradients, both inter-particle and within the bed.


Residence time distributions and short circuiting.
Afterburn in the dilute phase and cyclones.

Singer investigated catalyst mixing patterns in various commercial catalytic cracking


units (reactor/regenerator/stripper sections) via the use of certain radioactive
isotopes2. The measured distributions indicate that although the dense beds in the
regenerator approach good mixing, there are substantial deviations from perfect
mixing attributable to catalyst by-passing and regions of relatively immobile catalyst.
Over the years, in order to improve the radial mixing characteristics and residence
time distributions (short circuiting) of the turbulent/bubbling bed systems,
considerable attention has been placed on:

Dual diameter vessels

Fluidization bed length/diameter ratios

Air distribution, grid pressure drop and plugging patterns

Spent catalyst addition and withdrawal points, tangential swirls, deflector


plates, baffles and entry elevation within the fluidized bed

Cyclone dipleg discharge orientation

2. Catalyst Mixing Patterns in Commercial Catalytic Cracking, I&EC, 49.

Most of these intrinsic mixing problems were eliminated with the high efficiency style
combustor. Figure 11 compares the theoretical particle residence time distributions
of a modern high-efficiency style combustor with that of a conventional bubbling
bed. The basic difference in response curves is due to both the fluidization regime
(fast-fluidized) and the solids entry/exit configuration. The combustor regenerator
more closely approaches a plug flow reactor system where it is impossible for a
spent catalyst particle to leave the regenerator without passing through the dilute
phase combustion zone.

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FIGURE 11
THEORETICAL RESIDENCE TIME DISTRIBUTIONS

Regarding radial/axial mixing, it is still highly desirable for the lower (5 feet)
combustor section to be operated with a pseudo-dense phase acceleration zone.
The relatively high slip and low voidage enhances the effective fast-fluidized bed
thermal conductivity, allowing rapid heat transfer between the hot recycled and
relatively cold spent catalyst particles up to the pre-combustion temperature. This
produces uniform radial temperatures in the lower combustion zone.

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COKE BURNING KINETICS AND OPTIMIZATION


The coke deposited on the catalyst consists primarily of carbon and hydrogen along
with relatively small amounts of sulfur, nitrogen and metals. This discussion will
focus on the carbon and hydrogen species. The amount of hydrogen in coke has
typically decreased over the years to levels of 6-7 wt-% with the use of high
conversion, zeolite catalysts and modern stripper designs.
Catalyst regeneration, as a carbon removal process, is widely accepted as being
first order with respect to carbon concentration and oxygen partial pressure:
dC / dt KCPo2

Where:
K
= Rate constant, hr-1 atm-1
C
= Wt-% carbon on catalyst
PO2 = oxygen partial pressure, atm
The reaction rate constant will be dependent on temperature and can be
represented via an Arrhenius type equation:

dC / dt Koe

E
CPo2
RT

(1)

where:
E =
R
=
T
=

Activation Energy
Gas Constant
Temperature, R

This relationship for the rate of carbon burning from fluid catalytic cracking catalysts
was found experimentally to hold over a wide range of temperatures with diffusional
limitation not controlling. A similar expression can be used for the hydrogen content
of the coke, with the oxidation of hydrogen proceeding more rapidly than that of
carbon:

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dH / dt K oe

E
HPo2
RT

(2)

Where:
Ko Ko
H = Wt-% hydrogen on catalyst
When discussing coke combustion rates and kinetics, it is important to differentiate
between net coke yield and coke concentration (analogous to heat and
temperature). The net coke yield is set by the unit enthalpy balance with little direct
impact on the rate of coke combustion of individual particles.
Delta Coke

This is a dependent variable, which is difficult to accurately predict due to its


dependency on feedstock quality, processing conditions and catalyst formulation.
This term also sets the final regenerator temperature via:

TRegen TRx C / CpHcomb H

FG

air

Hloss

With a few simplifying assumptions, such as a plug flow combustor and total
combustion of coke to CO2, the differential equations (1) and (2) can be solved
numerically in order to gain insight into the impact and optimization of such process
variables as:

Temperature
Catalyst recirculation
Oxygen partial pressure
Carbon and hydrogen concentration

on the overall coke combustion rates.

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Pre-combustion Mix Temperature and Catalyst Recirculation

As discussed in a previous section, controlled catalyst recirculation to the


combustor serves to:

increase residence time via combustor hydraulics


raise pre-combustion temperatures (Figure 10)

Pre-combustion temperature is the mix temperature of the cold spent catalyst, hot
recycled catalyst, and combustion air:
Tmix

0.275F CCR TRegen 0.275 CCRTRx 0.273BTB


0.273B 0.275F CCR 0.275 CCR

Where:
B
F
CCR
TB
0.275
0.273

=
=
=
=

lb air/hr
Cat Recirculation, wt ratio of CCR
Cat Circulation Rate, lb/hr
Blower Temp, F

= specific heat of catalyst, BTU/lb/F


= specific heat of air, BTU/lb/F

The table below shows the substantial impact of recirculated catalyst on the
combustion rates via the increased initiation temperature Tmix.
Recycle

Coke Concentration

Mix Temperature

Regen Time

Zero

0.8 to 0.05 Wt-%

913

121 sec's

1.5 CCR

0.8 to 0.05 Wt-%

1161

44 sec's

For identical conditions the overall combustion time is reduced by a factor of 3. In


reality this would be reduced further by additional internal recirculation (solids slip).

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Regenerator Temperature and Coke Concentration

These two parameters are strongly interdependent since the final regenerated
catalyst temperature is set by:
TRegen = TRx + C/Cp [HComb - HAir - Hlosses]

Where:
C = Cspent - Cregen
With Cregen --> 0 for most operations
The impact of temperature alone on the rate of carbon combustion is exponential
and quite dramatic:
Temperature
Relative combustion rate

1100F

1200F

1300F

1400F

2.5

18

And slows dramatically with carbon concentration on catalyst:


Carbon Reduction
Relative time required
For combustion

1.0 to 0.9 Wt-%

0.15 to 0.05 Wt-%

10

At constant temperature, oxygen partial pressure, and delta coke reduction.

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Oxygen Partial Pressure

This parameter is set by the combination of regenerator operating pressure, excess


air, and oxygen concentration in the supply air. The relationship between the rate of
combustion and oxygen partial pressure is linear. Figures 12 and 13 show the
relative effect of total pressure and excess oxygen on the regeneration time at
various temperatures.

FIGURE 12
RELATIVE EFFECT OF EXCESS OXYGEN
CONCENTRATION ON REGENERATION TIME
AS A FUNCTION OF TEMPERATURE
1.
2.
3.
4.

Total pressure assumed constant at 30 psig


Plug flow regeneration system
Carbon reduced from 1.10 to 0.3 wt-% on catalyst
Excess O2 change made by adjusting main air rate

Regenerator Time, sec

100

5% Excess O2

2% Excess O2
10
1120

1140

1160

1180

1200

1220

Temperature, oF

1240

1260

1280

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FIGURE 13
Relative Effect of Total Pressure on Regeneration Time
Requirement at Various Temperatures

Regeneration Time, Sec

1. Plug flow assumed.


2. Carbon level reduced from 1.10 TO 0.3 wt-%

150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0

1150F
1200F
1250F

10

20

30

40

Total Pressure, psia

50

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COMBINED PROCESS VARIABLES

With some simplifying assumptions, all the process variables and their interactions
can be mathematically modeled via equations (1) & (2) in order to achieve
additional understanding and optimization of the combustor performance.
As an example of the model's use, Figure 14 and Table 8 show the calculated time
dependent responses of the numerous products of combustion for the following set
of typical combustor operating conditions:

Typical Process Conditions

Regenerator pressure
lb air/lb coke
Hydrogen in coke
Coke on spent catalyst
Recycle catalyst temperature
Blower discharge temperature
Catalyst recycle
Reactor temperature
% oxygen in air
CO2/(CO2+CO)

30.0 psig
14.18
6.0 wt-%
0.8 wt-%
1344F
320F
1.5 Xs
980F
21 mol%
1.0

Calculated Time Dependent Variables

Particle Temperature, F
Carbon Concentration, wt-%
Hydrogen Concentration, wt-%
Flue Gas Oxygen Concentration, mol%
Assumptions:

1. Complete combustion
2. Plug flow regeneration

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FIGURE 14
COMBUSTOR COMPOSITION PROFILES
25

1500

1450

20
1400

10

1300

1250

W
t- %
1200

Ca
rbo
nW

Flue Ga
s
t- %

O2 mol
-%

1150

1100
0

10

15

20

25

30

Time (seconds)

35

40

45

50

55

60

Temperature

o
Temp, F

en
og
dr
Hy

Composition

1350
15

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TABLE 8
FCC COMBUSTOR MODEL
CALCULATED TIME-DEPENDENT VARIABLES

Time

Temp, F

Carbon
wt-%

0
1
2
3
4
5
10
15
20
25
30
35
40
45
50
55
60

1160
1177
1182
1206
1218
1230
1272
1295
1310
1319
1325
1330
1333
1335
1336
1338
1339

0.752
0.708
0.663
0.616
0.574
0.532
0.358
0.246
0.174
0.126
0.097
0.076
0.060
0.046
0.039
0.032
0.026

Hydrogen
wt-%

0.046
0.036
0.028
0.022
0.016
0.012
0.002
0.001
-------------------------------------------------------

Flue Gas O2
mol%

21.0
18.3
17.7
16.2
14.8
13.7
8.5
7.0
5.5
4.6
3.9
3.5
3.2
2.9
2.7
2.6
2.5

Total Combustion and CO Promoter

In the absence of a CO combustor promoter, large variations in CO2/CO ratios are


observed. At the catalyst surface it is believed that the ratio of CO2/CO is an
intrinsic function of the temperature at the burning site ("Arthur's ratio"). However,
the CO exiting the burning site may be further oxidized to CO2 at a rate dependent
on temperature, CO, O2, and H2O partial pressures, active metals on the catalyst,
carbon/oxygen distributions within the fluidized bed, and even the catalyst
presence.

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This burning of CO in the dilute phase known as "afterburning" can produce large
flue gas temperature increases above those in the dense phase. This is due to the
relative heats of combustion:
C

CO 3,960 BTU/lb

CO2 14,150 BTU/lb

Heat Combustion, BTU / lb Coke

Heat of Combustion vs.


CO2/CO Ratio in Flue Gas
17000

Total Combustion
(16,500 BTU / lbCoke)

16000
15000
14000
13000
12000
11000
1

CO2/CO mol Ratio


As the amount of CO combustion is increased to 100%, the air required for
combustion also increases. This is partially offset by the improved utilization of the
heat of combustion, but full CO combustion will require a larger blower than a partial
CO combustion operation if the catalyst is regenerated reasonably clean.

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Combustion Air Requirement


vs. CO2/CO in the Flue Gas
Air/Coke (wt-Ratio)

15

Complete Combustion
with 2% Oxygen
in Flue Gas

14
13

Complete Combustion
with No Oxygen
in Flue Gas

12
11
10
1

CO2/CO mol Ratio

In the absence of catalyst, a flue gas stream of 3/1 CO2/CO mol composition
undergoing complete combustion to CO2 could see a temperature increase
> 600F. (Note: this temperature increase is moderated due to the sensible heat of
any entrained catalyst.)
In the 1970's, in order to exploit the higher activity, more coke selective zeolite
catalysts, operations with high temperature, once through total combustion were
utilized for the processing of conventional high quality vacuum gas oils. Table 9
shows a comparison between old and modern operations.

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TABLE 9
CATALYST FORMULATION AND PROCESS DESIGN MODIFICATIONS

Components
H2S
C2
C3

C4
C5+ Gasoline
LCO
CLO
Coke

Amorphous Catalyst
Wt-%
LV-%
0.5
4.5

6.75
11.95
45.4
12.8
8.7
9.4
100

54.4
12.4
7.6

Process Conditions
Bed cracking = 935F
CFR = 1.3
Partial burn
Capacity = Base
RONC = 92.5

RE-Y Zeolite
Wt-%
LV-%
0.4
3.75

6.45
11.45
50.2
12.55
9.4
5.8
100

59.8
12.0
8.0

Process Conditions
Riser cracking = 980F
CFR = 1.0
Total combustion
Capacity = 1.7 x Base
RONC = 91.8

From the unit enthalpy balance:


100

Hfeed

+ HRx + Hdiluents + Hrecycle BTU/Lb feed


= wt% coke on feed
BTU/Lb coke
Hcomb - Hair - Hlosses

The total combustion, no recycle operation resulted in substantially lower coke


yields (9.4 > 5.8 Wt-%), higher liquid volume yields, and capacity increases (1.7) at
equivalent conversion. These changes resulted from several major process
changes, described below:

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Hcomb:
Hrecycle:

9055
14,150 BTU/lb coke
Zero BTU/lb feed

With the combustor operation, complete CO combustion (< 50 ppm CO in flue gas)
can be achieved thermally, without promoter at temperatures greater than 1270F
and 2 mol % excess oxygen in the flue gas.
However, Mobil discovered that certain Group VIII metals, particularly platinum,
could be used at very low levels (1-3 wt ppm) to effectively catalyze the combustion
of CO to CO2 either as an integral part of the fresh FCC catalyst or as a separate
additive. In the combustor operation these additives are also frequently used but at
lower concentrations than the conventional bubbling bed regenerators.
The optimization of the combustor operation is simply the optimization of coke
burning kinetics, with a slight twist over conventional bubbling bed systems because
of the fast-fluidization regime. The combustor operation is normally quite stable, and
with only a little attention from the operator, optimal conditions can be maintained
without difficulty.
The focus of where to begin lies in only two areas: carbon on regenerated catalyst
and afterburning control. If these are both within acceptable values, no further
optimization is required. To adjust these values, we need to examine the areas of
control for the combustor.
Temperature

The primary control point for optimization is the combustor temperature. Although
the other factors are important, the temperature can be considered the one truly
independent variable for the operator.

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The catalyst recirculation slide valve controls the combustor temperature by


adjusting the amount of hot catalyst recycled to the vessel. It is normally operated
on TRC control. With adequate excess oxygen, combustor density and normal
velocity, an upper combustor temperature of 1275F should be sufficient. This
temperature may need to be increased for the following reasons:

Dilute temperatures are too high due to afterburn

Combustor density is low due to high air rates

Flue gas oxygen is low due to blower limits

CRC is high due to above situations

The ability to increase temperature in the combustor is, however, limited. Once the
recirculation slide valve is full open, no further increase in temperature can be
gained with hot recycle catalyst. The effect of other factors, such as the use of CO
promoter or increased coke operation, can lead to additional temperature
increase.
It should be noted that a flow-through catalyst cooler can limit the effectiveness of
the recirculation catalyst to raise combustor temperature. The cooled catalyst flow
will require additional hot catalyst recycle to maintain desired temperatures.
Somewhat compensating is the high coke operation that calls for the catalyst
cooler in the first place. However, if it becomes necessary, the cooled catalyst slide
valve can be adjusted to help optimize the combustor temperature.
Density

Density and velocity together determine the residence time of the catalyst within the
combustor. It is desirable to maintain at least 6 lb/ft3 density in the combustor and if
possible, 9 - 10 lb/ft3 should be a normal operating target.

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The combustor density is a dependent variable, since the temperature controls the
recirculation slide valve, unit capacity determines the velocity based on air rate, and
spent catalyst flow is dependent on the catalyst/oil ratio. However, where possible
the density (residence time) should be increased for the following situations:

CRC is high due to insufficient combustion time

Dilute temperatures are too high due to afterburn

Increased density will promote better thermal mixing and will increase residence
time to help resolve these conditions. Also keep in mind that as density increases,
the combustor catalyst inventory increases and the upper regenerator level will
decrease.
Velocity

Combustor velocity is a dependent variable determined by the amount of air needed


to complete the combustion and thus is not a variable available to the operator to
optimize other combustor conditions. However, excessive levels of flue gas oxygen
(>2.5%) provide little benefit and only serve to increase combustor velocity
unnecessarily.
A good range for combustor velocity is 4 to 5.5 ft/s. The lower end of the range is
generally better when there is a choice. When velocity exceeds 5.5 ft/s, the unit can
become combustion limited and increased afterburning may be observed. At high
combustor velocities due to capacity demands, CO promoter can be a valuable
addition. Although velocities in excess of 6 ft/s have been observed commercially,
they have been run in a promoted operation.
Combustor velocity may be too high if the following conditions are observed:

Afterburn increases despite other efforts to minimize

CRC increases even with high combustor temperature

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Excess Oxygen

The air rate and regenerator pressure will determine the oxygen partial pressure in
the combustor. Although higher levels of excess oxygen via increased air rate are
beneficial to the combustion kinetics, they are counterproductive to the unit
economics. Velocity will increase as air rate is increased, negating some of the
advantages of higher oxygen partial pressure. Thus, flue gas oxygen should be
maintained at or below 2 mol%.
There are certain situations when an increase in oxygen beyond normal flue gas
levels may be warranted:

Velocity is low and combustor temperature cannot be increased further

CRC is high despite other efforts to minimize

One element that can be considered to increase oxygen partial pressure in the
combustor without increasing air rate is the use of pure oxygen injection. In certain
situations this may be economically feasible.
CO Combustion Promoter

If all other conditions in the combustor are optimized, the use of promoter will not be
required. However, it is perhaps inevitable that the FCC unit will be pushed to the
limits such that the combustor conditions will generally exceed optimum values. In
this case, the use of promoter can provide an additional measure of safety for
controlling afterburn and avoiding excessive dilute phase temperatures.
Particularly when maximum unit capacity is required beyond design levels, the use
of promoter can be beneficial. The following conditions might suggest that promoter
should be considered:

Velocity is high, density is low and recirculation catalyst is maximized

Dilute temperatures are high due to the previous conditions

Afterburn is high despite high combustor temperatures

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Maximum Capacity

Since many units operate on the basis of pushing the FCC capacity to the limit, it is
appropriate to discuss what will happen in the combustor. Prior comments on the
operating variables have addressed some of the concerns of higher capacity
operation, but an overall perspective is needed.
In general, pushing capacity to the maximum will result in a combustor operating at
high velocity, low density and low catalyst residence time. Directionally, this will tend
to increase afterburn and carbon on regenerated catalyst.
From earlier data shown regarding coke burning kinetics, carbon is reduced to
levels around 0.15 wt% very quickly, but to get to 0.05 wt% requires substantial
additional time. In a maximum capacity operation, there may not be sufficient time in
the combustor to reach carbon levels of 0.05 wt% or below.
It is important to point out that this is not all bad, and in fact may be economically
advantageous. With the use of promoter to maintain control of after burning, it is
possible to allow the CRC to increase as a trade off for more feed capacity.
Although effective catalyst activity is reduced, the reduction may be small enough to
justify the higher capacity operation.
Optimization Summary

All of the above variables need to be thoroughly understood, especially how they
interact with each other. Application of this knowledge properly will result in arriving
at the best operation for each particular unit. Optimization should be considered as
a continuous effort, since what is optimal in one set of circumstances may not be in
another.
As a final note, it should be emphasized that UOP is always interested in obtaining
feedback on the operation and experiences of these units from the refiner. Our
Technical Service department is always available to provide assistance or
consultation as needed. Only through working together can we hope to continue to
improve our designs and their performance capability.

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MAIN COLUMN BOTTOMS AND SLURRY SETTLER

INTRODUCTION

The main column bottoms system on an FCC presents some unusual mechanical
and operating problems. The vapors entering the column are superheated and
contain catalyst fines which may cause erosion or plugging. Heavy oil cascading
down the disc and doughnut (side-to-side on some units) trays cool and condense
the heavy vapors so that they can be fractionated. The catalyst fines are washed
down to the bottom of the column by this cascading stream.

COKE

Many units have some coke buildup in the reactor, vapor line, and bottom of the
main column. The amount in the reactor and vapor line can be minimized by good
insulation. The coke buildup in the main column is influenced by three factors:
1.

Hydrocarbon characteristics

2.

Temperature

3.

Residence Time

Some hydrocarbons have a greater tendency to thermally crack and produce coke
than others. The Conradson or Ramsbottom carbon residue tests may be used to
get some idea of this tendency, but it is difficult to compare one stock with another.
The amount of catalytic cracking that has taken place in the reactor will influence
the coke production of the hydrocarbons in the main column. The operation of the
FCC unit and of the upstream units that produce FCC feed are controlled by other,
more important variables than the main column bottoms coke make. Temperature
and residence time control are used to minimize the bottoms coke problem.

157048
Process Variables
Page 63

The maximum allowable temperature in the bottom of the tower is usually given as
700F (370C). Experience with a particular feed may raise or lower this somewhat,
but it is better to run lower to prevent coke problems. Many refiners use 680-700F
(360-370C) as the normal operating point.
The major control on the bottoms temperature is by the composition of the material,
but the quench line may also be used to sub-cool the bottoms material. This line
returns cool oil directly to the bottoms level, instead of to the disc and doughnut
trays. It is generally used at high throughput, when there is adequate flow to the
discs and doughnuts, and the heat input to the column is high.
Residence time refers only to the time spent in the column, not in the entire slurry
system. The oil begins to cool as soon as it leaves the tower. There may be some
minor coking in the slurry settler and associated piping, but usually this is not
enough to affect plant operations. If the oil is in the tower too long, at too high a
temperature, serious coking can plug the bottom. Removal is difficult, because
chipping away with hammers usually leads to lining damage. Other methods, such
as chemical cleaning, are usually ineffective.
At low charge rates, the bottoms circulation through the exchangers must be
reduced to heat balance the tower. The oil cascading down the discs and
doughnuts decreases to a point where the trays run dry. Because the hot reactor
vapors are not cooled, they can cause warping and distortion of both the disc and
doughnut trays and those above as this large volume of vapors tries to pass up the
column. Catalyst fines will be carried up into the HCO and LCO circuits, which can
be quite serious, because these areas are not designed for fines removal. Product
specifications will be adversely affected.
The solution to this problem and that of long residence times at low circulation rates
is to use the minimum flow line which bypasses the exchangers and returns oil
directly to the column, over the disc and doughnut trays. The flow over these trays
should be at least 50 gpm/ft tower ID (37.3 m3/hr/meter tower ID). This line is
usually used on startup, when the charge rate is low and the tower is cool. As

157048
Process Variables
Page 64

charge rate increases, the flow rate through the minimum line is decreased to force
oil through the heat exchange circuits. There should always be a small amount of oil
flowing through the line, so that the oil does not set up. The same is true for the
quench line to the bottom of the fractionator.
Some units have used a large impingement baffle to break up the reactor vapors as
they enter the column. Many of these baffles proved to be a good starting point for
coke, and the baffles were removed. Inevitably, there is some coke buildup; pieces
may break off with thermal shock or other stresses. If a chunk of coke could enter
the bottom line, it could cause plugging or pump damage. A coke trap made of Type
405 or 410 stainless steel is used at the bottom of the column to keep these large
chunks out of the line. Smaller pieces of coke pass through it and are caught by the
pump suction screens. These can be cleaned on stream, while the larger chunks of
coke might prove difficult to remove from the line.

CATALYST CARRYOVER

The amount of catalyst carryover from the reactor will depend on unit design,
cyclone efficiency, catalyst type, and unit throughput. Unusual problems such as
high reactor level, cyclone failure through cracks or plugged diplegs, or pressure
surges can increase the catalyst carryover to unacceptable levels. A conventional
unit of older design (single stage cyclones) should lose less than 0.4 LB/bbl charge
over to the main column, with most of this returning with the slurry recycle. A new
unit with a riser "Tee" and high efficiency cyclones should lose less than 0.05
LB/bbl.
It is not practical to actually measure the catalyst content of the main column inlet
vapors. The catalyst content of the circulating bottom stream is, however, a good
indication of the catalyst losses. A general assumption may be made that very little
catalyst is entrained up into the HCO or LCO products. If this is not the case, the
bottoms circulation over the disc and doughnut trays should be increased as much
as possible, within the limits imposed by other operating variables. The lower part of

157048
Process Variables
Page 65

the tower should be inspected carefully at the next turnaround to determine if the
problem is here.
The main column bottoms pump discharge manifold is constructed to direct the
catalyst fines and coke particles out of the circulating system. The lines to the
various exchangers come off the top of the manifold. The line to the slurry settler
will come off the end of the manifold from the bottom. If there is no settler, the
reactor recycle and bottoms product lines will both come off the bottom of the
manifold. This obviously will not achieve a complete removal of catalyst fines or
coke, but it will help prevent a buildup in the main column bottoms circulating
system.

SLURRY SETTLER

The slurry settler process flow is shown in Figure 16 in Process Control section.
Main column bottoms enter the settler through a tangential nozzle; this gives it a
swirling motion that promotes a more even distribution of the heavy oil as it moves
up towards the outlet. The catalyst fines settle out and are carried back to the
reactor. The carrying medium will depend upon the operation.
1.

Low activity catalyst with large amounts of recycle:

This would be typical of older units that require the high recycle rates to get desired
conversion. The recycle consists of main column bottoms and HCO, which is cooler
and has a higher flowing specific gravity than the bottoms material. The HCO is
injected into the upper diluent point and flows down with some of the bottoms and
most of the catalyst that enters the settler. A plant operating in this mode would
have a CFR of 1.2 to 2.0.

157048
Process Variables
Page 66

2.

Higher activity catalyst with little or no recycle:

The use of the new higher activity catalysts and better reactor design enable the
refiner to crack most of the feed on the first try. The heavy oil product make is
lower; it is also a more refractory material which tends to go to coke and dry gas
when recycled to the reactor. The carrying material used in this case may be HCO,
but for many units, raw oil is the better choice. The bottom diluent injection point is
used to minimize the amount of raw oil that will go up into the settler. If the raw oil
thermally cracks or goes out with the CSO, it may cause problems with the CSO
product specifications. To help prevent this, the flow back to the reactor should
always be higher than the diluent flow to the settler.

SETTLER OVERHEAD

The amount of CSO that comes off the top of the settler will also depend upon the
operation. The decreased heavy oil make of the newer units can lead to a buildup of
catalyst in the main column because there is less main column bottoms leaving the
tower to take it out. This refers to oil leaving the system, not to the bottoms
circulation streams. The concentration of fines in the tower may build up enough to
cause serious erosion and plugging problems. The most effective solution is to use
a return line from the top of the settler to the main column disc and doughnut trays.
The flow to the settler can then be increased by the amount of oil which is returned
to the main column relatively free of catalyst.
Typical settler flow rates are shown in Table 11. For this table, it was assumed that
catalyst is coming overhead from the reactor at a rate of 100 LB/day. The catalyst
can only leave the system through the outlet to the settler; therefore, the
concentration will be equal to the amount of catalyst (100 LB/day), divided by the
flow to the settler.

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Process Variables
Page 67

TABLE 11
SLURRY SETTLER FLOW
CASE A

CASE B

CASE C

10,000

10,000

10,000

Main Column Bottoms


To Slurry Settler, BPD

1500

500

1500

Main Column Bottoms Catalyst


Concentration, lb/bbl

0.067

0.20

0.067

500

500

500

CSO Product, BPD

1,000

500

500

Recycle to Reactor, BPD

1,000

500

500

1,000

Feed to FCC, BPD

Diluent, BPD

CSO Return to Main Column, BPD

Case A would be an operation with lower activity catalyst and a higher CSO product
make. Case B would be a conversion to higher activity operation, decreasing the
amount of recycle and the CSO product. Neither Case A or B uses a return line
from the top of the settler to the main column. Case C is similar to B in that a higher
activity catalyst is used, with a small amount of main column bottoms produced. The
use of the return line from the top of the settler back to the main column allows the
flow to the settler to be increased to 1500 BPD. A limit on flow to the settler is the
velocity of fines settling. The liquid velocity should never exceed 30 BPD/ft2 (50
m3/d/m2) of settler cross sectional area. Above this, there may be problems with
catalyst carry over into the overhead stream.

157048
Process Variables
Page 68

FCC UNITS WITHOUT SLURRY SETTLER

Some of the new units have incorporated a reactor cyclone configuration which
decreases the amount of catalyst carryover to the main column. The reactor riser
ends with a pair of outlet arms, and a two stage cyclone system on the reactor
outlet eliminates most of the catalyst in the overhead vapors. With this system,
some refiners have elected not to use a slurry settler. The recycle to the reactor and
the bottoms product come directly from the main column bottoms pump discharge
manifold.

PLUGGING

There are occasional problems with plugging in the lines or exchangers of catalyst
bearing streams. If there is a plant upset which causes large amounts of catalyst to
go overhead, such as a sudden dip in column pressure, immediate action should be
taken to remove the extra catalyst from the system. Increased slurry recycle and
clarified oil product would be the two most important steps. These should be
continued until the laboratory confirms that the BS & W content of the bottoms
stream is back to normal.
In the event of a major upset that completely fills the bottoms of the column with
catalyst, care must be taken to avoid further complications. Catalyst holds heat fairly
well and conducts it poorly, so the cool-down period may be on the order of several
days. The thermocouples in the column will be well insulated by the catalyst close to
the wall, so the readings will probably be lower than the actual temperature of most
of the catalyst. Introduction of cold oil or wash water will produce severe pressure
surges that may damage the column internals. The oil soaked catalyst is both a fire
and breathing hazard. The shutdown for cleanout can be estimated at one week, a
good argument against hasty measures that could lead to excessive catalyst
carryover to the column.

157048
Process Variables
Page 69

MAIN COLUMN BOTTOMS EXCHANGERS

To prevent catalyst plugging or erosion in the exchangers, UOP calls for the
following velocities in the tubes:
1.

Straight tubes: maximum velocity 8.0 ft/sec, minimum 4.00 ft/s.

2.

U-tubes: maximum velocity 8.00 ft/sec, minimum 4.00 ft/s.

In general, the optimum velocity is 8.00 ft/s. Straight tube construction is


recommended. It is important to think of these numbers when changing raw oil
charge or exchanger flow rates. Plugged exchangers are difficult to clean. A catalyst
bearing stream is never routed through the shell side of an exchanger because the
catalyst fines will settle to the bottom of the exchanger. There will be a progressive
loss of heat transfer area as more and more tubes are covered by the fines.

MAIN COLUMN BOTTOMS HEAT REMOVAL

The main column bottoms circulation rate is adjusted to control the column's heat
removal requirement. The bottoms stream generally exchanges heat with the raw oil
feed and is utilized in the production of superheated steam in the steam generators.
A reduction or increase in the bottoms heat removal must be compensated by an
increase or reduction in heat removal in another section. Provided no other changes
are made, the overhead reflux rate will compensate for any changes in bottoms
heat removal. As illustrated in Table 12, a decrease in the bottoms stream heat
removal results in an increase in reflux rate. The bottoms stream heat removal
should be adjusted to minimize the reflux rate and maintain good product
distillations.

157048
Process Variables
Page 70

TABLE 12

Feed Rate, BPD

17550

17550

Overhead reflux rate, BPD


Net ovhd light gas yield, MMSCFH
Net ovhd liquid yield, BPD
Ovhd heat removal, MM-BTU/hr

10488
13.81
7973
42.81

11581
13.81
7993
45.24

Net heavy naphtha yield, BPD


Circ. heavy naphtha heat removal
MM-Btu/HR

2782

2782

12.32

12.32

1790

1790

10.17

10.17

967

967

31.0

28.57

Net LCO yield, BPD


Circ. LCO heat removal,
MM-BTU/hr
Net bottoms yield, BPD
Circ. bottoms heat removal,
MM-BTU/hr

GASOLINE/DISTILLATE PRODUCTION

The main column draw temperatures are dependent on the stream's composition
and vary with changes in draw rate. As the gasoline product draw is reduced, liquid
will drop down the column to the LCO draw tray and require an increase in LCO
product draw. The reduced gasoline draw rate will result in a lighter gasoline
product having a lower ASTM distillation end point and a lower draw tray
temperature. The LCO product also becomes lighter because of light material
dropping to the LCO draw tray. The LCO initial boiling point temperature will
decrease with a slight decrease in the draw tray temperature. Table 13 illustrates
the changes which result to the main column and product streams as the LCO yield
is increased by reducing the gasoline endpoint and yield.

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Process Variables
Page 71

TABLE 13

Gasoline:
API
Product rate, BPD
90% BP temp., F
RONC
MC overhead temp., F

57.9
15800
372
90.7
311

57.2
16200
381
90.6
316

56.3
16600
392
90.4
323

Light cycle oil


API
Product rate, BPD
Flash point, F
10% BP temp., F
90% BP temp., F
End point, F
MC draw temp., F

20.1
6000
198
462
624
664
482

19.8
5600
204
471
624
664
485

19.3
5200
212
482
624
664
499

Slurry
API
Product rate, BPD

6.2
2800

6.2
2800

6.2
2800

GASOLINE CUT PROPERTIES

Gasoline or any other liquid stream can be broken up into numerous cuts, each
having distinct properties. Examining the cuts which comprise a typical gasoline
sample will show how overall product quality can be improved.

157048
Process Variables
Page 72

A FCCU gasoline sample from a high severity operation was broken up into nine
cuts, each having a narrow TBP range as illustrated in Table 14. The properties of
the individual cuts are shown in Figures 6 and 7.
TABLE 14
Cut No.

1
2
3
4
5
6
7
8
9

Cumulative
Vol -%
20
30
40
50
60
70
80
90
100

TBP Fraction, F
75 - 93
93 - 145
145 - 181
181 - 210
210 - 250
250 - 286
250 - 286
286 - 334
334 - 387
387+

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Process Variables
Page 73

FIGURE 15: FCC GASOLINE CUT PROPERTIES


Avg. BoilingPoint Temp, F

400

300

200

100

0
1

Gasoline Cut
100

API Gravity

80

60

40

20
1

Gasoline Cut
100

RONC

96

92

88

84

80
1

Gasoline Cut

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Process Variables
Page 74

FIGURE 16: FCCU GASOLINE CUT PROPERTIES


1.2
1

Sulfur, wt %

0.8
0.6
0.4
0.2
0
1

5
Gasoline Cut

100

Bromine

Number

90
80
70
60
50
40
30
20
10
0
1

80

Gasoline Cut

Paraffin/Naptha

70

Aromatic

Olefin

Liquid Vol %

60
50
40
30
20
10
0
1

Gasoline Cut

157048
Process Variables
Page 75

The sulfur content of gasoline increases sharply in the last 387+ TBP fraction as
indicated in the Wt-% SULFUR graph. The overall sulfur content of gasoline hence
could be reduced by lowering the gasoline end point temperature.
The RONC graph of the various cuts indicates a reduction in octane at CUT 4
(181-210 TBP) and CUT 9 (387+ TBP). A slight increase in the overall gasoline
octane can be obtained by reducing the end point temperature of the gasoline. If it
were possible to remove CUT 4, gasoline octane could be further increased.

157048
Process Variables
Page 76

ROUTINE PROCESS VARIABLE CONTROL


REACTOR REGENERATOR SECTION

This tabulation of process conditions is intended to assist the operator in selecting


the optimum operating conditions for different operations. It may be noted here that
process units rarely operate at their design conditions.
Variable

Operating Conditions

Raw oil charge rate

As desired.

Raw oil temperature

To balance coke yield, conversion, and RON


requirements.

Slurry recycle rate

Normally at minimum.

HCO or raw oil to


slurry settler

Equal to or slightly less than total flow of slurry


recycle to reactor, or until clarified oil gravity
changes.

Heavy recycle rate

Heavy recycle rate can be varied to adjust


conversion product yields or increase coke yield.

Combined feed temperature

Normally as high as possible provided neither


reactor nor regenerator temperature is excessive.

Reactor temperature

As necessary to obtain desired conversion and


RON.

Reactor pressure

Equals fractionation column receiver pressure plus


fractionation pressure drop.

Reactor level (Riser


cracking operation)

To cover top stripping grid.

Reactor level (Bed cracking


operation)

Minimum level needed to achieve desired


conversion.

Emergency steam to riser

Used to initiate catalyst circulation on startup and


to avoid plugging the riser on an emergency
shutdown. Normally not used.

157048
Process Variables
Page 77

Variable

Operating Conditions

LCO or gasoline to riser

Used to control regenerator temperature when the


unit is "behind in burning".

Stripping steam

Just enough to strip catalyst. This value can be


arrived at by observing the effect of decreasing the
stripping steam on regenerator temperature.
1.5-2 lb/1000 lb catalyst circulation is typical.

Steam to feed nozzle

Normally adjusted to maximize feed distributor


pressure drop within feed pump hydraulic
constraint. Usually 1-2 wt% of feed.

Regenerator air rate

As necessary to control regenerator temperature


spread or to give good control using automatic
snort. On total CO burning units to obtain 1-4%
oxygen in flue gas.

Regenerator dense
phase temperature

Normally cracking conditions are varied to


optimize regenerator dense phase temperature.
Too cold and catalyst will not be well regenerated.
Too hot and reaction with oil will be thermal with
resultant loss of gasoline and increase in gas.

Regenerator dilute phase


or flue gas temperature
(on conventional partial
CO burning units)

The difference between regenerator dense, dilute


and flue gas temperatures is an indication of the
amount of excess oxygen present, and is the
criterion by which the air rate is varied.

Regenerator pressure
(conventional)

Equals the reactor pressure plus the reactor


regenerator differential pressure.

Regenerator pressure (with


flue gas power recovery)

Regenerator pressure controlled, reactor-regenerator differential allowed to swing within reasonable


limits.

Regenerator level

The catalyst level can vary from about 35" to 80"


of H2O with the unit inventory and regenerator
velocity.

Reactor-regenerator
differential pressure

Varied to obtain stable slide valve differentials and


minimum utility consumption.

157048
Process Variables
Page 78

Variable

Operating Conditions

Slide valve differential


pressure

Dependent on vessel differential and catalyst


condition. Over-rides are normally set at 1-2 psi.

Steam to spray and


torch nozzles

Flow will be almost zero except when sprays are


in service.

Torch oil rate

Used on startup and to control afterburning on


partial CO combustion units.

Torch steam pressure

Only used when necessary to atomize torch oil


and normally 5-10 psi higher than regenerator
pressure.

157048
Process Variables
Page 79

TABLE 15
MAIN COLUMN
Variable

Operating Conditions

Main column bottoms


temperature

Adjust clarified oil yield and quench to hold long


enough to prevent coking.

Circulating slurry rate

As necessary to control fractionating column heat


removal requirements. To minimize top reflux to
obtain minimum gap (25-40F) on gasoline
between 90% and E.P.

Slurry return temperature

Of little interest. Dependent on cleanliness of


exchangers, number in service and circulation
rate.

Clarified slurry yield, or


main column bottoms
yield if no slurry settler

As necessary to control fractionating column


bottoms temperature and level.

Main column bottoms BS&W

Adjust flow to slurry settler, clarified oil return to


main column, and slurry recycle. If no slurry
settler, adjust bottoms recycle and bottoms
product.

Heavy recycle oil circulation

Rate is set as desired to transfer heat to various


reboilers.

Heavy recycle deck


temperature

Depends on distillation range on heavy recycle


and on tower pressure.

Light cycle oil yield

Depends on charge rate and conversion, and is


varied to maintain desired properties of light cycle
oil. Also used to control bottoms level.

Flush oil

As required to keep catalyst out of instruments.


Normally 1500-2000 BPD, but this will vary
between different units.

157048
Process Variables
Page 80

Variable

Operating Conditions

Light cycle oil


stripping steam

Enough to meet flash point specifications.

Light cycle oil


deck temperature

Depends on distillation range of light cat gas oil


and on tower pressure.

Unstabilized gasoline top


reflux rate

Is varied to control tower top temperature and


depends on amount of heat removed lower in
column.

Circulating top
reflux temperature

Depends on water temperature and flow rates.

Fractionator column top


temperature

Varied to control endpoint of unstabilized


gasoline.

Overhead receiver pressure

Can be varied as discussed.

Overhead receiver
temperature

Should always be as cold as is economically


possible.

Unstabilized gasoline yield

Depends on charge rate and conversion.

Wet gas molecular weight

Minor variations in density will be due to changes


in receiver conditions, but major changes will be
due to increased hydrogen production. At low
densities, the compressor will have an increased
tendency to surge.

Wet gas flow

Dependent on compressor speed but must be


adequate to handle production plus spillback for
control. Must be above minimum to keep out of
surge.

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Process Variables
Page 81

TABLE 16
GAS CONCENTRATION SECTION
Variable

Operating Conditions

Wet gas compressor


Variable speed

Run at minimum governor until spillbacks close.

Fixed speed centrifugal

Butterfly valve opens away from limiting stop as


spillbacks close.

Fixed speed reciprocating

On spillback control.

Wet gas spillbacks


High pressure separator
Temperature
Pressure
Primary absorber
Top and intercoolers
temperatures

Vary as needed to hold main column overhead


receiver and interstage pressure. Used to keep
centrifugal machine out of surge.
80F-100F (27-38C)
Rides on primary absorber backpressure.
Less than 100F (38C)

Intercooler flow rates

As needed for good absorption efficiency.

Pressure

Rides on sponge absorber backpressure.

Sponge absorber
Top temperature

As cool as economically practical.

Lean oil flow rate

As needed for good absorption efficiency. Do not


flood tower.

Pressure

Controlled to give good absorption efficiency and


hold correct backpressure on HPS.

157048
Process Variables
Page 82

Variable

Operating Conditions

Stripper Overhead vapor flow


rate

Controlled by heat input to column to give


sufficient C2- and H2S stripping.

Heat input to column

Controlled to give proper overhead vapor rates.

Pressure

Rides on high pressure separator backpressure.

Debutanizer
Top temperature

Controls reflux to give desired RVP of gasoline.

Top reflux temperature

Should be as cold as economically possible.

Reboiler heat

As required to give good fractionation.

Pressure

Varied as needed for good fractionation, but must


be high enough to allow condensation of C3-C4
stream by air fin fans or cooling water.

157048
Process Calculations
Page 1

PROCESS CALCULATIONS
INTRODUCTION
Throughout the years the Fluid Catalytic Cracking process has been a very versatile
and flexible tool for the refiner, and has become the basic conversion step in the
modern refinery. This process has survived and prospered because of its ability to
handle the many changes in catalyst, operating conditions, and feedstocks that have
occurred over the years.
The FCC Unit produces large volumes of high octane gasoline, olefinic LPG, fuel oil
(LCO and MCB), fuel gas, steam, and electricity. The yields are mainly determined by
process variables (i.e. feedstock, operating conditions, mechanical features, and type of
catalyst). Process variables have varying degrees of interdependence and may change
frequently producing changes in the yield structure of the products. A performance test
conducted at least once a week is recommended to evaluate the effect of process
variables on yield. The tests can be used to chart a history of the unit and to find
conclusions at different operating conditions.
The performance test provides accurate yield structures at a particular set of operating
conditions and provides a base point for further testing. The Performance Test normally
includes a heat balance, material balance, and a pressure survey. In those cases where
more information is desired, a Mechanical Evaluation Test is recommended. The refiner
can use this test to assess the potential of the unit and determine possible bottlenecks.
This section explains how to accomplish an acceptable Heat and Material balance and
how to do some of the most important calculations in the FCC Unit. An FCC
Performance Test Procedure is available on request from the Technical Service
Department. This procedure explains in detail how to conduct a performance test in the
FCC Unit.

157048
Process Calculations
Page 2

MATERIAL BALANCE
A material balance on an FCC Unit is done by drawing an envelope around the unit in a
manner that flow rates are known for all streams. This envelope includes the Reactor,
Regenerator, Main Column, and Gas Concentration sections. Normally, the Gas
Concentration Unit includes the primary absorber, sponge absorber, stripper column,
and debutanizer column.

1.

Data

Flow rates, flowing temperatures and laboratory analyses are required for each stream.
Pressure is also needed for the gas streams. The following table shows the information
needed to do a material balance:
INPUT DATA FOR HEAT AND MATERIAL BALANCE
Stream

Flow Temp. Pressure

API

Distillation

Feed

Yes

Yes

Yes

D-1160

Air*

Yes

Yes

MCB

Yes

Yes

Yes

D-1160

Yes

LCO

Yes

Yes

Yes

D-86

Yes

Gasoline

Yes

Yes

Yes

D-86

LPG

Yes

Yes

Sponge Gas

Yes

Yes

Meter Factor
Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Flue Gas
Notes

GC

*Ambient temperature and relative humidity of air are needed.


Reactor, Regenerator, and combined feed temperature are needed for Heat Balance

The method for including extraneous streams is straight forward as long as flow rates
and analyses are known. These additional streams coming into the Main Column and
Gas Concentration Unit are subtracted from the product streams.

157048
Process Calculations
Page 3

2.

Liquid Streams

Calculate corrected liquid flow rates using the following equation:


Q = K R (Gf)1/2 / Gb
Where:

Q = flow rate
K = flow meter constant ("K" factor)
R = chart reading
Gb = base gravity @ 60F
Gf = gravity at flowing temperature

The flowing gravity Gf is calculated using the following equation:


Gf = Gb x VCF
Where:

VCF = Volume correction factor


VCF = EXP [ (-o) T(1+0.8 o T) ]

0.9545

Where:
Go = density at 60F in kg/m3
T = observed temperature in F
T= T - 60
o = coefficient of thermal expansion at 60F, (1/F)

926
173
113

The set of correlations for the coefficient of thermal expansion based on API Data
Tables are:
o = (Ko + K1 Go + K2 Go )/ Go
Where:

0.00039779

157048
Process Calculations
Page 4

Product
Crude Oils

API Range
0 100

Ko

K1

K2

341.0957

0.2438

Gasoline

52 85

192.4571

Gasoline/Jet

48 52

1489.0670

-0.0018684

Jet Fuels

37 48

330.3010

Fuel Oils

0 37

103.8720

0.2701

0.3488

Lubricating Oils

-10 45

For FCC Raw Oil Feedstock (VGO); Ko = 341.0957, K1 = 0, K2 = 0


The following rounding is applied to the input and output of all routines.
Temperature:
Density:
VCF:

0.1F
0.1 API or 0.5 kg/m3
five significant figures for computation

Example: Raw Oil Charge


K = 3,380 in BPSD
R = 8.9
Gb = 0.9260
VCF = 0.9545
Gf = 0.9260 x 0.9545 = 0.8839
Q = 3,380 x 8.9 x (0.8839)1/2 / 0.9260= 30,542 BPSD
Q = (BPSD) x 5.614583 ft3/bbl x (Gb x 62.3635 lb/ft3 H2O)/24 hr/day
Q = 412,615 lb/hr
Similar calculations are done for all C5+ liquid streams. LPG streams are treated as follows:

157048
Process Calculations
Page 5

Estimation of VCF for LPG


The following equation approximates VCFs from API Tables #33 and #34:

VCF 10 A*Gb B T 60 1.0


Where:
T
Gb
A
B

=
=
=
=

Flowing Temperature, F
Specific Gravity @ 60F, in g/ml
2.64641798
1.40583481

157048
Process Calculations
Page 6

3.

Gas Streams

Calculate corrected gas and air flow rates as follows:


Q = K x R x (Pf/(Tf x SG))1/2
Where:

Q = flow rate
K = flow meter constant ("K" factor)
R = flow meter reading
Pf = Pressure at flowing conditions (absolute)
Tf = Temperature at flowing conditions (absolute)
SG = specific gravity of gas = MWgas/MWair (1.0 for air)

Example: Sponge Gas


Q = K x R x [(Pf/(Tf x SG))]1/2
Where:

K = 91,848 scfh
R = 6.5 chart reading
Pf = 173 psig + 14.7 = 187.7 psia
Tf = 113F + 460 = 573R
SG = 0.7054 from Sponge gas calculations
MW = 18.9 from Sponge gas calculations

Q = 91,848 x 6.5 x [(187.7)/(573 x 0.7054)]1/2 = 406,837 scfh


M = Mass Flow = scfh x MW/379.67 = 20,261 lb/hr
Where:

379.67 is the conversion factor for scf / mol

Similar calculations are done for all gas, vapor, and air streams.

157048
Process Calculations
Page 7

4.

Calculate Coke

The coke make is calculated from the Heat Balance. (Refer to Heat Balance calculation
section.)

5.

Calculate the as Produced Yields

A product yield is defined as the product rate divided by the raw oil rate.
The volume percent of each product stream is:
Vol-% (A) = (A, bpsd)100/Fresh Feed, bpsd
The weight percent is:
Wt-% (A) = (A, lb/hr)100/Fresh Feed, lb/hr
Where:

A = any product stream

157048
Process Calculations
Page 8

6.

Weight and Liquid Volume Recoveries

Once the weight and the volume flows are known for each stream, the Weight recovery
and the Liquid volume recovery can be calculated. Proper data analysis requires that
the Weight recovery must be 100.0 2.0 wt-%. Errors outside this range are significant
and cast doubts on the validity of the test data. The Sponge Gas used to calculate the
Weight recovery should not include the inert gases (N2, O2, CO, CO2). In addition, the
as-produced Liquid Volume recovery does not include the C3+ from the sponge gas.
Weight % Recovery = (Products, lb/hr x 100)/(Fresh Feed + Extraneous Feeds) lb/hr
Liquid Volume % Recovery = (Products, bpsd x 100)/(Fresh Feed + Extraneous
Feeds)bpsd

7.

Conversion

Conversion is defined as the volume percentage of raw oil converted to gasoline and
lighter components. This is calculated as:
Conversion, Vol% =

Feed - LCO - HCO - MCB


100
Feed

This conversion is called as-produced or apparent conversion because is not corrected


for cut-points. The corrected or true conversion is calculated using the same equation
after the gasoline and LCO yields are corrected for cut-points.
8.

Gasoline and LCO Yield Adjustments

It is important to correct the gasoline and LCO yields on a constant cut-point basis. It is
inaccurate to compare gasoline yields at different 90% or EP temperatures. The gasoline
yield must also be adjusted by removing the C4's and adding the C5's and C6's from the
LPG and Sponge Gas streams. The procedures to adjust the liquid yields and to calculate
the C4's in the gasoline are attached in this section.

157048
Process Calculations
Page 9

9.

Gasoline Selectivity

The gasoline selectivity is the corrected gasoline yield divided by the true conversion:
Gasoline Selectivity =

10.

(Corrected Gasoline Yield)


100
True Conversion

LPG and Sponge Gas Calculations

These procedures use the mol percentage from the GC analysis, the molecular weight,
and the specific gravity to calculate the flow rate of each component. Also, the stream
specific gravity and molecular weight are calculated. The procedure is attached in this
section.

11.

C3 and C4 Recovery

The C3 and C4 recovery indicate how the Gas concentration is performing. The C3
recovery is calculated as:

C3 Recovery, Vol% =

C3 in LPG
100
(C3 in LPG + C3 in Fuel Gas)

The C4 recovery is calculated as:


C4 Recovery, Vol% =

C4 in LPG
100
(C4 in LPG C4 in Fuel Gas C4 in Gasoline)

157048
Process Calculations
Page 10

FCC Unit Material Balance


Refiner: _______________________________

Location: _______________________

TI - Tag

FE - Tag

Gravity

Vol.Corr.

Flowing

Meter

Temp. F

Readings

Gb@60F

Factor

Gravity Gf

"K"

Fresh Feed (FF)

TI10

Main Col Bottoms


(MCB)

TI-20

lb/Hr

Vol%

Wt%

8.90

0.9260

0.9545

0.8839

3,380

30,538

412,601

4.80

1.0412

0.8806

0.9169

418

1,843

28,005

6.04

6.79

9.00

0.9200

0.9838

0.9051

700

6,515

87,450

21.33

21.19

7.60

0.7599

0.9489

0.7211

2,118

17,987

199,434

58.90

48.34

7.20

0.5612

0.9653

0.5418

632

5,964

48,833

19.53

11.84

0.00

0.00

FRC-20
462

TI-30

Light Cycle Oil


(LCO)

BPSD

FRC-10
173

Date: __________

FC-30
101

Gasoline (DebBt)

TI-40

FRC-40

LPG

TI-50

LPG (ELPG)
Extraneous Feed

TI-

Coke

See attached Heat Balance calculation sheet.

148
FRC-50
87
FRC-

25,187

6.10

6,589

18,821

4.56

6,996

20,887

PE-Tag
Press, psig
8

TI-60

Sponge Gas (SGas)

FC-60
113

Gas (HGas)
Extraneous Feed

TI-

9a

Air to Regenerator
(Dry Back)

TI-70

9b

1.00

5.00

1.00

W/o Inerts

0.00

44.5

46,000

81,721

374,251

56

325

520

2,382

56

635

1,260

5,771

83,502

382,405

PI-72

FIC-74
230

1,518

PI-70
6.83

FIC-72

TI-74

Air to Distributor 2

W/o Inerts
173

PRC-

FIC-70

230
9c

0.6519

FC-

TI-72

Air to Cat. Cooler

PRC-60
6.50

415

SCFM

PI-74
6.20

1.00

Total Air to Regen (Wet Basis)

As produced Calculations

10

Weight Rec Inert Free

= [MCB lb/hr+LCO lb/hr+DebBt lb/hr+LPG lb/hr+SGas lb/hr+Coke lb/hr]*100/


[FF lb/hr+ELPG lb/hr+EGas lb/hr] =

98.82

Wt%

11

Liquid Vol. Recovery

= [MCB bpsd+LCO bpsd+DebBt bpsd+LPG bpsd]*100/[FF bpsd+ELPG bpsd]

105.8

Vol%

12

Conversion

= [FF bpsd-MCB bpsd-LCO bpsd]*100/[FF bpsd]

72.6

Vol%

For Liquids

BPSD = Units K [SQRT(Gf)]/Gb

lb/hr = [BPSD (Gb) (5.6146ft3/bbl) (62.3689lb/ft3)]/(24h/d) = (14.591) ( BPSD) (SG)

For Gases or Air

SCFM = K Units SQRT{psia/(R*Gb)}

LV%

= (stream, bpsd)(100)/(FF, bpsd)

lb/hr = (scfm MW 60min/hr)/379.5


Wt% = (stream, lb/hr)(100)/(FF, lb/hr)

uop1292rc

157048
Process Calculations
Page 11

FCC Unit Material Balance Continuation


Refiner: _______________________________

Location: ____________________

Yields Adjustment for Gasoline @ 380F - 90% and LCO @600F - 90%.
IBP, F
10%, F
70%, F
90%, F
EP, F
Gasoline
LCO

319

460

MCB

524

710

569

Date: _____________

API

BPSD

lb/hr

367

410

54.71

17,987

618

653

22.30

6,515

87,450

4.40

1,843

28,005

26,346

314,889

Totals

199,434

Gasoline
Gasoline Factor (F1)

= [(380-T90)/(EP-T90)](1/9)+1

= [ ( 380 367 )/(410-367)]

(1/9) + 1=

LCO Factor (F2)

= [(380-IBP)/(T10-IBP)](1/9)

(1/9) =

cGasoline, BPSD

= (Gasoline, bpsd)(F1) + (LCO,bpsd)(F2)

[ ( 380 - 319 )/(460-319)]

18,587

1.034 F1
0.05 F2

cBPSD

60.9

cLV%

c API

= API + 37.5(LV% - cLV%) / LV%

52.13

c API

0.771

cSG

cGasoline, lb/hr

= cBPSD x cSG x 14.591

208,974

c lb/hr

50.6

cWt%

lb/hr

BPSD

C4's in Gasoline

3,390

380

C5's + C6's in LPG

423

46

C5's + C6's in SGas

248

26

C5's + C6's in Extr Feeds

Gasoline Yield Adjustment for C4's, C5's, & C6's.

13 Corrected Gasoline, BPSD

= cGasoline-C4's+C5's+C6's Extr(C5+C6)

18,587

corrBPSD

60.9

corrLV%

14 Corrected Gasoline, lb/hr

= cGasoline-C4's+C5's+C6's-Extr(C5+C6)

208,974

corrlb/hr

50.6

corrWt%

15 Corrected API

= ((141.5*BPSD*14.591)/(lb/h*24))-131.5

52.13

corrAPI

LCO
LCO Factor (F3)

= [(600-T70)/(T90-T70)](0.2)+0.7 =

[ (600-569)/ (618-569)] (0.2) +0.7 =

0.827 F3

MCB Factor (F4)

= [( 600-IBP )/( T10-IBP )]( 0.1 ) =

0.041 F4

Gasoline Factor (F5)

= Gasoline - cGasoline

[ ( 600 524
( 17,680) -

16 Corrected LCO, BPSD

= [(LCO bpsd)F3 + (MCB bpsd)F4 + F5]/0.9

17 Corrected LCO API


18 Corrected LCO, lb/hr

)/ (710-524)]

(0.1) =

(18,587) =

-907 F5

5,059

corrBPSD

16.6

corrLV%

= API + 5( LV%-corrLV% )/LV%

23.42

corrAPI

0.913

corrSG

= corrBPSD x corrSG x 14.591

67,416

corrlb/hr

16.3

corrWt%

2,392

corrBPSD

7.8

corrLV%

35,780

corrlb/hr

8.7

corrWt%

MCB
19 Corrected MCB, BPSD

= Total C5+ Liq. Yield - Corr Gasoline - Corr LCO =


= 17,689+6,515 +1,843-18,587 -5,059

20 Corrected MCB, lb/hr

= Total C5+ Wt. Yield - Corr Gasoline - Corr LCO =


= 196,715+

87,450+

28,005-208, 974-67, 416

21 Corrected API

= [( 141.5 * BPSD * 5.6146 * 62.3689 )/( lb/h * 24 )] - 131.5

6.5

corrAPI

22

= [FF bpsd - corrMCB bpsd - corrLCO bpsd]100/[FF bpsd]

75.6

corrVol%

True Conversion

*Note that Total C5+ yield = cGasoline + LCO + MCB

API = (141.5/SG) - 131.5

Note- The Factor equations are valid only if the as produce 90% temperatures are between 360-400F for gasoline and 580-620F for LCO.
The Factor Equations were developed from the 90% plus 10% Method. Used this method if the 90% Temp. are not in the specified range.

157048
Process Calculations
Page 12

Sponge Gas Calculations Example


Refiner: ______________________________Location: _____________________________ Date: _______________
A

C=AxB

g/100mol

Ib/hr

sp gr

0.04
0.00
1.47
4.31
5.82

1.3
0.0
64.7
120.7
186.7

14
0
716
1,335
2065

28.29
2.57
28.21
15.83
15.55
0.48
1.48
0.59
0.25
0.24
0.25
0.12
0.06
0.00
0.00
0.00
0.00
0.26
94.18
100.00

57.0
87.6
452.6
476.0
436.2
21.2
62.3
34.3
14.5
13.5
14.0
6.7
3.4
0.0
0.0
0.0
0.0
22.4
1,702
1,888

Component

MW

mole%

O2
CO
CO2
N2
Total Inertes

32.00
28.01
44.01
28.01
(t)

H2
H2S
C1
C2
C2=
C3
C3=
iC4
nC4
1-C4=
i-C4=
t-C4=
c-C4=
1,3-C4==
i-C5
n-C5
C5=
C6+
Total Products
TOTAL

2.02
34.08
16.04
30.07
28.05
44.10
42.08
58.12
58.12
56.11
56.11
56.11
56.11
54.09
72.15
72.15
70.14
86.18
(T)

MW = TC/TB =
18.9
SG = MW/28.966 =
0.6519
Mole % Inerts=tB=
5.82
Wt% Inerts=100tD/TD= 9.89
Inerts = tD =
2,065 Ib/hr

F
bpsd (scfh)

(168)
(0)
(6,170)
(18,091)
(24,429)

631
969
5,006
5,265
4,825
234
689
379
161
149
155
74
37
0
0
0
0
248
18,821
20,887

0.5077
0.5220
0.5631
0.5844
0.6013
0.6004
0.6100
0.6271
0.6272
0.6248
0.6312
0.6496
0.6640

Pres. Psig = 173


Temp. F = 113
Meter Units = 6.5
Meter K = 91,100

(118,745)
(10,787)
(118,409)
(66,445)
(65,270)
31.6
90.4
46.2
18.8
17.0
17.7
8.4
4.1
0.0
0.0
0.0
0.0
25.6
259.8
(404,086)

=14.7=psia
+ 460=R

187.7
573.0

Gas with Inerts: V = Vol. Flow = KxUnitsxSQRT{psia/(R*SG)} = 419,742 scfh


M = Mass Flow = scfh x MW/379.5 =
20,887 Ib/hr
Inert-free Gas:

Mass = (M Inerts) = M(100-wt%Inerts)/100 =


Vol. Flow=(V)-(tF)=V-(V x M%Inerts/Tmoles) =

bpsd = [Ib/hr x24]/[ SGx5.614583ft3/bblx62.3689lb/ft3]

18,821 Ib/hr
395,313 scfh

scfh = V x Mol%/TB

D = C x M/TC = C x Total Mass Flow/(Total gr/100 mol)

157048
Process Calculations
Page 13

Debutanizer Overhead (LPG) Calculation Example:


Refiner: ______________________________Location: _____________________________ Date: _______________
A
Component

MW

B
mole%

C=AxE

g/100mol

SG

E=C/D

F=MxCftC G=VxE/tE

cc/lOOmol

lb/hr

H2S

34.08

0.0

0.0

0.7871

C2

30.07

0.0

0.0

0.3563

C2=

28.05

0.0

0.0

0.3680

C3

44.10

12.1

533.6

0.5077

1,051

5,216

704

C3=

42.08

36.2

1523.3

0.5220

2,918

14,891

1,955

iC4

58.12

10.7

621.9

0.5631

1,104

6,080

740

nC4

58.12

3.8

220.9

0.5844

378

2,159

253

1-C4=

56.11

8.5

476.9

0.6013

793

4,662

531

i-C4=

56.11

12.4

695.7

0.6004

1,159

6,801

776

t-C4=

56.11

9.2

516.2

0.6100

846

5,046

567

c-C4=

56.17

6.2

347.9

0.6271

555

3,401

372

1,3-C4==

54.09

0.3

16.2

0.6272

26

159

17

i-C5

72.15

0.4

28.9

0.6248

46

282

31

n-C5

72.15

0.2

14.4

0.6312

23

141

15

C5=

70.14

0.0

0.0

0.6496

C6+

86.18

0.0

0.0

0.6640

100.0

4,996

TOTAL (t)

8,899

48,838

bpsd

0
5,962

LPG S.G. =

tC/tE = 0.5614

Temperature, 0F

87

LPG MW =

tC/tB = 50.0

Vol. Corr. Factor

0.9653

Flow Gravity, Gf

0.5419

Meter Units
Meter K

=
=

7.2
631.5

V=Vol.Flow=Units x K x [SQRT(Gf)]/SG

5,962 bpsd

M = Mass Flow = (BPSD x SG x 5.6146ft3/bb1 x 62.3689lb/ft3)/24hr/d =


=

48,838 lbs/hr

157048
Process Calculations
Page 14

Propane and Butane Recovery Calculation Example:


(1)
(2)
Sponge Gas
Component
C3
C3=
Total C3s (t)

bpsd
32
90
122

234
689
923

bpsd
704
1,956
2,660

lb/hr
5,215
14,888
20,103

(5)
(6)
Stabilized Gasoline
(Debut. Bottoms)
bpsd
lb/hr
0
0
0
0
0
0

iC4
nC4
1-C4=
i-C4=
t-C4=
c-C4=
1,3-C4= =
Total C4s (T)

46
19
17
18
8
4
0
112

379
161
149
155
74
37
0
956

740
253
531
776
567
372
17
3,257

6,078
2,159
4,661
6,800
5,045
3,400
159
28,301

0
47
34
34
112
44
109
380

lb/hr

(3)
(4)
Debutanizer Overhead

0
399
299
299
997
399
997
3,390

C3 Recovery = t(4) * 100 / [t(2) + t(4)] =

95.6

wt-%

C4 Recovery = [T(4) + T(6)] * 100 / [T(2) + T(4) + T(6)] =

97.1

wt-%

157048
Process Calculations
Page 15

Yields Adjustment Composite 90% Plus 10% Method

This method uses the ASTM distillation of the liquid products to create a composite
curve and correct the yields to any specified 90% temperatures.
Procedure

1. Using the ASTM distillation and a straight line interpolation equation, calculate
the LV% distilled every 20F for all the product streams.
%x=[(Tx-Ta)/(Tb-Ta)](%b-%a)+%a

Straight line interpolation equation

%a < %x < %b
Ta < Tx < Tb
2. Calculate the composite volume and percent every 20F using the following
equations:
Cumulative BPD @ Tx =
BPD = [(%Gasoline) (BPSD Gasoline) + (% LCO) (bpsd LCO) + (% MCB)
(bpsd MCB)}/100
Cumulative LV% @ Tx = 100 BPD/Total BPD
3. Calculate Corrected Gasoline 90% @ 380F or Specified 90% Temperature:
Corrected Gasoline (Composite Yield @ 380F)/(0.9)
4. Calculate Corrected LCO 90% @ 600F or Specified 90% Temperature:
Corrected LCO = (Composite Yield @ 600F)-(Corr Gasoline)/(0.9)
5. Calculate Corrected MCB by difference:
Corrected MCB = Total Liquid Yield Correct Gasoline Correct LCO

157048
Process Calculations
Page 16

Data:
(%)
IBP
10%
30%
50%
70%
90%
EP
BPSD

Gasoline
(F)
94
124
165
222
294
367
410

LCO
(F)
319
460
503
533
569
618
653

MCB
(F)
524
710
759*
807*
876*
1100*
1200*

Total

17,680

6,515

2,227

26,422

Note - *These temperatures are not needed.


%x = ((Tx-Ta)/(Tb-Ta))*(%b-%a)+%a
%a < %x < %b
Ta < Tx < Tb
i,e,
= ((100-94)/(124-94))*(10-0) +0 = 2.5
BPD = [(%Gasoline)(BPSD Gasoline) + (% LCO)(bpsd LCO)+(% MCB)(bpsd MCB)}
/ 100
%

= 100 BPD / Total BPD

157048
Process Calculations
Page 17

Data:
Tx, F
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
367
380
400
410
420
440
460
480
500
520
540
560
580
600
618
620
640
660
680
700

Gasoline

LCO

MCB

%x
0.0
2.0
8.7
17.8
27.6
35.3
42.3
49.3
55.0
60.6
66.1
71.6
77.1
82.6
88.1
90.0
93.0
97.7
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0

%x

%x

0.0
0.1
1.5
2.9
3.4
4.3
5.7
6.5
7.2
8.6
10.0
19.3
28.6
37.9
53.9
65.0
74.5
82.7
90.0
90.6
96.3
100.0
100.0
100.0

0.0
0.9
1.9
3.0
4.1
5.1
5.2
6.2
7.3
8.4
9.5

Composite
BPD*
0
354
1,532
3,148
4,873
6,235
7,475
8,716
9,724
10,706
11,688
12,667
13,640
14,701
15,726
16,134
16,728
17,643
18,100
18,147
18,239
18,332
18,938
19,544
20,150
21,210
21,958
22,600
23,156
23,656
23,696
24,092
24,358
24,382
24,406

Percent
0
1.34
5.80
11.91
18.44
23.60
28.29
32.99
36.80
40.52
44.24
47.94
51.62
55.64
59.66
61.06
63.31
66.77
68.51
68.68
69.03
69.38
71.67
73.97
76.26
80.27
83.10
85.54
87.64
89.53
89.68
91.18
92.19
92.28
92.37

Corrected Gasoline =
=

(Composite Yield @ 380F) / (0.9)


(16,728 / 0.9) = 18,587 BPD

Corrected LCO

=
=

((Composite Yield @ 600F) - (Corrected Gasoline)) / (0.9)


(23,156 18,587) / 0.9 = 5,077 BPD

Corrected MCB

=
=

(Total Liquid Yield Corrected Gasoline Corrected LCO)


(26,422 18,587 5,077) = 2,759 BPD

157048
Process Calculations
Page 18

REACTOR AND REGENERATOR HEAT BALANCE

Burning coke in the regenerator provides all the heat necessary for the operation of
the unit. Yet, roughly 30-40% of the heat generated by the combustion of coke exits
the regenerator in the form of hot flue gas. The remainder is absorbed by the
regenerated catalyst which carries it to the reactor riser where it is used to vaporize
and heat up the combined feed to the desired cracking temperature.
The amounts of energy associated with the unit's operation are determined from a
catalyst section heat balance. The energy balance equation at steady state may be
written as:
Energy in + Energy produced = Energy out + Energy consumed

(1)

Regenerator Energy Balance

Energy in

= Energy (air + spent catalyst + coke)

Energy produced

= Combustion heat of coke

Energy out

= Energy (flue gas + regenerated catalyst + removed +


radiation losses)

Energy consumed

= 0

If the Regenerator temperature is the reference temperature then,


-H Air - H Spent Catalyst - H Coke + H Combustion of coke =
Hremoved + Hradiation losses

or:

H Spent Catalyst = H Combustion of Coke - H Coke - H Air - Hremoved Hlosses


(2)

157048
Process Calculations
Page 19

Reactor Energy Balance

Energy in

= Energy (feed + regenerated catalyst + diluents)

Energy produced

= 0

Energy out

= Energy (reactor vapors + spent catalyst + radiation losses)

Energy consumed = Heat of reaction


If the Reactor temperature is the reference base temperature, then
-Hfeed - Hdiluents + Hregenerated catalyst = Hradiation losses + Heat of Reaction
or
Hregenerated catalyst = Hfeed + Hdiluents + Hradiation losses +
Heat of Reaction

(3)

The enthalpy change for the spent and regenerated catalyst is given by
Hspent catalyst = mass flow Cp (Rg Temp - Rx Temp)

(4)

Hregenerated catalyst = mass flow Cp (Rx Temp - Rg Temp)

(5)

At steady conditions,
Hspent catalyst + Hregenerated catalyst = 0

(6)

157048
Process Calculations
Page 20

Regenerator Heat Balance


Flue Gas
Spent Cataly st
Coke
Ra diati on Los ses
H Combustion
of Coke
He at Remov al

Regenerated Catal ys t
Air

Reactor Heat Balance


Reactor Vapors
Regenerated Catalyst

H Reaction

Spent Catalyst
Coke
Feed

Diluents

Radiation Losses

157048
Process Calculations
Page 21

Combining equations (2), (3) and (6)


H Combustion of coke = H Air + H Coke + Hremoved +
Hregen.rad. losses + Hfeed + Hdiluents +
Hrx rad. losses + Heat of Reaction

(7)

The equation (7) demonstrates that all the energy in the Reactor-Regenerator
system is provided by the combustion of coke. The radiation loss term in this
equation is not a major item, but since vessel insulation is not perfect, some
radiation losses do occur. The term Hremoved refers to the heat duty of catalyst
cooler(s). The heat of reaction is the energy required to convert the feed to products
via the catalytic reaction mechanism.
The heat produced by the combustion of coke, equation (7), can be calculated from
the coke product rate and the mode of the regeneration operation. If all the CO
were burned to CO2 in the regenerator, more heat would be available per pound of
carbon than when the unit runs in this normal partial combustion mode. The heat
liberated by carbon combustion to CO2 is 14,150 BTU/lb (7,860 kcal/kg or 32,910
kj/kg) of carbon whereas heat for combustion to CO is only 3,960 BTU/lb (2,200
kcal/kg or 9,210 kj/kg).
Conversion Factors:
kcal/kg 1.8 = BTU/lb
BTU/lb 2.326 = kJ/kg
kcal/kg 4.187 = kJ/kg
The heat of reaction is endothermic. Energy is consumed by the reaction which
breaks the heavy hydrocarbon molecules into smaller, light hydrocarbon products.
The heat of reaction must be calculated from the energy balance using equation (7).
The most important value that can be calculated from the energy balance is the
catalyst/oil weight ratio. This ratio is important because it is a major factor in
hydrocarbon conversion and coke lay-down.

157048
Process Calculations
Page 22

The following sample outlines the energy balance calculation method:


1.

Data Required

This heat balance is for a 30,565 BPSD feed case with the FCC Unit in total
combustion mode. The process conditions are:
Temperatures:

Pressures:

Reactor
Combined Feed
Lift Gas
Lift Steam
Feed Steam
Stripping Steam

970F
375F
100F
380F
380F
380F

Regenerator
Regenerated Catalyst
Flue Gas
Average Hottest in Rg
Air Blower Discharge
HP Boiler Feed Water
Catalyst Cooler Steam

1371F
1368F
1375F
399F
220F
463F

Catalyst Cooler Steam

452 psig

157048
Process Calculations
Page 23

Flow Rates:

Fresh Feed
(No Recycle)
Lift Gas
Lift Steam
Feed Steam
Stripping Steam
Total Air to Regenerator*
Catalyst Cooler Steam
Catalyst Cooler Blowdown

3,250 lb/hr
12,900 lb/hr
1,800 lb/hr
5,000 lb/hr
382,405 lb/hr
56,033 lb/hr
6,952 lb/hr

Total air includes: air to combustor, air to upper regenerator, and air to catalyst
cooler.

Flue Gas Composition, mol%


(by GC Method)

CO
CO2
O2 + Ar
N2
SO2
NO2

2.

412,923 lb/hr

=
=
=
=
=
=

0.0
15.50
3.47
81.03
0.0
0.0

Flue Gas Composition Adjustment

Unlike an Orsat analysis, a GC analysis includes Argon with the Oxygen. The first
step is to adjust the flue gas O2 content for Argon (Ar). The Ar content is assumed
to be 1.2% of the nitrogen, therefore,
Ar = (0.012) (81.03) = 0.97 mol%.

157048
Process Calculations
Page 24

The corrected analysis is now:


CO
CO2
O2

=
=
=
=
=
=

N2 + Ar
SO2
NO2

3.

0
15.50
3.47 - 0.97 = 2.5

81.03 + 0.97 = 82.0


0
0

Combustion Air Corrected to a Dry Basis

A psychometric chart is used to determine the moisture content of the regeneration


air. At atmospheric conditions of 62F and a relative humidity of 97%, the moisture
content is:
Moisture Content =

0.01152 lb H2O
lb dry air

Wet Air = 380,200 lb/hr


Dry Air = 380, 200 lb/hr wet air

1 lb dry air
(1 + 0.01152) lb wet air

= 375, 870 lb/hr

Water in Air = 380,200 lb/hr - 375,870 lb/hr = 4,330 lb/hr

4.

Calculate Flue Gas Rate

The flue gas rate can be calculated from the regeneration air rate. These two
streams are related by the inert N2 + Ar content which remains constant through the
catalyst regeneration. From a Nitrogen balance,
Since, moles =

Weight
Molecular Weight

157048
Process Calculations
Page 25

Then
Dry Air = (375,870 lb/hr)/(28.966 MW) = 12,976 lb mol/hr
mol/hr (N2 + Ar) in dry air = mol/hr (N2 + Ar) in flue gas
79 mol inerts
lb mol FG
82 mol inerts
12, 976 lb mol

100 mol air


hr
100 mol FG
hr

Flue Gas (FG) = 12,501 lb mol/hr

5.

Calculate the Carbon (C) Content of Coke

The carbon (C) content of the coke is calculated from the flue gas composition. One
mol of C is burned for each mole of CO or CO2produced.
C + O2 + H2 + S + N = CO + CO2 + H2O + SO2 + NO2 + O2
C=

0 mol CO + 15.503 mol CO2


1 mol C
12, 501 lb mol

mol CO/CO2
hr FG
100 mol FG

C = 1,938 lb mol/hr of carbon

6.

Calculate the Hydrogen Content of Coke

The hydrogen (H2) content of the coke must be calculated from an O2 balance:
O2 in regeneration air = excess O2 in flue gas +
+ O2 reacted to CO (0.5 mol O2/mol CO)
+ O2 reacted to CO2 (1 mol O2/mol CO2)
+ O2 reacted to H2O (0.5 mol O2/mol H2O)
+ O2 reacted to SO2 (1 mol O2/mol SO2)
+ O2 reacted to NO2 (1 mol O2/mol NO2)

157048
Process Calculations
Page 26

Where:
O2 in regen. air =

12, 976 lb mol dry air


21 mol O 2
2,725 lb mol

=
of O2
hr
hr
100 mol air

Excess O2 in FG =

O2 reacted to CO =

12, 501 lb mol FG


2.5 mol O2
312 lb mol

=
of O2
hr
hr
100 mol FG
12, 501 lb mol FG
0 mol CO
0.5 mol O2

hr
100 mol FG
mol CO

= 0 lb mol/hr O2
O2 reacted to CO2 =

12, 501 lb mol FG


15.5 mol CO 2
1 mol O2

hr
100 mol FG
mol CO2

= 1,938 lb mol/hr of O2
O2 reacted to SO2 =

12, 501 lb mol FG


0 mol SO2
1 mol O2

hr
100 mol FG
mol SO2

= 0 lb mol/hr of O2
O2 reacted to NO2 =

12, 501 lb mol FG


0 mol NO2
1 mol O2

hr
100 mol FG
mol NO 2

= 0 lb mol/hr of O2
O2 reacted to H2O (by difference) is:
O2 Reacted to H2O = 2,725 - 312 - 0 - 1,938 - 0 - 0 lb mol/hr O2 = 475 lb mol/hr of O2
The hydrogen burned by oxygen in the regenerator is:
H2 burned by O2 =

475 lb mol
2 mol H2
950 lb mol

=
hr O2
mol O2
hr H2

157048
Process Calculations
Page 27

7.

Calculate Coke from Carbon and Hydrogen

The mass of coke combusted to CO + CO2 + H2O is:


from carbon =

1, 938 lb mol
12.01 lb C
23, 275 lb

=
hr C
lb mol C
hr C

from hydrogen =

950 lb mol
2.016 lb H
1, 915 lb

=
hr H2
lb mol H2
hr H

Total = 23,275 + 1,915 = 25,190 lb/hr coke

8.

Calculate Coke Yield Percent

The quantity of coke produced from the fresh feed is:

Coke Yield =

Coke, lb/hr100
FF,lb/hr

Coke Yield =

25, 190 lb/hr coke


412, 923 lb/hr raw oil

9.

100 = 6.10 wt - % coke

Calculate Hydrogen in Coke

The H2 content of the coke is:


H2 in Coke =

H2 in Coke

H2 ,

lb/hr(100)
Coke, lb/hr

1,915 lb/hr H
25,190 lb/hr coke

100 = 7.6 wt - % hydrogen

157048
Process Calculations
Page 28

10. Calculate the Air/Coke Ratio

Air to Coke =

(Air, lb/hr)(100)
Coke, lb/hr

Air to Coke =

375,870 lb/hr dry air


lb of dry air
= 14.92
25, 190 lb/hr coke
lb of coke

11. Calculate the Heat of Combustion of Coke

Combustion heats are calculated based on the average hottest temperature in the
regenerator. The dense, dilute, cyclones, and flue gas average temperatures are
calculated and the hottest is used as basis.
The average hottest temperature is 1375F.

Hc (2C + O2

2CO) = 46,216 + 1.47 (1375F) = 48,237

= (0

BTU
lb mole

BTU
lb mole

of O2 reacted to CO) (2) 48, 237

lb mole
hr

= 0 BTU/hr

Hc (C + O2

CO2) = 169,135 + 0.5 (1375F) = 169,822

= (1,938

BTU
lb mole

BTU
lb mole

of O2 reacted to CO2) (1) 169, 822

lb mole
hr

= 329.12 106 BTU/hr

157048
Process Calculations
Page 29

Hc (2H2 + O2

2H2O) = 104,546 + 1.585 (1375F) = 106,725

= (475

BTU
lb mole

BTU
lb mole

of O2 reacted to H2O) (2) 106, 725

lb mole
hr

= 101.389 106 BTU/hr


HCombustion of Coke = (0 + 329.12 + 101.39) 106 = 430.51 106 BTU/hr
Using as basis 1 lb of coke
H combustion of coke =

430.51 10 6 BTU/hr
25, 190 lb/hr coke

= 17,090 BTU/lb coke


This heat of combustion must be corrected for the cokes hydrogen content
according to the equation
Correction

= 1133 - 134.6 (wt-% H)


= 1133 - 134.6 (7.6) = +110 BTU/lb coke

The net heat of combustion of coke is:


HCombustion = 17,090 + 110 BTU/lb coke = 17,200 BTU/lb coke

157048
Process Calculations
Page 30

REGENERATOR HEAT BALANCE


Basis: 1 lb of coke
12. Heat Consumed to Heat Up the Regeneration Air

Since H = mass Cp T
Air is heated from the main air blower discharge temperature of 399F to the
average hottest temperature of 1375F at an average specific heat of 0.26 BTU/lb
F.
375, 870 lb/hr air
0.26 BTU
HAir =
(1375- 399F)
= 3, 787 BTU/lb coke
25,190 lb/hr coke
lb F

13. Heat Consumed to Heat up the Regeneration Air Water Vapor


Water vapor is heated from 399 to 1375F at an average specific heat of 0.5 BTU/lb
F.
0.5 BTU
4, 330 lb/hr H2 O
HH O

(1375 - 399F) = 83.9 BTU/lb coke


2
lb F
25, 190 lb/hr coke

14. Heat Consumed to Heat Up the Coke


Coke is heated from the reactor temperature of 970F to the average hottest
temperature of 1375F at an average specific heat of 0.4 BTU/lb F.
HCoke = (1375-970F) 0.4 BTU/lb F = 162 BTU/lb coke

157048
Process Calculations
Page 31

15. Heat Consumed to Generate Steam in the Catalyst Cooler


Enthalpies for water and steam are obtained from steam tables.
Water in at 220F
Steam out at 463F

= (188 BTU/lb) (56,033 + 6,952 lb/hr) = 11.841 106 BTU/hr


= (1,205 BTU/lb) (56,033 lb/hr) = 67.52 106 BTU/hr

Blowdown out at 463F = (441 BTU/lb) (6,952 lb/hr) = 3.066 106 BTU/hr
Catalyst cooler duty = (67.52 + 3.066 - 11.841) 106 BTU/hr = 58.75 106 BTU/hr
Or

HRemoved =

58.75 106 BTU/hr


= 2, 332 BTU/lb of coke
25,190 lb/hr of Coke

16. Regenerator Heat Balance


Using a typical regenerator heat loss rate of 250 BTU/lb coke, the heat consumed to
heat up the catalyst is:
RgHeat = (HComb Coke) - HCoke - HAir - HH2O - HLoss - HRemoved
Hregen = 17,200 - 3,787 - 84 - 162 - 2,332 - 250
= 10,585 BTU/lb Coke

157048
Process Calculations
Page 32

17. Calculate the Catalyst Circulation Rate


The catalyst is heated from the reactor temperature of 970F to the regenerated
catalyst temperature of 1371F at an average specific heat of 0.275 BTU/lb F.
Since Q = m Cp T then m = Q/Cp T
(Coke lb/hr)(Rg Heat BTU/lb Coke)
(0.275 BTU/lb F) (Cat T - RXT)

CCR =

CCR =

25,190 lb/hr coke 10,585 BTU/lb coke


40, 299 lb/min
0.275 BTU/lb F (1371 - 970F) 60 min/hr

or
CCR =

40, 299 lb/min


= 20.15 ton/min
2,000 lb/ton

18. Calculate the Catalyst/Oil Ratio


C/O =

CCR lb/hr
FF lb/hr

C/O =

40, 299 lb/min catalyst 60 min/hr


= 5.86 wt/wt
412,923 lb/hr fresh feed

19. Calculate the Regenerator Efficiency


Rg Eff =

Rg Heat 100
HCombustion of Coke

(10, 585 BTU/lb of Coke) (100)


17, 200 BTU/lb of Coke

= 62% (This number will be higher without catalyst cooler)

157048
Process Calculations
Page 33

20. Calculate the Delta Coke Wt-%:


Coke

(100) (Coke, lb/hr)


25, 190 100
=
= 1.04 wt%
Cat. Circ. lb/hr
40, 299 60

REACTOR HEAT CALCULATIONS


1 lb of fresh feed is used as basis in the following calculations.

21. Heat Consumed to Heat and Vaporize the Combined Feed


Enthalpies for the raw oil feed are obtained by using the equation as discussed after
this section. The UOP K to use for entering the enthalpy table is calculated from
UOP Method 375 as discussed in the following section. UOP K Factor is a function
of API and Engler distillation. A high UOP K value of 12.5 indicates a more
paraffinic (saturated chain) hydrocarbon, while a lower value of 11.2 occurs for a
more aromatic (unsaturated cyclic) stock. Higher UOP K paraffinic feeds crack
easier yielding higher conversion at a given reactor temperature.
Raw Oil: UOP K = 11.8

API Gravity = 21.3

At the 375F riser inlet temperature,

Hraw oil

= 252 BTU/lb

At the 970F reactor temperature,

Hvapor

= 760 BTU/lb

Hraw oil = 412,923 lb/hr (760-2891 BTU/lb) = 194.487 106 BTU/hr


The heat required to heat up the combined feed is the Hraw oil multiplied by the
Combined Feed Ratio (CFR),
where, CFR =

(raw oil + recycle) lb/hr


= 1.0
raw oil lb/hr

So, Hcomb feed = 194.487 106 BTU/hr

157048
Process Calculations
Page 34

Hcomb feed =

194.487 106 BTU/hr


= 471 BTU/lb raw oil
412, 923 lb/hr raw oil

22. Heat Consumed to Heat Up the Lift Gas:


The lift gas is heated from 110F to 970F at an assumed average specific heat of
0.5 BTU/lb F.
Hlift gas =

3, 250 lb/hr lift gas (970 - 110F) 0.5 BTU/lb F


= 3.4 BTU/lb raw oil
412, 923 lb/hr raw oil

23. Heat Consumed to Heat Up Lift Steam, Feed Steam and Stripping Steam
Steam is heated up from the header temperature of 380F to the reactor
temperature at 970F at an average specific heat of 0.485 BTU/lb F.
Hsteam =

(5, 000 + 12, 900 + 1, 800) lb/hr (970 - 380 F) 0.485


412, 923 lb/hr raw oil

= 13.8 BTU/lb raw oil

24. Heat of Inert Gas Carried from Regenerator to Reactor by Regenerated


Catalyst
The inerts gas can be calculated from the sponge gas stream and the procedure is
at the end of this section. If this number is unknown, use 0.007% of fresh feed. Use
an average specific heat of 0.275 BTU/lb F.
Hinerts = (inerts wt%) (Cp) (RxT - RgT)
= 0.007 0.275 (970 - 1371) = -0.8 BTU/lb raw oil

157048
Process Calculations
Page 35

25. Reactor Heat Balance


The total heat consumed in the reactor equals the sum of the heats consumed for
the combined feed, lift gas, all steam, the reactor losses, plus the heat of reaction.
Using a typical reactor heat loss rate of 2 BTU/lb raw oil, the heat balance is:
Rx Heat = Hcomb feed + Hlift gas + Hsteam + Hinerts + Hloss + HRxN
Hreactor = (471 + 3.4 + 13.8 - 0.8 + 2) BTU/lb raw oil + Hreaction
Hreactor = 489.4 BTU/lb raw oil + Hreaction

26. Overall Heat Balance


The heat consumed in the reactor is supplied by the hot catalyst circulated to the
riser. At steady state, the heat consumed in the reactor must balance the heat
produced in the regenerator. The reactor heat is based on a per lb of fresh feed
basis while that of the regenerator is on a per lb of coke basis. These two can be
equated using the raw oil to coke weight fraction to determine the heat of reaction:
lb coke

Hregenerator BTU / lb coke


= Hreactor [BTU/lb raw oil]
lb raw oil

10, 585 BTU


25, 190 lb/hr coke

= 489.4 BTU/lb raw oil + Hreaction


lb coke
412, 923 lb/hr raw oil
Hreaction = 119 BTU/lb raw oil

157048
Process Calculations
Page 36

FCC Unit Heat Balance Example


Refiner:
Location:
Combustion Air Correction to a Dry Basis
(a) Ambient Temperature
=
62
F
(b) Relative Humidity
=
97
%
(c) Sat. Vapor Pressure = 10^[6.40375-(3165.36/(F+392.565))]
= 0.275586177
psia
(d) lb H2O/lb dry air = [0.00622*(b)*(c)]/[14.7-0.01*(b)*(c)]
= 0.011520532
lb/lb
(e) Total Air to Regen
= 380,200
lb/hr
(f) Total Dry Air = (e)/[1+(d)]
= 375,870lb/hr
(h) H2O in Air = (e) (f)
= 4,330
lb/hr

Date:
Flue Gas Composition Adjustment:
GC, mol-%
Corrected for Ar*
(i)
CO =
0.00 CO =
0.00
15.50 CO2 =
15.50
(j)
CO2 =
3.47 O2 - (0.012*N2) =
2.50
(k)
O2 =
81.03 N2 + O2 - Cor O2 =
82.00
(L)
N2 =
0.00 SO2 =
0.00
(m)
SO2 =
0.00
(n)
NO2 =
0.00 NO2 =
Total
100.00
100.00
*Correction required only for GC not for Orsat analysis.

Temperatures:
Rg=Regenerator, Rx=Reactor
(o) Flue Gas Line
=
1368
F
(p) Rg Avg Cyclone Outlet
=
1368
F
(q) Rg Avg Dilute
=
1375
F
=
1371
F
(r) Rg Avg Dense (RgT)
(s) Avg Hottest Rg Temp
=
1375
F
Oxygen Balance:
(y)
(L) * (2 * 21 ) / 79 2(n) - 2(m) - 2(k) - 2(j) - (i)
(z)
2.016*(y) =12.01[ (i) + (j) ] + 32.06*(m) + 46.01*(n)
(1a)
Hydrogen = 2.016 * (y) * 100 / (z)
(1b)
Air = 28.966 * 100 * (L) / [ 79 * (z) ]
(1c)
Coke = Dry Air / [ Air / Coke ] = (f) / (1b)
(1d)
Fresh Feed
S.G. = 0.926
(1e)
Coke Yield = (1c) * 100 / (1d)

(t)
(u)
(v)
(w)

=
=
=
=
=
=
=

Air to Rg
Rx Temp
Hot Rg T Air T
Rg Dense T Rx T

7.6
201.5
7.6
14.9
25,187
412,923
6.10

=
=
=
=

399
970
976
401

F
F
F
F

mol H2 / 100 mol Flue Gas


lb coke / 100 mol Flue Gas
wt-% Hydrogen in Coke
Air/Coke, lb/lb
lb/hr of Coke
lb/hr Feed
wt-% Coke (of Fresh Feed)

Combustion of Coke
Basis: Average Hottest Regenerator Temperature:
(1f)
Hc(CO) = 46,216 + 1.47 * (s)
=
48,237 BTU/lb-mol
(1g)
Hc(CO2) = 169,135 + 0.5 * (s)
=
169,823 BTU/lb-mol
(1h)
Hc(H2O) = 104,546 + 1.585 * (s)
=
106,725 BTU/lb-mol
H Comb = [ (1f) * (i) + (1g) * (j) + (1h) * (y) ] / (z)
=
17,091 BTU/lb-mol
(1i)
(1j)
Correction Factor = 1133 134.64 * (1a)
=
109
BTU/lb-mol
H Combustion Coke = (1i) + (1j)
=
17,200 BTU/lb-mol
(1k)
Regenerator Heat Balance
Basis: 1 lb of Coke
(1m)
H coke = 0.4 BTU/lb-mol F * (w)
H air = (1b) * 0.26 BTU/lb F * (v)
(1n)
H H2O = (h) / (1c) * 0.485 BTU/lb F * (v)
(1o)
H Radiant Losses
(1p)
(1q)
Cat Cooler Heat Duty
H removed = Cooler Duty / Coke = (1q) * 10^6 / (1c)
(1r)
(1s)
Rg Heat = (1k) (1m) (1n) (1o) (1p) (1r)
(1t)
Rg Eff = Rg Heat * 100 / HcombCoke = (1s) * 100 / (1k)
(1u)
Cat/Oil = (1s) * (1e) / 100 * (0.275 BTU/lb F) * (w)
(1v)
Cat Circ = (Cat/Oil) * (FF) / 60 = (1u) * (1d) / 60 min/hr)
Coke = 100 * Coke / (60 * Cat Circ) = 100 * (1c) / 60 * (1v)
(1w)

=
=
=
=
=
=
=
=
=
=
=

160
3,787
81
250
58.7
2,331
10,590
61.6
5.86
40,313
1.04

BTU/lb coke
BTU/lb coke
BTU/lb coke
BTU/lb coke
MM-BTU/hr (calculated separately)
BTU/lb coke
BTU/lb coke
% Regenerator Efficiency
Catalyst-to-Oil Ratio
Catalyst Circulation, lb/min
Coke, wt-%

157048
Process Calculations
Page 37

FCC Unit Heat Balance Example Continuation


Refiner:
Location:

Date:

Reactor Heat Calculations:


Basis: 1 lb of Coke
(2a)
Rx Temp (RxT)
(2b)
Combined Feed Temp. (CFT)
(2c)
Fresh Feed (FF)
(2d)
FF Enthalpy @ CFT (H @ CFT)*
(2e)
FF Enthalpy @ RxT (H @ RxT)I
(2f)
Recycle (Recy)
(2g)
Recy Enthalpy @ CFT (E @ CFT)*
(2h)
Recy Enthalpy @ RxT (E @ RxT)*
*See Following Pages for Enthalpy Calculation Method

=
=
=
=
=
=
=
=

970
375
412,923
289
760
0
0
0

F
F
lb/hr
BTU/lb
BTU/lb
lb/hr
BTU/lb
BTU/lb

(2i)
(2j)
(2k)
(2m)
(2n)
(2o)
(2p)
(2q)
(2r)
(2s)

Inerts from Rg with catalyst (Inerts)


Inerts Specific Heat (Cp)
Lift Gas (LGas)
Lift Gas Temp (LGasT)
Lift Gas Specific Heat (LGas Cp)
Steam Temp (StmT)
Steam Specific Heat (Stm Cp)
Stripping Steam
Lift Steam
Feed Steam

=
=
=
=
=
=
=
=
=
=

2,748
0.275
3,250
110
0.5
380
0.485
5,000
12,900
1,800

lb/hr
BTU/lb F
lb/hr
F
BTU/lb F
F
BTU/lb F
lb/hr
lb/hr
lb/hr

(2t)
(2u)
(2v)
(2w)
(2y)
(2z)

Heat consumed by FF = (FF) * (H @ RxT H @ CFT) / (FF)


Heat consumed by Recycle = (Recycle) * (E @ CFT E @ RxT) / FF
Heat Consumed by Steam = (Total Stm) * (Stm Cp) * (RxT-StmT) / FF
Heat Consumed by Lift Gas = (LGas) * (LGas Cp) * (RxT-StmT) / FF
Heat from Inerts = (Inerts) * (Inerts Cp) * (RxT-RgT) / FF
Reactor Heat Loss

=
=
=
=
=
=

471
0
13.7
3.4
-0.7
2

BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF

(3a)

Rx Heat = (H FF) + (H Recy) + (H Stm) + (H Lgas) + (H Inrts) + (H Loss) + (H Rxn)


=
489.3

BTU/lb FF + H Reaction

(Rg Heat BTU/lb Coke) * (Coke lb/hr) / (FF lb/hr) = Rx Heat = BTU/lb + H Rxn
(3b)

H Rxn = [(Rg Heat BTU/lb Coke) * (Coke lb/hr) / (FF lb/hr)] BTU/lb =

157

H Rxn BTU/ lb FF

157048
Process Calculations
Page 38

uop K Factor from API and Engler Distillation


Data:

ASTM Distillation:
Vol%
Temperature, F
10
660
30
781
50
887
70
1015
90
1075

Specific Gravity:

0.9258

1. Calculate the volumetric average boiling point as the average of the 10, 30, 50, 70
and 90 vol-% temperatures.
VABP = (T10% + T30% + T50% + T70% + T90%) / 5
VABP = (660 + 781 + 887 + 1015 + 1075) / 5
=

883.6

2. Calculate the Engler slope as F per percent (F/%) by subtracting the 10 vol-%
temperature from the 90 vol-% temperature, and dividing the difference by 80.
Slope = (T90% T10%)/80

5.1875

3. Calculate the Cubic Average Boiling Point (CABP):


CABP = VABP * A + B
Where:

A = (0.000297 * Slope + 0.001438)*Slope + 1.0


A = 1.01545
B = (-0.581 * Slope 1.339)*Slope
B = -22.5809
4. Calculate UOP K:
UOP K

CABP 459.69
SG

= 11.89

157048
Process Calculations
Page 39

Enthalpy of Heavy Petroleum Fractions


The Following equations can be used to calculate the Enthalpies for the feed and recycle
streams on the FCC unit.
Liquid Enthalpy Equation:

Equation source is API Procedure 4.7.B4

A1 =

(-1171.26 + (23.722 + 24.907 * SG) * UOP K)

A1 =

A1 + (1149.82 46.535 * UOP K) / SG

A1=

A1 / 1,000

A2 =

(1 + 0.82463 * UOP K) * (56.086 13.817 / SG) / 1,000,000

A3 =

- (1 + 0.82463 * UOP K) * (9.6757 2.3653 / SG) / 1E+09

The enthalpy of liquid FCC feedstock at the riser inlet conditions is:
Hin = A1 * (TE 259.67) + A2 * (TE 259.67) + A3 * (TE 259.67)
Where:

TE

Combined Feed Temperature, (F + 459.67)

SG

Fresh Feed Specific Gravity

UOP K

Fresh Feed UOP K

Vapor Enthalpy Equation: Equation source is a curve fit from UOP PD Chart PD-189
F1 =

3.0186E-04 * SG + 3.9975E-06 * UOP K * (UOP K 13.8584)

F2 =

0.67036000 * SG + 0.00675130 * UOP K * (UOP K 24.7770)

F3 =

85.52390000 * SG 4.73260000 * UOP K * (UOP K 21.9249) 459.6742

Enthalpy of feed in fully vaporized condition is:


Hout = F1 * (T) F2 * T + F3
Where: T

Reactor temperature, F

157048
Process Calculations
Page 40

Heat of Combustion of Coke, BTU/lb-Mole


Table:
Temperature, F

77

1,100

1,200

1,250

1,300

1,350

1,400

CO

47,565

47,847

47,980

48,050

48,123

48,199

48,274

CO2

169,332

169,677

169,735

169,760

169,784

169,808

169,835

H2O Vapor

104,129

106,279

106,448

106,529

106,610

106,687

106,765

Equations:
Hc(CO)
=
Hc(CO2)
=
Hc(H2O)
=
Where:

46,216 + 1.47 * (T)


169,135 + 0.5 * (T)
104,546 + 1.585 * (T)

T is in F

157048
Process Calculations
Page 41

MECHANICAL EVALUATION
The Mechanical Evaluation Test should cover all facets of the FCC Unit, including the
reactor, regenerator, main column, and the gas concentration unit. All major pieces of
equipment should be part of this test, including vessels, pumps, compressors, heat
exchangers, and piping hydraulics. The procedure for this test is long and involved,
but the information can be very useful for the Refiner and for UOP. If the Refiner
wants to revamp the unit, it is important to determine maximum throughput and actual
equipment limitations. Most of the information will be collected only once, although
parts of it (such as exchanger surveys) can be repeated to follow fouling or other
potential problems.
The lists and data sheets included in this section can be used as guidelines in
collecting the required data, although the Refiner may have to modify certain parts for
his particular unit. It is important to finish collecting the data within as short a time as
possible. A single survey is generally satisfactory and it is no necessary to use long
term average data. The Unit should be operating smoothly to get realistic and good
quality data. Label the data collected and prepare a report in an orderly fashion.

157048
Process Calculations
Page 42

GENERAL INFORMATION LIST


This list is only a guideline. Please modify or expand as required.
1.

Ambient Air Conditions


a.
Temperature
b.
Relative Humidity
c.
Barometric Pressure
d.
Wind Velocity and Direction (show on rough plot plan)

2.

General Description of Unit


a.
Process Flow Diagram, including flow meter and control valve locations
b.
Plot Plan showing Layout of Vessel and Equipment
c.
Operational Mode (partial or complete CO Combustion)

3.

Units used (USA, Imperial, Metric) and Standard Conditions (0C, 760 mm;
60F, 14.7 psia)

4.

Limiting Factors
a.
Environmental
Constraints
(CO
emissions,
special
specifications)
b.
Utility Limitation (shortage of steam or electricity, etc.)

5.

Performance Data
a.
Accurate Flow and Weight Balance including sample analyses

product

157048
Process Calculations
Page 43

HYDRAULIC AND PROCESS SURVEY LIST


1.

Single gauge pressure survey of every point in reactor-regenerator circuit,


including air into regenerator and flue gas out to point of discharge.

2.

Slide valve positions and hydraulic oil pressure at each valve.

3.

Air blower suction and discharge pressures, total and net (to regenerator) flow
rates, relative humidity and temperature of air, with manufacturers data and
performance curve for comparison.

4.

Electrical or steam consumption for blower driver.

5.

Power recovery units should add flue gas temperatures and pressures around
expander, butterfly valve positions, electrical power consumed or generated
and single gauge pressure survey of third stage separator.

6.

For electrostatic precipitator, or other flue gas treaters, take temperatures in


and out, power consumption, and amount and size distribution of particulates
removed.

7.

Complete flue gas sample before and after flue gas treater.

8.

Catalyst consumption and losses.

9.

Single gauge pressure survey of main column and gas concentration section
(use one low pressure and one high pressure gauge, depending on location, for
better accuracy). Include feed flow rate and temperature, reflux flow rate and
temperature, reboiler heat input, overhead temperature and pressure and
enough other data to calculate a heat and weight balance around the column.

10.

Samples of main column overhead receiver gas and liquid; and gas,
hydrocarbons, and water samples from high pressure receiver for phase
equilibrium studies.

157048
Process Calculations
Page 44

11.

Compressor suction and discharge pressures, flow rates, composition, and


temperatures, with manufacturers performance curve for comparison. Include
amounts and compositions of liquids drained from knockout drums.

12.

Compressor driver type and power consumption.

13.

All pump suction and discharge pressures, flow rates, liquid compositions or
boiling ranges, and power consumption of driver, with manufacturers
performance data for comparison.

14.

Data on streams not usually measured, such as LCO to the sponge absorber,
including flow rates, temperatures, composition or boiling range, and single
gauge pressure survey of circuit.

15.

Pressures, temperatures, and flow rates of flushing oil to instruments and pump
seals and glands.

16.

Utility consumption/product data:


Steam (all pressures)
Air (plant and instrument)
Purges to instruments, packing glands, and expansion joints (specify air,
steam, nitrogen, or fuel gas), with single gauge pressure survey of utility lines at
purge points).
Cooling water
Boiler feed water
Steam condensate
Utility water
Treating chemicals for boiler feed water (type and amount)
Inhibitor and anti-corrosion chemicals used

157048
Process Calculations
Page 45

EXCHANGERS INFORMATION LIST


1.

Flow through exchangers on both sides (gas and liquid), composition or boiling
range, and mass flow.

2.

Temperatures in and out of both sides, also between shells and bundles.

3.

Pressures in and out of both sides, also between shells and bundles.

4.

Any material bypassed around exchangers (give rough sketch).

5.

If air coolers: air temperatures in and out, air velocity out, motor amps, note any
belt slippage, variable pitch position, louver position, etc.

6.

In preparing data, submit overall heat transfer coefficient and specifics on


exchangers.

157048
Process Calculations
Page 46

FIRED HEATERS INFORMATION LIST


1.

Process flow (volume and mass, composition, molecular weight and boiling
range).

2.

Single gauge pressure survey for both process and fuel system.

3.

Fuel type (gas or oil) and analysis (composition, sulfur, gravity, etc.), pressure
and temperature of fuel at heater.

4.

Fuel consumption.

5.

Steam or air pressure for fuel oil atomization.

6.

Temperatures throughout the heater, such as firebox, convection points, stack,


air preheat, and all process points.

7.

Draft in firebox and stack.

8.

Design information: type of furnace, materials of construction, and number,


layout and materials of tubes; including dimensions of furnace.

9.

Burner data: rating, design, number. Note any unusual problems such as
plugged or inoperative burners.

10.

Refiner should obtain sufficient data to calculate heat flux from both process
and fire side, heat release, heater efficiency and steam balance.

157048
Process Calculations
Page 47

157048
Process Calculations
Page 48

Reactor-Regenerator Pressure Survey


Refiner:
Location:
To Main Column

Date:

Time:
By:

I
19 18 17 16 15 14
12

13

Steam
Generator

Orifice Chamber

Flue Gas
SV

11

20

10
ESP

Flue Gas to
Stack

G
8

Slide Valves % Open


Regenerated
Recirculating
Spent
Flue Gas A
Flue Gas B

Cat Cooler
Slidevalve

22

Feed

5
D

Process Flow

DFAH

Feed Rate
Air Rate

Main Air
Blower

1
Atmospheric
Air

Pressure Survey: _____________Units of Pressure


1
2
3
4
5
6
7
8

11
12
13
14
15
16
17
18

A
B
C
D
E
F
G
H

157048
Process Calculations
Page 49

157048
Process Calculations
Page 50

157048
Process Calculations
Page 51

MAIN COLUMN SUMMARY BOTTOMS

page ____________________________
date ____________________________
Item No.: _____________________________
by ____________________________
Service: __________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: _________________ Reflux Ratio:_________________________________
Type of Trays: _____________________________________________________________
Main Column Bottoms

Circulating
HCO
LCO

Circ.

Quench

CSO

Other

Mass Flow

_______

_______

_______

_______

_______ ________

Temperature Out
Return
Pressure

_______
_______
_______

_______
_______
_______

_______
_______
_______

_______
_______
_______

_______ ________
_______ ________
_______ ________

Distillation
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
API or S.G.

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

BS & W

_______

_______

_______

_______

_______ ________

Steam to Stripper

_______

_______

_______

_______

_______ ________

________
________
________
________
________
________
________
________
________
________
________
________
________
________
________

(Sketch system showing flows, P, T, Q on separate page) __________________________


Weight balance _______________________ Heat balance _________________________
Deviations from UOP Specifications: ___________________________________________
________________________________________________________________________

157048
Process Calculations
Page 52

MAIN COLUMN SUMMARY


CYCLE OIL PRODUCTS AND OVHD.

page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: ________________ Reflux Ratio: ________________________________
Type of Trays: ____________________________________________________________
HCO
Product

LCO
Product

Naphtha
Product

Reflux

Net
Ovhd.
Liquid

Ovhd.
Gas

Mass Flow,

_______

_______ ________ _______

_______

_______

Temperature

_______

_______ ________ _______

_______

_______

Pressure
Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3/C3=
iC4
nC4/C4=
iC5
nC5
C6+
Avg. Mol. Wt.
Gravity
Distillation

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

________
________
________
________
________
________
________
________
________
________
________
________
________

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

Steam to Stripper

_______

_______ ________ _______

_______

_______

Flash Point

_______

_______ ________ _______

_______

_______

IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP

157048
Process Calculations
Page 53

COLUMN SUMMARY

page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: _________________ Reflux Ratio:_________________________________
Type of Trays: _____________________________________________________________
Net
Off
Ovhd.
Feed
Reflux
Gas
Btms.
Liquid
Other
Mass Flow

_______

_______

_______

_______

_______ ________

Temperature
Pressure

_______
_______

_______
_______

_______
_______

_______
_______

_______ ________
_______ ________

Composition, ______ % _______


_______
H2
N2
_______
H2S
_______
H2O
_______
C1
_______
_______
C2
C3
_______
iC4
_______
_______
nC4
iC5
_______
_______
nC5
C6+
_______
Avg. Mol. Wt.
_______
Gravity
_______
Distillation
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

________
________
________
________
________
________
________
________
________
________
________
________
________

IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

(Sketch system showing flows, P, T, Q on separate page) __________________________


Weight balance _______________________ Heat balance _________________________
Deviations from UOP Specifications: ___________________________________________

157048
Process Calculations
Page 54

ABSORBER SUMMARY

page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: ________________ Reflux Ratio: ________________________________
Type of Trays: ____________________________________________________________
Gas
In

Liquid
In

Gas
Out

Liquid
Out

Pumparound
Upper
Lower

Mass Fl
Temperature

_______
_______

_______ ________ _______


_______ ________ _______

_______
_______

_______
_______

Pressure

_______

_______ ________ _______

_______

_______

Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Avg. Mol. Wt.
Gravity
Distillation, _______
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________

_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______

(Sketch system showing flows, P, T, Q on separate page) __________________________


Weight balance ______________________ Heat balance ________________________
Deviations from UOP Specifications: ___________________________________________

157048
Process Calculations
Page 55

CENTRIFUGAL COMPRESSOR DATA


page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No. of Stages: _____________________________________________________________
OPERATING CONDITIONS/PERFORMANCE
Flow Rate:
____________
Suction Pressure:
____________ psig
Discharge Pressure: ____________ psig
Differential Head:
____________
Polytropic :
____________
Operating Speed:
____________ rpm

Suction Temperature:
Discharge Temperature:
Power:
MW:

________
________
________
________

F
F
hp

Type of Seal:
_________________________________________
Lube/Seal Oil System: ________________________________________
Buffer Gas:
(yes/no)
Buffer Gas Rate: ______________ SCFH
Automatic Surge Control:
(yes/no)
DRIVER
Motor Manufacturer: _________________________________________
Rating:
____________________ Service Factor:
______________
Insulation Class: ____________________ Voltage/phase/cycle:
Turbine Manufacturer:_________________________________________
Speed:
______________
Steam Supply: _______ psig
Steam Rate: ______________
Steam Exhaust: _______ psig
Gear Manufacturer:
Rating:
Type:

______ F
______ F

_________________________________________
____________________ Service Factor: _____________
____________________ Power Loss:
_____________

Deviations from UOP Specification: ____________________________________________


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 56

RECIPROCATING COMPRESSOR DATA


page ___________________________
date ___________________________
by ___________________________

Item No.: ______________________________


Service: _______________________________
Manufacturer: ___________________________ Cylinder Lubrication:
____________
Type, Model: ___________________________ Clearance Pockets:
(yes/no)
No. of Stages, No. of Cylinders: ___________ Sparing Description:
____________
OPERATING CONDITIONS/PERFORMANCE
Flow Rate:
____________
Suction Temperature:
_________ F
Suction Pressure:
____________ psig Discharge Temperature: _________ F
Discharge Pressure: ____________ psig HP/stage:
_________ hp
MW:
____________

Operating Speed:
____________ rpm
Cylinder Diameters:
_________
Piston Speed:
____________ ft/s
# of Suction/Discharge Valves: _________
Actual Rod Loadings, T/C:
________________________________________ lbf
Max Allowable Rod Loadings, T/C: ________________________________________ lbf
DRIVER
Motor Manufacturer:
Rating:
Insulation Class:

________________________________________
____________________ Service Factor:
_____________
____________________ Voltage/phase/cycle:

Turbine Manufacturer: ________________________________________


Speed:
_______________
Steam Supply:
_______ psig
Steam Rate: _______________
Steam Exhaust: _______ psig
Gear Manufacturer:
Rating:
Type:

______ F
______ F

________________________________________
____________________ Service Factor: _____________
____________________ Power Loss:
_____________

Deviations from UOP Specification: ___________________________________________


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 57

CONTROL VALVE SUMMARY


page ___________________________
date ___________________________
Item No.: ______________________________

by ___________________________

Service: __________________________________________________________________
Description of Valve: _____________________

Design CV: ______________________

Mfgr. and Catalog No.: ______________________________________________________


Positioner? _______________________________________________________________

Actual

Design

Percent open (valve position)

____________

Flow rate:

______________________

____________

__________

Upstream pressure:

______________________

____________

__________

Downstream pressure: ______________________

____________

__________

Flowing temperature:

____________

__________

______________________

Deviations from UOP Specification: ____________________________________________


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 58

AIR FIN COOLER SURVEY

page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: _____________________________________________________________
No. of Bundles: _______________________ No. of Passes: _____________________
No. of Tubes per Pass: _________________ Fans/bundle: ______________________
Tube Size _______________ ID x _______________ Gauge x _____________ Length
Piping Geometry: ______________________ Type*: ____________________________
Overall Heat Transfer Coefficient: _____________________________________________
Inlet
Outlet
Air

In
Out
No. fans on__________________________
Louver position_______________________
Mass flow
Q (calc.)
Composition, ____ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Avg. Mol. Wt.
Relative Humidity

Pressure
______________
______________

Temperature
_____________
_____________

______________
_____________
______________
_____________
Pitch control ________________________
Air
______________
______________

______________

Process
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________

157048
Process Calculations
Page 59

Gravity
Distillation, ______
IBP
10%
30%
50%
70%
90%
EP

_____________
_____________
_____________
_____________
_____________
_____________
_____________

Deviations from UOP Specification: ____________________________________________


________________________________________________________________________
________________________________________________________________________
*Include sketch of piping geometry if different from UOP standard practice types.

157048
Process Calculations
Page 60

FLOW METER SUMMARY


page ___________________________
date ___________________________
Item No.: ______________________________

by ___________________________

Service: _________________________________________________________________
Type of Fluid: ___________________________

Normal Units of Flow: ______________

______________________________________
Type of Meter: ____________________________________________________________

Meter Reading: ___________________________________________________________


Pressure

________________

Temperature

________________

Sp. Gr.**

________________

Meter Factor

________________

Corrected Flow Rate

________________

Mass Flow Rate

________________

Avg. mol. wt.

________________

Molar Flow Rate

________________

**Sketch piping layout, showing distances in nominal pipe IDs.

157048
Process Calculations
Page 61

HEAT EXCHANGER SURVEY

page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No. of Bundles: ____________________________________________________________
No. of Passes/Bundle: __________________ Tubes per Pass: ____________________
Tube Size ______________ ID x _______________ Gauge x ______________ Length
Heat Exchange Surface Area/Bundle: __________________________________________
Piping Geometry (sketch if necessary): _________________________________________
Length of Service: __________________________________________________________
Design Heat Transfer Coefficient: ______________________________________________
Shell Side

Inlet

Stream
A

Outlet
Tube Side

Inlet
Outlet

Q (calc.) Shell side


Q (calc.) Tube side

______________
______________

Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Mass Flow
Avg. Mol. Wt.

A
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________

Pressure
______________

Temperature
_____________

______________

_____________

______________
______________

_____________
_____________

B
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________

157048
Process Calculations
Page 62

Gravity
Distillation, _______
IBP
10%
30%
50%
70%
90%
EP

______________
______________
______________
______________
______________
______________
______________

______________
______________
______________
______________
______________
______________
______________

Deviations from UOP Specification: ___________________________________________


________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 63

HEATER SURVEY
page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No. of Passes:_________________________ Tubes per Pass: ____________________
Tube Size ______________ ID x _______________ Wall x ________________ Length
Geometry (Process): ________________________________________________________
Geometry (Flue Gas): _______________________________________________________

Radiant

Inlet

Stream
A

Outlet

Pressure
______________

Temperature
_____________

______________

_____________

Convection I

Inlet
Outlet

______________
______________

_____________
_____________

Convection II

Inlet
Outlet

______________
______________

_____________
_____________

Convection III

Inlet
Outlet

______________
______________

_____________
_____________

Fuel Gas

______________

_____________

Fuel Oil

______________

_____________

Flue Gas Under Convection I

______________

_____________

Flue Gas Under Convection II

______________

_____________

Flue Gas Under Convection III

______________

_____________

Flue Gas Under Stack Damper

______________

_____________

Flue Gas Above Floor

______________

_____________

157048
Process Calculations
Page 64

HEATER SURVEY
page _______________________________
date _______________________________
by _______________________________

Stream
A
B
Mass Flow, ________
_____ _____
Composition, ______ %
_____ _____
H2
_____ _____
_____ _____
N2
_____ _____
O2
CO
_____ _____
_____ _____
CO2
_____ _____
H2S
_____ _____
SO2
_____ _____
C1
_____ _____
C2
_____ _____
C3
_____ _____
iC4
_____ _____
nC4
_____ _____
iC5
_____ _____
nC5
_____ _____
C6-205C (400F)
205C (400F)+
_____ _____
Avg. Mol. Wt.
_____ _____
Gravity
_____ _____
Viscosity
_____ _____
Total Sulfur, _______
_____ _____
Metals, ___________
_____ _____
Q (calc.) Absorbed
_____ _____
Q (calc.) Released
Heater Gross Efficiency
Excess Air, %
Tube Skin Temps:, _____
Burner Pressure ______________________

C
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____

D
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
____

E
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____

F
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____

_____

_____

G,H,
I,J,K
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______

% of Rating ____________________

Provide sketch showing piping and controls for process piping.


Deviations from UOP Specification: ___________________________________________
________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 65

CENTRIFUGAL PUMP SURVEY


page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No., Size and Style (Mfgrs. Designation) ________________________________________
________________________________________________________________________
Suction

Pressure
______________

Discharge

______________

Temperature
_____________

Other Information
Rated Flow (STP)
_____________
Seal Type? Single, Tandem, Double, Bellow
Sp. Gr.
_____________
Spillback? Yes/No
Viscosity
_____________
NPSHR?
_________________________
Static Suction Head _____________
Suction Specific Speed: ________________
Speed
_____________
Differential Head (flowing condition) _________________________________________
Driver Type:
___________________________________________________________
Manufacturer: ___________________________________________________________
No., Size, Rating and Style (Mfgrs. designation): __________________________________
Rating:
_________________
Insulation Class:
_________________
Service Factor: _________________
Voltage/Phase/Cycle: _________________
Motor:
Power consumption
Speed
Turbine:
Steam consumption
Steam supply

______________
______________
______________

Steam exhaust
Speed

Pressure
______________

Temperature
______________

______________

______________

______________

Supply copy of Mfgrs. pump curve and plot operating point.


Deviations from UOP Specification: ____________________________________________
________________________________________________________________________
________________________________________________________________________

157048
Process Calculations
Page 66

157048
Process Calculations
Page 67

SUPPLEMENTAL CALCULATIONS
REGENERATOR VELOCITIES
The following procedure shows how to calculate the superficial velocity in the
combustor, upper regenerator, and cyclones. This section presents two methods to
calculate the velocities in the regenerator. The first method is more precise but
requires more information and it is more laborious than the second method.

Method A
1.

Required Information

The FCC Unit is in total combustion mode for this case and with no catalyst cooler.
The process conditions are:
Temperatures:

Average Dense
Average Dilute
Average Cyclones
Air to Regenerator
Ambient
Relative Humidity

1371F
1375F
1375F
399F
62F
97%

Pressures:

Regenerator
Combustor
Cyclones

32 psig
34 psig
31 psig

Areas:

Combustor Cross sectional


Regenerator Cross sectional
First Stage Cyclones
Second Stage Cyclones

300 ft2
452 ft2
24.5 ft2
21.3 ft2

157048
Process Calculations
Page 68

Flow Rates:

Flue Gas:

Air to Regenerator
83,615 scfm
= (scfm x 28.76 lb/mol x 60 min/hr)/(379.5 scf/mol)
= 380,200 lb/hr
CO
CO2
O2
N2 + Ar
SO2
NO2

2.

=
=
=
=
=
=

0
15.50
2.5
82.0
0
0

Combustion Air Correction to a Dry Basis

A psychometric chart is used to determine the moisture content of the air. At


atmospheric conditions of 62F and a relative humidity of 97%, the moisture content
is:
Moisture Content =

0.01152 lb H2O
lb dry air

Wet Air = 380,200 lb/hr


Dry Air = 380, 200 lb/hr wet air

1 lb dry air
(1 + 0.01152) lb wet air

Water in Air = 380,200 lb/hr - 375,870 lb/hr = 4,330 lb/hr

= 375, 870 lb/hr

157048
Process Calculations
Page 69

3.

Calculate Flue Gas Rate

The flue gas rate can be calculated from the regenerator air rate. These two
streams are related by the inert N2 + Ar content which remains constant through the
catalyst regeneration.
Since, moles =

Weight
Molecular Weight

then,
Water in Air = (4,330 lb/hr)/(18 MW) = 241 mol/hr
Dry Air = (375,870 lb/hr)/(28.966 lb/mol) = 12,976 lb mol/hr
mol/hr (N2 + Ar) in dry air = mol/hr (N2 + Ar) in flue gas
79 mol inerts
lb mol FG
82 mol inerts
12, 976 lb mol

100 mol air


hr
100 mol FG
hr

Flue Gas (FG) = 12,501 lb mol/hr

4.

Calculate the Water Produced by the Hydrogen Content of Coke

The overall reaction occurring in the regenerator is:


C + H2 + S + N + O2 = CO + SO2 + NO2 + H2O + O2

157048
Process Calculations
Page 70

The water produced by the hydrogen (H2) content of the coke can be calculated
from an O2 balance:
O2 in regeneration air = excess O2 in flue gas +
+ O2 reacted to CO (0.5 mol O2/mol CO)
+ O2 reacted to CO2 (1 mol O2/mol CO2)
+ O2 reacted to H2O (0.5 mol O2/mol H2O)
+ O2 reacted to SO2 (1 mol O2/mol SO2)
+ O2 reacted to NO2 1 mol O2/mol NO2
where:
O2 in regen. air =

12, 976 lb mol dry air


21 mol O 2
2,725 lb mol

=
of O2
hr
hr
100 mol air

Excess O2 in FG =

O2 reacted to CO =

12, 501 lb mol FG


2.5 mol O2
312 lb mol

=
of O2
hr
hr
100 mol FG

12, 501 lb mol FG


0 mol CO
0.5 mol O2

= 0 lb mol/hr O2
hr
100 mol FG
mol CO

O2 reacted to CO2 =

12, 501 lb mol FG


15.5 mol CO 2
1 mol O2

=1,938 lb mol/hr of O2
hr
100 mol FG
mol CO2

O2 reacted to SO2 =

12, 501 lb mol FG


0 mol SO2
1 mol O2

= 0 lb mol/hr of O2
hr
100 mol FG
mol SO2

O2 reacted to NO2 =

12, 501 lb mol FG


0 mol NO2
1 mol O2

= 0 lb mol/hr of O2
hr
100 mol FG
mol NO 2

157048
Process Calculations
Page 71

O2 reacted to H2O (by difference) is:


O2 Reacted to H2O = 2,725 - 312 - 0 - 1,938 - 0 - 0 lb mol/hr O2 = 475 lb mol/hr of O2
Since
H2 + 1/2O2 = H2O
Then
The water produced by Hydrogen and Oxygen in the regenerator is:
H2 O Produced by O2 =

5.

475 lb mol
2 mol H2O
950 lb mol

=
hr O2
mol O2
hr H2

Calculate the Wet Flue Gas Rate

The total moles per hour of wet flue gas are:


Wet Flue Gas = Dry Flue Gas + Water from Air + Water from H2 in Coke =
12,502 mol/hr + 241 mol/hr + 949 mol/hr = 13,692 mol/hr
The actual cubic feet per second (ACFS) of the flue gas can be calculated by using
the Ideal Gas equation of state
PV = nRT
Where
R
Prg
Pcomb
Pcycl
Tcomb
Tdense
Tdilute
Tcycl

then

=
=
=
=
=
=
=
=

V = nRT/P

10.7 (psia x ft3)/(mol x R)


32 psig + 14.7
= 46.7 psia
34 psig + 14.7
= 48.7 psia
31 psig + 14.7
= 45.7 psia
1,275F + 460
= 1,735 R
1,371F + 460
= 1,831 R
1,375F + 460
= 1,835 R
1,368F + 460
= 1,828 R

157048
Process Calculations
Page 72

ACFS @Tcomb = 13,692 mol/hr x 10.73 x 1,735/(48.7x3600 sec/hr) = 1,454 ft3/sec


ACFS @Tdens

= 13,692 mol/hr x 10.73 x 1,831/(46.7x3600 sec/hr) = 1,596 ft3/sec

ACFS @Tdilute = 13,692 mol/hr x 10.73 x 1,835/(46.7x3600 sec/hr) = 1,599 ft3/sec


ACFS @Tcyc

6.

= 13,692 mol/hr x 10.73 x 1,828/(45.7x3600 sec/hr) = 1,632 ft3/sec

Calculate Superficial Velocities

Regenerator Superficial Velocity


= (ACFS @ Tdens, ft3/sec) / (Rg Cross Sect Area, ft2)

= 3.5 ft/sec

First stage Cyclones Superficial Velocity


= (ACFS @ Tdilute ft3/sec) / (Total Inlet Area, ft2)

= 65.2 ft/sec

Second Stage Cyclones Superficial Velocity


= (ACFS @ Tcyc, ft3/sec) / (Total Inlet Area, ft2)

= 76.6 ft/sec

Combustor Superficial Velocity


= (ACFS @ Tcomb, ft3/sec) / (Comb Cross Sec Area, ft2)

= 4.8 ft/sec

157048
Process Calculations
Page 73

Method B
1.

Required Information

This method does not require the flue gas analysis. The process conditions are:
Temperatures:
Pressures:
Area:
Flow Rates:

2.

Average Dense
Regenerator
Regenerator Cross sectional
Air to Regenerator

1371F
32 psig
452 ft2
83,615 scfm

Calculate the Actual Cubic Feet per Second

The volumetric flue gas rate can be calculated by using the Ideal Gas equation of
state
PV = nRT

then

R = PV/nT

For air we have

R = P1V1/n1T1

For the Regenerator Air

R = P2V2/n2T2

Combining the last two equations

P1V1/n1T1 = P2V2/n2T2

Or

V2 = P1V1T2 x n2
T1P2
n1

Where:
P1
T1
V1
P2
T2

=
=
=
=
=

0 pisg + 14.7
60 F + 460
83,615 scfm/(60 s/m)
32 pisg + 14.7
1,371F + 460

=
=
=
=
=

14.7 psia
520 R
1,393.6 ft/s
46.7 psia
1,831 R

157048
Process Calculations
Page 74

n2/n1

1.04 Assumed. This factor is due to the combustion of


Hydrogen to in the coke to water.

Then
V2

(14.7 psia)(1,393.5 ft/s)(1,831R)(1.04) = 1,606 ft3/s


(520R)(46.7 psia)

3.

Calculate Regenerator Superficial Velocity

The superficial velocity is calculated by dividing the volumetric flow rate by the cross
sectional area:
1,606 ft3/s
=
3.6 ft/s
2
452 ft
The molar expansion factor n2/n1 can be approximated if the flue analysis is
available by using the following equation:

Rg Velocity

n2/n1

2 - (79/N2%)

Where N2% is the Nitrogen percent form the flue gas analysis.

157048
Process Calculations
Page 75

REGENERATOR AIR DISTRIBUTOR PRESSURE DROP


The pressure drop across the regenerator air distributor can be calculated by the
following formula:

P =

q2
C2 A2 (2g) 144

where:
P
q
r
C
A
g

=
=
=
=
=
=

pressure drop, psi


air rate at flowing conditions, ft3/sec
density of air at flowing conditions, lb/ft3
orifice coefficient, 0.60-0.80
total cross sectional area of holes, ft2
acceleration due to gravity, 32.2 ft/sec2

The perforated grid air distributor is designed for a pressure differential of about 0.71.2 psi. This will give good air distribution for fluidization without causing catalyst
attrition. If the pressure differential is too high, the high velocity can cause attrition.
If the pressure differential is too low, less than 0.5 psi, it can cause poor distribution
of air and distributor erosion problems.

157048
Process Calculations
Page 76

REACTOR STRIPPER DENSITY


The following procedure shows how to calculate the density in Reactor Stripper.
The density indicator is a differential type instrument and for this case the range is
0-145 inches of water.

1.

Calculate the Distance Between Taps

Lower Instrument Tap Elevation:


59' 8 7/8" or 59.7396'
Upper Instrument Tap Elevation:
74' 4 1/8" or 74.3438'
Distance Between Taps:
74' 4 1/8" - 59' 8 7/8" = 14' 7 1/4" or 175.25"

2.

Calculate the Density


Instrument Readout: 75%
Instrument Span: 0-145 inches H2O
75% x 145 inches H2O = 108.75 inches H2O
108.75 in H 2 O

1
12 in
lb/in 2
144 in 2
lb

= 38.7 3
2
175.25 in
ft
27.705 in H 2 O
ft
ft

157048
Process Calculations
Page 77

Notes:
i)

The Spent Catalyst Stripper Density is expected to range from 30 to 45 lb/ft3.

ii)

In cases when the pressure taps are under the stripper baffles the distance
between taps should be replaced by the distance between the bottom edges of
the baffles.

157048
Process Calculations
Page 78

REACTOR STRIPPER LEVEL


This procedure shows how to calculate the level in the reactor. The level controller
is a differential type instrument and for this case the range is 0-300 inches of water.

1.

Calculate the Distance Between the Taps

Lower Instrument Tap Elevation:


62' 3 7/8" or 62.3229'
Upper Instrument Tap Location:
127' 0" - 3' 3" - 1' 6" = 122' 3" or 122.2500'
Distance Between Upper Tap and Lower Tap:
122' 6" - 62' 3 7/8" = 60' 2 1/8" or 60.1771'

2.

Data Required
Instrument Readout:
Instrument Span:

50%
0-300 inches H2O

Stripper Density of 36.25 lb/ft3 (From Stripper Density Calculation)


Assume Reactor Vapor Space Density of 1 lb/ft3
Distance Between Upper Tap and Lower Tap = 60.1771'
Elevation of Lower Tap = 62.3229'
Normal Reactor Catalyst Level = 84.500'
Cyclone Dipleg Outlet = 79.5417'
300 in H2O x 50% = 150 in H2O

157048
Process Calculations
Page 79

3.

Method A - This is rough method.


lb/in 2
144 in 2
ft 3
150 in H 2 O

= 21.51 ft of Catalyst
27.705 in H 2 O
36.25 lb
ft 2

Distance Relative to Normal Catalyst Level =


(62.32 + 21.51) - 84.50 = - 0.67 (i.e. ~ 8" below normal level)

4. Method B - This method is more precise than Method A since consider the
reactor vapor density.
X + Y = 60.18 ft => Y = 60.18 - X
Where:

X = Catalyst height.
y = Reactor vapor height from catalyst bed to upper pressure tap.
60.18 ft = distance between pressure taps.

lb
lb/in 2
144 in 2 X (36.25 lb)

+ (60.18 - X) 1 3
150 in H 2 O
2
3
27.705 in H 2 O
ft
ft
ft

779.64 lb/ft2 = 35.25 X lb/ft3 + 60.18 lb/ft2


Then
X = 20.41 ft above Lower Level Tap
Distance Relative to Normal Catalyst Level =
(62.32 + 20.41) - 84.50 = - 1.77 (i.e. 1' 9 1/4" below normal level)

157048
Process Calculations
Page 80

Notes:
i)

The Spent Catalyst Stripper Density is expected to range from 30 to 45


Lbs/Ft3.

ii)

In cases when the lower pressure tap is under the stripper baffle the distance
between taps should be replaced by the distance between the bottom edge of
the baffle and the upper tap.

157048
Process Calculations
Page 81

REACTOR RISER RESIDENCE TIME


Residence time, the time that hydrocarbons spend in the riser, is another design
variable utilized in controlling reaction severity. This variable is of particular
importance in operation using high activity zeolitic catalyst. Typical residence time
for current designs is two to three seconds.
Conversion is proportional to residence time in that it increases with prolonged
contact of catalyst and feedstock. Gasoline yields increase with residence time up
to a point after which over-cracking may occur. This results in a loss of gasoline
yields and a significant increase in conversion.
The method used to calculate riser residence time is as follows:

= VR/[(1/3)(VF) + (2/3) (VP)]

= Residence time in seconds

VR = Riser volume, ft3


VF

= Volume of vaporized feed, steam, lift gas, water, and inerts calculated at
the average conditions at the point of feed injection, ft3/s.

VP

= Volume of vaporized products, steam, lift gas, water and inerts calculated
at the average conditions at the point of feed injection, ft3/s.

It should be noted that prior to the residence time calculation, the average
temperature and pressure at the point of feed injection must be estimated to obtain
VF and VP.

157048
Process Calculations
Page 82

The riser pressure at the point of feed injection can be approximated by assuming a
5 psig pressure drop, hence:
Riser Pressure = Reactor dome pressure + 5 psi
The average temperature at the point of feed injection is calculated as:

Tavg

0.2753C / O TR CPo To L / O CPL TL 0.495W / O TW S / O TS W / O HWL H Rx H OL


0.2753C / O CPo 0.495W / O S / O L / O CPL

Where:
C/O

Catalyst to Oil wt. ratio, calculated in reactor-regenerator heat


balance section

S/O

Steam to Oil wt. ratio

W/O

Water to Oil wt. ratio

L/O

Lift gas to Oil wt. ratio

TR

Regenerator dense bed temperature, F

TO

Oil feed temperature, F

TL

Lift gas feed temperature, F

TS

Steam feed temperature, F

TW

Water feed temperature, F

CPO

Specific heat of vaporized oil feed, Btu/lb/F

157048
Process Calculations
Page 83

CPL

Specific heat of lift gas, Btu/lb/F

HOL

Latent heat of vaporization of oil feed at inlet temperature, To,


Btu/lb

HWL

Latent heat of vaporization of water at inlet temperature, Tw,


Btu/lb

HRX

Heat of reaction, Btu/lb, calculated in reactor-regenerator heat


balance section

Tavg

Average temperature at point of feed injection, F

157048
Process Calculations
Page 84

HYDROGEN BALANCE
This document describes a manual method for calculating the Hydrogen balance for
an FCC Unit.

Data required:
A normalized to 100% recovery product summary in wt-%
A breakdown of the C4- components
The distillation and API of each C5+ product
The distillation and API of the feed
API Technical Data Book Figure 2B1.1
"Characterizing Boiling Points of Petroleum Fractions"
Figure 2 - UOP Chart 409B-12
"Hydrogen Content of Liquid Petroleum Hydrocarbons"

Description of the Calculation Method:


Step 1. Determine the molecular weight of Hydrogen per molecule for each C4product, e.g. H2S, H2, C1, C2, C2=, etc. See column 3 of the attached example.
Step 2. Determine the percentage Hydrogen in each C4- product component by
dividing the molecular weight of Hydrogen per molecule by the molecular weight of
each component. In the attached example this is column 3 divided by column 4
times 100. The result is given in column 5.

Step 3. Calculate the Volume Average Boiling Point (VABP) for each of the heavier
products (C5+ gasoline, LCO, and MCB). See Figure 2B1.1 comments for
procedure and definitions.

Step 4. Calculate the Engler Slope for each of the heavier products (C5+ gasoline,
LCO, and MCB). See Figure 2B1.1 comments for procedure and definitions.

157048
Process Calculations
Page 85

Step 5. Determine the Mean Average Boiling Point from API Figure 2B1.1.
Step 6. Determine the Hydrogen content of the hydrocarbon liquid from Figure 2.
See the lower half of column 5 in the attached example.
Step 7. Multiply the wt% normalized yield pattern for each component by the
percentage Hydrogen in each product component. In the attached example this is
column 2 times column 5. The result is given in column 6.
Step 8. Calculate the percentage of Feed Hydrogen in each component by dividing
the Wt% Hydrogen in each product component by the Wt% H2 in the feed. In the
attached example this is the value in column 6 divided by the Wt% H2 in the feed
(13%).

157048
Process Calculations
Page 86

Hydrogen Balance Summary


1

Mass Balance

wt-%

#H/Molecule

MW

%H2

H2 wt-%

% Feed H2

Results
Feed:

100.00

Values from Figures 2B1.1 & Fig. 2

13.00

100.00

H2S

0.04

2.0158

34.08

0.06

0.0021

0.02

H2

0.23

2.0158

2.02

1.00

0.2280

1.75

C1

0.89

4.0361

16.04

0.25

0.2245

1.73

C2

0.81

6.0474

30.07

0.20

0.1622

1.25

C2=

0.91

4.0316

28.05

0.14

0.1303

1.00

C3

1.30

8.0632

44.10

0.18

0.2375

1.83

C3=

4.64

6.0474

42.08

0.14

0.6662

5.12

IC4

2.69

10.0790

58.12

0.17

0.4665

3.59

NC4

0.63

10.0790

58.12

0.17

0.1094

0.84

C4=

4.88

8.0632

56.11

0.14

0.7007

5.39

C5+ Gasoline

44.55

LCO

27.60

MCB
Coke
Total Products

13.80

6.15

47.29

Values to the right

11.30

3.12

23.99

5.22

were determined from Chart

10.20

0.53

4.10

5.62

2B1.1 & Fig 2.

4.44

0.25

1.92

39.74

12.98

99.82

100.00

See attached method.

Total

Laboratory Summary for Gasoline


Distillation D-86

(R)^1/3

SpGr

0.7286

IBP

96.8

556.8

---------

API

62.02
214.7

10%

131.9

591.9

8.3962

VABP

20%

145.4

605.4

8.4596

Engler Slope

2.40

30%

163.4

623.4

8.5426

Correction Factor

6.0

40%

182.3

642.3

8.6280

CABP, R Uncorrected

672.8

50%

203.9

663.9

8.7237

CABP, F Corrected

206.8

60%

230.9

690.9

8.8404

CABP, R Corrected

666.8

70%

259.7

719.7

8.9616

UOP K

11.99

80%

291.2

751.2

9.0904

Total Sulfur, wt%

0.0032

90%

323.6

786.3

9.2193

Octane (F1 C)

92

EP

371.3

831.3

---------

RVP @ 378C, kg/cm

Recovered Volume

99.5

0.5

Residue Volume

39.6

157048
Process Calculations
Page 87

Hydrogen Content of Liquid Petroleum


Hydrocarbons

157048
Process Calculations
Page 88

157048
Process Calculations
Page 89

Comments on Figure 2B1.1


Purpose:
The various average boiling points which are used to characterize petroleum fractions are correlated
in Figure 2B1.1 with the ASTM D86 distillation properties of the fraction. If these boiling points are
required for mixtures (or portions of a mixture) for which the composition is known, using the defining
equations (2-0.3) through (2-0.7) given in the introduction.
Reliability:
The reliability is unknown.
Notation:
The volumetric average boiling point of a petroleum fraction is the weighted average of the ASTM
D86 distillation temperatures after 10, 30, 50, 70 and 90 percent by volume have been distilled.

T10 T30 T50 T70 T90


5

. The slope is calculated assuming a linear ASTM D86 distillation curve

T90 T10
in degrees Fahrenheit per percent distilled.
90 10

between the 10 and 90 percent points

The relationships between the various average boiling points given in Figure 2B1.1 for petroleum
fractions are analogous to those defined by equations (2-0.3) through (2-0.7) for mixtures of
identifiable hydrocarbons.
Special Comments:
For ASTM D86 distillation temperatures above 475F, use the following correction for cracking:
log D 1.587 0.00473 T
(2B1.1-1)
Where:
D = correction to be added to T, in degrees Fahrenheit
T = observed distillation temperature, in degrees Fahrenheit
If the available distillation data are not from ASTM Method D86, they must be converted by the
methods of Chapter 3 to calculate the volumetric average boiling point.
Literature Sources:
This figure was developed by Smith and Watson, Ind. Eng. Chem. 29 1408 (1937). Equation
(2B1.1-1) was given by S.T.Hadden, Gulf Research and Development Company, Pittsburgh, Pa.,
private communication (1964).
Example:
Determine the molal average boiling point, weighted average boiling point, cubic average boiling
point, and mean average boiling point of a petroleum fraction having the following ASTM D86
distillation properties:
Distillation, percent by volume
10
30
50
70
90
Temperature, degrees Fahrenheit:
149 230 282 325 371

VABP

149 230 282 325 371


271 F
5

Slope

371 149
2.78 F %
80

Using Figure 2B1.1, the average boiling points are calculated from the volumetric average boiling
point:

MABP 271 30 241 F


WABP 271 7 278 F

CABP 271 7 264 F


MeABP 271 19 252 F

157048
Process Calculations
Page 90

Calculation of Flow Meter Constant K for Liquid Flow:


Gf

Q max N S D 2 Fa Fc hm
Gb

Where:
Qmax
N
D
d
S
Fa
Fc
Gf
Gb
hm
Note:

=
=
=
=
=
=
=
=
=
=

maximum flow rate at base conditions, (@ 60F)


constant based on flow units
Process pipe inside diameter
orifice diameter
discharge coefficient, f(d/D)
thermal expansion of plate
Reynolds correction factor
liquid specific gravity at flowing conditions
gas specific gravity at base condition (@ 60F)
maximum differential pressure (design basis)

N, S, Fa, and Fc can be found in L.Spinks Principles and Practices of Flow Meter Engineering

Example for Sponge Gas Meter


Flow, bpsd
N, for bpd
D
d
B = d/D
S
Fa
Viscosity, cS
Re
Fc
hm
Temp, F
Gb
Gf

=
=
=
=
=
=
=
=
=
=
=
=
=
=

34,000
194.3
7.981 in
5.034 in
0.6307
0.2672
1.001 for type 304 stainless steel plate
10
39,292; Re = 92.235*bpsd / (viscosity*D)
1.015
100 in H2O
173F
0.9266
0.8854 Gf = Gb*VCF = 0.9260 * 0.9562 = 0.8854

0.8854

Q max 194.3 0.2672 7.9812 1.001 1.015 100

0
.
9266

Q max 34,119 BPSD


The K constant can be calculated by using the following equation:

Q max* Gb 3,360 BPSD


10 Gf

Where: 10: maximum units meter reading, MR, then:

Gf
;
Q 3,360 MR
Gb

Q _________ BPSD

157048
Process Calculations
Page 91

Calculation of Flow Meter Constant K for Gas Flow:


Pf
Q max N S D 2 Fa Fc Y hm
Tf Gb Z
Where:
Qmax
N
D
d
S
Fa
Fc
Y
hm
Pf
Tf
Gb
Z
Note:

=
=
=
=
=
=
=
=
=
=
=
=
=

maximum flow rate at base conditions, (@ 60F)


constant based on flow units
Process pipe inside diameter
orifice diameter
discharge coefficient, f(d/D)
thermal expansion of plate
Reynolds correction factor
upstream orifice expansion factor
maximum differential pressure (design basis)
absolute flowing pressure upstream of the orifice, psia
absolute flowing temperature, R
gas specific gravity at base condition (@ 60F)
compressibility factor of gas

N, S, Fa, Fc, Y and Z can be found in L.Spinks Principles and Practices of Flow Meter Engineering

Example for Sponge Gas Meter


Flow, scfm
N
D
d
B = d/D
S
Fa
Viscosity, cP
Re
Fc
Y
hm
Pf
Tf
Cp/Cv
Gb
Z

=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=

8,375
=
lb/hr
=
26,100
128.78 for scfm and psi
6.065 in
3.5834 in
0.5908
0.2284
1.0003, for type 304 stainless steel plate
0.011
2,472,487; Re = 6.32(lb/hr)/(viscosity*D)
0.988
0.9944; Y = 1-(0.41-0.35B^4)(h/2)/(27.67Pf*(p/Cv))
200 in H2O
187.7 psia
573R
1.27
0.7054
0.965 f(Tr,Pr)
Tr = Tf/Tc
Pr = Pf/Pc

Q max 128.78 0.2284 6.065 2 1.0003 0.9881 200

Q max 10,490scfm
The K constant can be calculated by using the following equation:

Gb
Q max
1,539scm
K
Tf
10
Pf
Where: 10: maximum units meter reading, MR, then:

Q 1539 MR

Pf
Gb ;
Tf

Q _________ scfm

187.7
573 0.7054 0.965

157048
Treating
Page 1

FEED/PRODUCT TREATING
INTRODUCTION
FCC feeds contain a number of contaminants that affect yields, product quality,
plant emissions and corrosion in the main column and gas concentration unit.
These contaminants are handled by a combination of treating either the feed or
products as well as unit design. This subject is of increasing importance to refiners
with the ever tighter limits on emissions from the plant, especially SOx and NOx and
on limits in liquid product sulfur levels. The industry trend towards processing resid
feeds which typically have higher concentrations of sulfur, metals and carbon
residue makes this issue even more important.
In the United States new fuel specifications are will limit the sulfur concentration in
both gasoline and high speed diesel fuels to less than 50 wppm. This is an issue
critical to the FCC because in a typical refinery gasoline pool 98% of the total
gasoline pool sulfur comes from the FCC naphtha even though the FCC naphtha
makes up only 30-40% of the pool. Limits on fuel oil sulfur will also require a
reduction in the MCB product sulfur. In some areas the limits on SOx emissions will
be more restrictive requiring less than 300 ppm in the flue gas. In the coming years
these restrictions will likely become even more stringent.
FEED TREATING
Light and heavy vacuum gas oils are the most common FCC feedstock with an
increasing trend towards atmospheric resid. Also, there are economic incentives
towards processing lower priced crudes which typically contain higher levels of
contaminants.
Hydrotreating is the most common and effective method of improving the FCC feed
quality. Hydrotreating not only reduces the contaminant concentration but also
improves yields. Hydrogen addition to the feed, especially to the large polynuclear
aromatics, makes these molecules easier to crack resulting in higher conversion to
desired products with less coke and light gas make. Table 1 shows the impact of
hydrotreating on both the FCC feed properties and the FCC yields.

157048
Treating
Page 2

Table 1
Feed Hydrotreating Benefits
Feed Desulfurization
Feed Properties
Gravity, API
Sulfur, wt%
Nitrogen, wppm
Carbon Residue, wt%
Metals (Ni + V), wppm
Yields, wt%
H2S
C2LPG
Naphtha
LCO
MCB
Coke
Conversion, lv%
Key Product Properties
Naphtha RONC
Naphtha MONC
LCO Cetane Index
Product Sulfur, wppm
H2S
Naphtha
LCO
MCB
SOx , vppm in flue gas

Untreated

90%

98%

99%

20.5
2.6
880
0.4
5

23.5
0.25
500
0.25
2

24.8
0.06
450
0.1
1

26.0
0.02
400
0.1
<1

1.1
3.3
16.3
48.3
16.7
9.0
5.4
74.3

0.1
3.5
17.6
51.5
15.7
6.6
5.0
77.7

0.0
3.2
18.7
52.5
15.0
5.9
4.7
79.1

0.0
2.8
19.9
53.6
14.0
5.2
4.4
80.8

93.2
80.5
25.7

93.0
80.8
25.7

92.9
81.1
26.4

92.7
81.0
26.5

10,100
3,600
29,700
57,800
2,000

750
230
3,400
11,000
410

190
55
900
3,000
120

95
18
300
1,100
42

157048
Treating
Page 3

As more sulfur is removed the sulfur balance in the FCC shifts towards higher
percentage of the total feed sulfur going to the MCB product and SOx in the flue
gas. This is because the hardest to remove sulfur is in the heavy aromatic
compounds which tend to form coke or remain uncracked. From Table 1 the
percentage of sulfur in the feed ending up in the MCB product increases from 20 to
30% and the percentage of feed sulfur ending up in the naphtha decreases from 6.7
to 4.8% as the untreated feed is desulfurized by 98%.
Table 1 illustrates a case where hydrotreating is used primarily for reduction in
sulfur. In some units, especially those treating resid feeds, the reduction of carbon
residue and metals is more important. Hydrotreating can reduce feed metals and
carbon residue by 90% or more allowing processing of extremely contaminated
resid feeds in the FCC while still achieving good yields. This can also significantly
reduce the required fresh catalyst addition rate.
Nitrogen is also removed by feed hydrotreating. Some of the nitrogen in the FCC
feed is converted to ammonia which can cause salt formation and plugging in the
main column overhead. Basic nitrogen in the feed acts a temporary poison to the
FCC catalyst. Severely contaminated FCC feeds may contain as much as 4,000
wppm nitrogen while a clean feed may contain less than 500 wppm. Cyanides are
also formed from nitrogen in the feed which can cause blistering and corrosion in
the gas concentration unit. Wash water and proper control of the main column
overhead temperature is usually sufficient to prevent these plugging and corrosion
concerns so that these are usually not a significant factor when considering
hydrotreating as an option to improve profitability.
Oxygen may be present in the feed either chemically bonded in the hydrocarbon or
absorbed from storage. Dissolved oxygen may cause fouling of heat exchangers
when the temperature approaches 400F (200C). The best method for preventing
this is to blanket the raw oil tanks with either fuel gas or nitrogen. This is most
important for cracked feed stocks such as coker gas oil or highly olefinic feeds.
Once in the reactor the oxygen will quickly be converted to water, carbon oxides,
phenols, creosols or acids.

157048
Treating
Page 4

PRODUCT TREATING

FCC products contain undesirable material which must be either removed or


transformed into an inoffensive material if the product is to meet specifications for
use. The cycle oil, gasoline, LPG and fuel gas must be non-corrosive, stable in
storage and of acceptable odor. The specifications may also limit the allowable
amount of contaminants such as sulfur. Feed treating is effective in reducing nearly
all of these contaminants but it requires a very high capital investment.
The major undesirable constituents found in FCC products are:

1.

Sulfur compounds. In the gasoline and lighter compounds there are


particularly hydrogen sulfide, mercaptans, elemental sulfur, and carbonyl
sulfide. While the regenerator flue gas is not considered a product of the FCC,
reduction of SOx emissions from this stream is of increasing importance to
most refiners. SOx control is covered in more detail in the Environmental
section of this manual.

2.

Oil soluble or ionic metals, principally copper.

3.

Nitrogen containing compounds, such as pyridine, quinoline, and pyrrole. NOx


in the regenerator flue gas is also a common concern.

4.

Oxygenated compounds, including phenols and carbonic acids.

5.

Diolefinic hydrocarbons.

The degree of undesirability is modified and varies between groups of substances


as well as within families of compounds, depending upon the concentrations
present and the required product specifications. Synergistic and inhibiting
relationships are known to exist, as between thiophenols and olefins which intensify
gum formation, or between elemental sulfur and hydrogen sulfide which promote
copper strip corrosion. The distribution and concentration of objectionable

157048
Treating
Page 5

components in particular product are governed by FCC charge properties, catalyst


type and activity, the promotion of thermal cracking reactions, and fractionation
schemes. The following sections will discuss the impurities and what may be done
to render them harmless.
SULFUR
There are a variety of different sulfur compounds present in FCC product streams.
They vary in their potential damage, but overall rate as the most troublesome
impurity. Hydrotreating each product stream would remove them along with other
contaminants, but from both a process and cost basis this technique is rarely used
for LPG or gasoline treating. Hydrotreating is occasionally used for cycle oil treating.
Elemental Sulfur
Elemental sulfur may occur naturally, but because it is non-volatile it does not distill
to any product above the feed tray. Elemental sulfur formation can be a problem in
the gas concentration unit when oxygen in present. The most common source of
the oxygen is the wash water injected in the wet gas compressor interstage. It is
also possible that during startup catalyst circulation in the FCC oxygen will be
entrained into the reactor and enter the gas concentration unit which can cause
elemental sulfur formation for a short period after startup. The best solution to
minimize elemental sulfur formation is to eliminate all possible sources of oxygen
including using steam condensate for the wash water.
Elemental sulfur can also be found in the FCC gasoline or LPG products if there is
carry over of caustic from the Merox or other treating units.
Elemental, sometimes called free sulfur corrodes copper and consequently
produces a positive copper strip corrosion test. In the absence of H2S, as little as 5
wt. ppm free sulfur can give a failing copper strip test. If H2S is present, even in very
low concentrations, the amount of allowable sulfur is even less. When 0.3 wt. ppm
H2S is present, 0.5 wt. ppm elemental sulfur can give a filling copper strip test.

157048
Treating
Page 6

Elemental sulfur has a harmful effect on alkyl lead susceptibility for gasoline octane
improvement. Free sulfur will remain as a deposit when LPG is evaporated.
Removal of elemental sulfur is very difficult; hydrotreating or redistillation are two
costly removal methods. Chemical treatments such as scrubbing with sodium or
potassium polysulfide solutions or caustic-sodium sulfide, or reverse doctor treating
may be used but may not be completely effective. Certain additives may be helpful
in masking the sulfur corrosivity test. They should be used with caution. The best
treatment method is to avoid elemental sulfur formation by preventing H2S
oxidation.
Hydrogen Sulfide
Hydrogen sulfide results from the decomposition of sulfur compounds during the
cracking reaction and concentrates in the fuel gas and LPG products. It has an
obnoxious odor at low concentration, and is very poisonous. It paralyzes the
involuntary breathing function, leading to asphyxiation, unconsciousness and death.
Hydrogen sulfide in fuel gas will burn in a heater to form SO2. This acid gas may
cause corrosion and environmental problems due to its acidity when it dissolves in
water. In the presence of oxygen, H2S may oxidize in a product stream to form
elemental sulfur. H2S has a deleterious effect on lead susceptibility of FCC
gasoline. It promotes peroxide formation and prevents oxidation inhibitors from
functioning, thus reducing gasoline stability in storage. It is undesirable in HF acid
alkylation feedstocks as one pound of sulfur consumes about five pounds of
process acid, and H2S, along with some mercaptans, is sufficiently volatile to stay
with the C3 and C4 streams.

157048
Treating
Page 7

Dilute caustic soda or soda ash will remove H2S as well as CO2. The aqueous
caustic soda solution must be sufficiently dilute to prevent formation of sodium
sulfide crystals as the NaOH is converted to Na2S, and in the case of a dry feed, as
the solution dehydrates. Normal caustic concentrations are in the range of
10-15 Be to avoid Na2S crystallization.
The other principal treating method for the removal of H2S is regenerative
monoethanolamine (MEA) or diethanolamine (DEA) scrubbing. The stream to be
treated is contacted countercurrently with the amine to remove H2S, CO2, and COS.
The amine is then steam stripped to regenerate it. Although this treatment can
reduce H2S concentrations below 6 wt. ppm, it is equilibrium limited and therefore it
is normal to provide a dilute batch caustic scrubber following the amine scrubber as
a final cleanup and guard in case of an amine unit upset, e.g., when treating LPG.
Aside from pollution abatement benefits when operated in tandem with a sulfur
recovery process, amine treating usually becomes economically attractive strictly on
a chemical consumption basis when H2S levels exceed roughly 1000 ppm.
Mercaptans (RSH)
Mercaptans are found in all cracked products streams. Some of these may be
naturally occurring in the feed, but most mercaptans are formed during the cracking
reactions. Decomposition of other sulfur compounds or recombination reactions
between H2S and olefins are the major sources. There are two distinct types: alkyl,
open chain mercaptans, and aryl, aromatic mercaptans in which the SH group is
linked to a benzene ring structure. The aryl mercaptans are also known as
thiophenols and thiocresols. They tend to predominate over alkyl mercaptans in
FCC product streams boiling over 300F (150C).
The lower molecular weight mercaptans have a very obnoxious odor, particularly
noticeable due to their low vapor pressure. All mercaptans, like most sulfur
compounds, have a deleterious effect on lead susceptibility of motor gasolines.
Thiophenols promote gum and sludge formation reactions and cause storage
problems. Mercaptans can react with copper, particularly if basic nitrogen is
present, to form oil soluble cuprow compounds which can be oxidized to insoluble

157048
Treating
Page 8

copper oxide. The soluble copper can also then react with some oxygenated
compounds to form gelatinous copper phenolates.
Low molecular weight mercaptans may be extracted to some degree with caustic or
be sweetened, in a process which converts the mercaptans to less odiferous
disulfides. Mercaptans may be extracted from LPG to very low values, 0.5 wt. ppm
in some cases. Extraction of 50-95% of the mercaptans from gasoline is possible,
depending on boiling range. However, as mercaptans in FCC gasoline generally
represent only 10 to 35% of the total sulfur present, partial gasoline desulfurization
by extraction is usually not economical. The majority of FCC gasolines are currently
only sweetened to essentially eliminate mercaptans and produce a doctor negative,
or sweet, gasoline. Cycle oil is sometimes sweetened, but if low sulfur is desired,
the cycle oil must be hydrotreated.
Non regenerable caustic scrubbing to extract mercaptans is an old and expensive
process which may create or compound waste disposal problems. In many cases it
is not very effective. The most successful treating process for either extraction or
sweetening is the UOP Merox process. This process uses small amounts of caustic
to remove or transform mercaptans. A catalyst and oxygen supplied from
atmospheric air are used to regenerate the caustic. Further information on the
Merox process may be obtained from UOP.
Total gasoline sulfur may also be reduced by undercutting or reducing the endpoint
of the FCC gasoline. The sulfur concentration in the FCC gasoline increases rapidly
as the boiling range exceeds ~400 (200C). By reducing the endpoint of the
gasoline so that the heaviest 20% is included in the light cycle oil product the
gasoline sulfur content can be reduce by as much as 60%. Unfortunately, there are
significant product value losses associated with this for most refiners.

157048
Treating
Page 9

Carbonyl Sulfide (COS)


Carbonyl sulfide is produced during the cracking reaction. It boils slightly below
propane at -58F (-50C). Upon post fractionation the COS concentrates in LPG,
propane-propylene, and finally propylene as the distilled cuts are narrowed in
boiling range. COS concentrations in the LPG stream may range from 5 to 100
ppm; the amount usually rises with increased feed sulfur, but is very unpredictable.
COS, like some other sulfur compounds, should be considered toxic.
The principle concern with COS, aside from situations where product total sulfur
must be very low or zero, is its tendency to hydrolyze, forming corrosive H2S and
CO2. This hydrolysis proceeds slowly but is catalyzed by activated alumina or
molecular sieve desiccants. COS also partially reacts with MEA in acid gas
scrabbling systems to form high boiling by-products which are not steam
regenerable. COS is also a strong poison for polypropylene producers using FCC
propylene as a feed. Some polymerization catalysts are sensitive to as little as 5
ppb COS.
Carbonyl sulfide can be partially removed from the light product streams by
scrubbing with an aqueous DEA solution. Diethanolamine, unlike monoethanolamine, does not chemically react with COS and therefore is steam regenerable.
Aqueous DEA scrubbing can usually reduce COS levels to less than 10 ppm. A
reduction of COS to levels of one ppm or less can be effected with a batch scrubber
using MEA, sodium hydroxide, and water to remove COS by chemical reaction.
This system is not regenerable. For units producing polymer grade propylene
additional adsorbents or reactive treaters will commonly be used to remove COS
down to undetectable levels.
Copper
Copper is a powerful oxidation catalyst. It is usually picked up from contact with
copper or copper alloy surfaces, especially when ammonia or other basic nitrogen
and mercaptans are present. Copper catalyzes gum formation by promoting olefin
oxidation reactions faster than inhibitor additives can terminate these chain

157048
Treating
Page 10

reactions. Cracked distillates containing copper will form gum and gelatinous
precipitates in storage. Copper also contributes to distillate color stability problems
and catalyses oxidation of alkyl lead additives, leading to haze in some finished
gasolines.
Gross copper contamination can be removed by chemical treatment, such as dilute
acid scrubbing or clay percolation. If the copper does not exceed 1 mg/liter, it can
be rendered harmless with a copper deactivator. Dosage is roughly 10 wt. ppm
active agent for each mg/liter. The deactivator, a chelating agent, complexes with
the copper so that it cannot take part in any further reactions.
Nitrogen Compounds
There are usually two types of nitrogen found in gasoline and cycle oil. One type
would be neutral compounds such as pyrrole, and the other a basic compound such
as pyridine or quinoline. Ammonia is found in the reactor overhead vapors, but if
normal main column overhead water injection is maintained, the ammonia is
removed at this point.
Neutral nitrogen compounds are associated with sediment formation in fuel oils.
Basic compounds are typically more harmful. Pyridine has a characteristic odor
which is very unpleasant when combined with mercaptans. Both basic and neutral
nitrogen compounds are color precursors which affect distillate color stability. Their
effect on lead susceptibility and octane number varies between good and bad
depending on the particular compound in question. Both types of nitrogen
compounds may also promote oil soluble gum formation, but this has not been
firmly established at this time.
Neutral nitrogen compounds may be removed with either strong acid or strong
caustic-methanol solutions. Basic nitrogen compounds could be removed with dilute
acid in acid resistant equipment. If acid strength is too high, there may be problems
with olefin addition, sulfonation, and other acid catalyzed reactions. Hydrotreating
will decompose both types of nitrogen compounds to ammonia. This might be

157048
Treating
Page 11

suitable for cycle oils, but not for gasoline, because aromatics might be saturated,
with severe loss in octane number.
Oxygen
Oxygen compounds such as phenols and cresols are formed during the cracking
reaction from oxygenated compounds in the feed and from oxygen entrained with
the catalyst. They are generally not considered harmful and may be considered
beneficial as some act as oxidation inhibitors. Some of the phenols are suspected
of being color precursors. Caustic treating can be used to remove most of the
oxygen containing compounds, including most organic acids, when deemed
necessary.
Diolefins
Diolefins, especially conjugated diolefins, are reactive hydrocarbons which quickly
enter into gum and sediment forming reactions. These compounds are normally
found in significant concentrations only in thermally cracked products. However,
when FCC conditions allow cracking to occur in the absence of catalyst, diolefins
will be formed in amounts roughly proportional to the degree of thermal cracking
present.
A good example of this type of compound is butadiene. It stays in the C4 fraction as
it is concentrated through fractionation. If this stream is then used as alkylation
feed, the butadiene will polymerize to form tar. Higher order diolefins lead easily to
gum formation in the gasoline and cycle oil streams.
Diolefins can be removed without significant olefins removal by carefully controlled
mild hydrotreating or vapor phase clay treatment. Proper dosage of oxidation will
nullify their effects. Another solution would be to minimize formation of diolefins by
decreasing thermal cracking. This could be done by reducing the reactor
temperature, reducing the regenerated catalyst temperature or by mechanical
changes minimizes post riser residence time.

157048
Treating
Page 12

SUMMARY FCC PRODUCT TREATMENT METHODS


Contaminant

Concentration

Treatment

Copper

High

Dilute mineral acid


Clay percolation

Low (<1 mg/l)

Metal deactivator addition

Elemental sulfur

Redistribution
Hydrotreating
Reverse Doctor
Prevent formation by
minimizing free oxygen

Hydrogen sulfide, H2S

High (>1000 ppm)

MEA or DEA scrubbing

Low

Caustic soda, MEA or DEA


scrubbing

Any

Merox (Regenerative caustic)


Extractive for LPG or
Sweetening for Gasoline

Mercaptans, R-SH

Total Gasoline Sulfur


Carbonyl sulfide, COS

Undercutting of FCC gasoline

DEA-water scrubbing
Caustic-MEA-water scrubbing
(Batch operation only)
Silica-Alumina Adsorbents
PbO Treaters

Basic nitrogen compound

Water Wash (NH3)


Weak mineral acid

Neutral nitrogen compound

Strong acid
Strong caustic-methanol
solution

157048
Treating
Page 13

Contaminant

Concentration

Treatment

Oxygen compounds, phenols


or acids

Water Wash
Caustic soda

Diolefins

Mild hydrotreating
Vapor phase clay treating
Change FCC operations to
minimize formation

NOTE: Hydrotreating may be used to eliminate many of these contaminants. In


practice, however, it is used for cycle oil treating in some cases, rarely for LPG or
gasoline. Treating of the FCC feed is also effective in minimizing many of these.
Regenerative caustic treating, such as the Merox process, is a very common
treating method. Batch scrubbing using caustic, or regenerative MEA-DEA
scrubbing are also used. This may be in conjunction with a Merox unit or without it,
depending on the contaminant and on economic considerations.

157048
Analytical Methods
Page 1

ANALYTICAL METHODS
Introduction
Good analyses of the feed and product streams are essential for control and
evaluation of a Fluid Catalytic Cracker. It is extremely difficult to optimize a unit if
potential problems are not defined through the laboratory and process variables.
The following sections give a typical FCC sampling schedule and a brief outline of
some of the more common analytical methods.
There are a large number of laboratory tests which may be used. FCC products
vary widely, from clarified oil to fuel gas. This in turn leads to markedly different
analytical methods, such as six different types of distillations. The product being
tested and the type of result desired will determine which test is used.
Distillation
There are six distillation methods listed in this book. Two of them, UOP 1 and
ASTM D 86, cover the lighter fractions, from gasoline to gas oils. The UOP 1
method goes further; it continues past the typical decomposition point of 700F
(371C) into a thermal cracking of the sample with a dry residue (coke) remaining.
Two other methods, UOP 77 and 79, are fractionations in addition to distillations.
Either one can be used to separate certain fractions of a product for further
analysis. UOP 77 is more commonly used. UOP 79 is a high precision distillation
method which is used to determine true boiling points of petroleum fractions. The
test requires special equipment and the information obtained from this test is not
frequently needed. The two vacuum distillation methods, UOP 76 and ASTM D
1160, are used for heavy material. Reduced pressures, down to 1 mm Hg absolute
for D 1160 and 0.3 mm Hg absolute for UOP 76, permit distillation when the
temperature used for atmospheric techniques would lead to thermal cracking.
Sulfur

157048
Analytical Methods
Page 2

The six analytical methods for sulfur analysis can be initially divided into two groups,
gases and liquids. The Tutwiler method, UOP 9, gives a quantitative determination
of H2S in a gas stream. A second method, UOP 212, measures H2S, mercaptans,
and COS in light gases and LPG. The Tutwiler method does not give as detailed a
test as does UOP 212, but takes less time. There are four methods given for hydrocarbon liquid analysis. The Doctor Test, UOP 41, gives a qualitative determination
of mercaptans and H2S. UOP 163 will give a breakdown of mercaptan and H2S in
liquid streams. For total sulfur of lighter oils, the Lamp method, ASTM D 1266, is
used. For oils boiling above 350F (177C), ASTM D 1552 may be used to
determine total sulfur.
Octane
The Motor octane method, ASTM D 2700, is more severe, i.e., gives a lower rating
than does the Research method, ASTM D 2699. The correlation between the two is
not exact, so it is generally not easy to predict one octane from another. For similar
feedstocks and plant operation, the refiner may be able to make some general
predictions from past data.
Gas Chromatography
To determine the composition of light hydrocarbon gases and LPG streams
containing small amounts of C3 and C6 material, either UOP 539 or UOP 709 may
be used. Neither of these will separate argon from oxygen, or butene-1 from
isobutylene. UOP 709 is easier to run than UOP 539 and requires less elaborate
equipment, but UOP 709 does not differentiate between ethane, ethylene and
carbon dioxide. For exact determination of fuel gas from an FCC, UOP 539 would
be the better method. UOP 725 can be used to determine concentration of C5 and
lighter material in FCC gasoline.

157048
Analytical Methods
Page 3

Samples for UOP Analysis


Most refineries have laboratories for common analyses. Samples may be sent to
UOP if the refiner does not have the equipment, manpower, or wishes to check the
accuracy at his own lab. Samples which are sent to UOP for analysis sometimes go
astray, either in shipping or within UOP. In order to minimize delays caused by lost,
misplaced or unidentified samples, please observe the following rules.
1.

Identify each sample with refiner, location, unit, sample, date and technical
contact person at UOP responsible for the results. Make certain the sample
tag is well secured to the sample and remains legible, even if it is wet with
water or hydrocarbon.

2.

It has been found that gasoline or naphtha sample collection in clear bottles,
which are left exposed to sunlight (or ultraviolet lighting) either direct or
indirect, and whether or not the sample has been treated with oxidation
inhibitors, will result in a severe loss of octane rating within a very short time.
Every effort must therefore be made to see that only the brown or amber
sample bottles are used for daily samples and more important that all samples
shipped to UOP for analysis are taken in amber bottles, are kept in a cool dark
place until packaged for shipment, and are shipped as soon as possible after
sampling.

3.

When shipping samples, mail or phone shipping information (air waybill, flight
number, bill of lading, etc.) to UOP.

4.

Send a copy of the request for analysis with the samples; send the original to:
UOP
Technical Service Department
FCC Group
25 E. Algonquin Road
Des Plaines, IL 60017 USA

157048
Analytical Methods
Page 4

5.

Send samples to:


UOP LLC
Shipping and Receiving
50 E. Algonquin Road
Des Plaines, IL 60017 USA

6.

For larger Rush samples being sent to UOP by air, indicate the shipping
instructions as:
SHIP TO: UOP LLC
Chicago, Illinois 60017 USA
HOLD AT: O Hare Airport
CALL: (847) 391-3043 ON ARRIVAL

7.

All samples shipped from outside the United States require additional
paperwork to comply with the U.S. Environmental Protection Agencys Toxic
Substances Control Act (TSCA). The following are some of the guidelines for
importing samples into the United States. Always contact your customer
service or technical service representative for assistance before
shipping any samples to ensure that all regulations are followed.
The use of a freight forwarder (e.g. Burlington Air Express or Emery
Worldwide) is preferred for all imported samples.
Overnight couriers (e.g. DHL, Federal Express or UPS) may be used
only if the written TSCA certification authorized, signed and dated by
UOP is obtained prior to shipment and physically included with the
documentation in the shipped package.
All samples should be routed through Chicagos Ohare International
Airport
All imports must have the following documentation:

Bill of Lading (also known as a Master Airwaybill) which includes


vessel/flight information. The Bill of Lading must state: "Customs clearance
by Circle International". The Bill of Lading description field must begin with
the words TSCA Certified Chemical Sample.
Pro forma invoice (Attachment 1a and 1b: a blank form and example).
TSCA Certification (Attachment 2).
Analytical Requisition Form (Attachment 3)
Material Safety Data Sheet (MSDS) if the sample material is regulated as
hazardous by IATA, IMO or DOT.

157048
Analytical Methods
Page 5

The documentation on the above listed items must contain the


following information:
On the Proforma Invoice:
Shippers name, address, contact name, phone number and fax number.
Importers name, address, contact name, phone number and fax number (this
must include the UOP contact person within the U.S.). UOP has provided this
information except for Contact Person
Consignee/Delivery name, address, contact name, phone number and fax
number (this must include the actual delivery location). UOP has provided this
information.
Approximate market value (for Customs purposes), for each item, in U.S.
Dollars.
Sample descriptions in English.
Packing details the number and types of containers.
Net weights and Gross weights for each item, in kilograms.
Country of origin. This is the country where the sample was taken.
On the TSCA Certification Form:
Sample description in English, UOP has provided this information.
Date the sample is to be shipped, in English.
On the International Analytical Requisition Form:
Shippers name, address, contact name, phone number and fax number.
Sample shipping information: Carrier and flight information, phone number of
the carrier, airway bill no.
Fill in all pertinent sample and analytical request information as required.

All samples must be prepared according to the hazardous materials shipping


regulations of the International Air Transportation Association (IATA), if
shipped by air, or International Maritime Organization (IMO) if shipped by
sea.
Prior to shipping, the UOP Tech Service Sample Coordinator must be
notified of all imports before their arrival in the United States. Please fax a
copy of the Pro Forma Invoice, the Bill of Lading, TSCA Certificate, and
the Analytical Requisition Form to the UOP Technical Service Sample
Coordinator at 847-391-2253. UOP will then ensure proper Customs and
TSCA clearance.
Failure to send samples with the proper documentation and information will result in
a delay of Customs clearance or refusal of the sample.

157048
Analytical Methods
Page 6

Attachment 1a
Proforma Invoice
International Shipper/Exporter (Name & Address)
Invoice No:
Invoice Date:
Terms: Pro-Forma Invoice
Reference No:

Contact Name:
Contact Phone No.

Fax No.

DESCRIPTION
* * * NO CHARGE INVOICE * * *
QUANTITY:

GROSS WEIGHT:

MARKET
VALUE -DECLARED
FOR CUSTOMS
CLEARANCE
PURPOSES
ONLY

BOX(ES)
KGS.

COUNTRY OF ORIGIN (where sample was taken) __________________________


MARKS: AS ADDRESSED
IMPORTER OF RECORD
UOP LLC
25 EAST ALGONQUIN RD.
DES PLAINES, IL 60017
ATTN:

CONSIGNEE / DELIVERY ADDRESS:


UOP LLC
SAMPLE RECEIVING
50 EAST ALGONQUIN RD.
DES PLAINES, ILLINOIS 60017-5016
ATTN: UOP Tech Service Sample Coordinator

UOP Contact Name


Refinery Representative Signature

US DOLLARS
$

DESCRIPTION OF SAMPLE(S):

PACKED IN

AMOUNT

Refinery Representative Name: please print

I HEREBY CERTIFY THAT THIS INVOICE IS TRUE AND CORRECT.


ORIGINAL INVOICE

157048
Analytical Methods
Page 7

Attachment 1b
Example
Proforma Invoice
International Shipper/Exporter (Name & Address)
Mountain View Refining
1000 Mountain View Dr.
Boulder City
Refining Country
Contact Name: Joe R. Engineer
Contact Phone No. (12) 3 456 -7890 Fax No. (12) 3-098-7654

Invoice No:
Invoice Date:
Terms: Pro-Forma Invoice
Reference No:

DESCRIPTION

* * NO CHARGE INVOICE * * *
QUANTITY: Three 1 liter catalyst samples

AMOUNT

US DOLLARS
$

DESCRIPTION OF SAMPLE(S): R-134 CCR Platforming Catalyst


Two regenerated samples and one spent sample
PACKED IN

GROSS WEIGHT:

BOX(ES)
3.5

KGS.

COUNTRY OF ORIGIN (where sample was taken) Refining Country


MARKS: AS ADDRESSED
IMPORTER OF RECORD
UOP LLC
25 EAST ALGONQUIN RD.
DES PLAINES, IL 60017
ATTN:

Robert S. UOP

CONSIGNEE / DELIVERY ADDRESS:


UOP LLC
SAMPLE RECEIVING
50 EAST ALGONQUIN RD.
DES PLAINES, ILLINOIS 60017-5016
ATTN: UOP Tech Service Sample Coordinator

UOP Contact Name

Joe R. Engineer
Refinery Representative Signature

Joseph R. Engineer
Refinery Representative Name: please print

I HEREBY CERTIFY THAT THIS INVOICE IS TRUE AND CORRECT.


ORIGINAL INVOICE

MARKET
VALUE -DECLARED
FOR CUSTOMS
CLEARANCE
PURPOSES
ONLY

157048
Analytical Methods
Page 8

Attachment 2a
TSCA Certification Form

To: Area Director of Customs


Date:
Description of Sample:
Only one of the following should be selected:

( X ) TSCA Positive Certification


I certify that all chemical substances in this shipment comply with all
applicable rules or orders under TSCA and that I am not offering a
chemical substance for entry in violation of TSCA or any applicable
rule or order under TSCA.
OR

( ) TSCA Negative Certification


I certify that all chemicals in this shipment are not subject to TSCA

Signature (Authorized UOP LLC employee)

Printed Name (Authorized UOP LLC employee)

157048
Analytical Methods
Page 9

Attachment 2b
TSCA Certification Form

Example Form

To: Area Director of Customs


Date: August 23, 1999
Description of Sample: R-134 CCR Platforming Catalyst: Spent
Only one of the following should be selected:

( X ) TSCA Positive Certification


I certify that all chemical substances in this shipment comply with all
applicable rules or orders under TSCA and that I am not offering a
chemical substance for entry in violation of TSCA or any applicable
rule or order under TSCA.
OR

( ) TSCA Negative Certification


I certify that all chemicals in this shipment are not subject to TSCA

Signature (Authorized UOP LLC employee)

Angelo P. Furfaro

Printed Name (Authorized UOP LLC employee)

157048
Analytical Methods
Page 10

Attachment 3
International Analytical Requisition Form - UOP Technical Service
TO: UOP Technical Service Sample Coordinator
391-2253

Phone 847-391-2620 FAX: 847-

UOP Technical Service Contact


391-2253

Phone 847-391-

Fax 847-

Phone

Fax

Customer:

Refinery
Address
Contact Name

Liquid & Gas Sample(s)


Analysis Required:

Description

Check if
MSDS is
Included

Rush
or
Standard

Catalyst & Adsorbent Sample(s):


Sample Location:

Process or unit:
Catalyst Type

Regenerated or Coked
Standard

Billing Information:
Address:

Attention:
Sample Shipping Information:
Shipped Via:
Phone Number of Carrier:

Airwaybill No.:

Analysis Required

Check if
MSDS is
Included

Rush
or

157048
Analytical Methods
Page 11

Minimum Sample Size


Analysis

Minimum
(cm3)

Heavy Oil (Clarified Oil, Slurry, Raw Oil, Heavy and Light Cycle Oil)
API
Distillation
Viscosity
Vacuum Distillation
Conradson Carbon
Ash (sample to be taken and shipped in a wide mouth sample container)
Sediment and Water
Sulfur
Nitrogen
Metals
Pour Point
Color

100
250
150
300
150
300
150
20
15
100
200
50

Gasoline, LPG
API
Distillation
Hydrocarbon Types by GC
C5- by GLC
RVP
Mercaptan Sulfur
Total Sulfur
Octane Research
Motor
Leaded or Clear
Catalyst

100
210
150
50
1000
100
100
1000
for each
type
1000

NOTE: Individual samples can be taken from one large sample of each product,
usually about 1-2 gallons (3.5-7.0 liters).

157048
Analytical Methods
Page 12

TYPICAL TEST SCHEDULE

STREAM AND TEST


Raw Oil Charge
Gravity
Viscosity
Vacuum Distillation
Conradson
Carbon Residue
BS & W
Sulfur
Total Nitrogen
Metals Content by Wet Ash
(May be sent to Outside Lab)
Pour Point
Basic Nitrogen
Heptane Insolubles
UOP K

TEST NUMBER

FREQUENCY
Normal Startup

D-1298 or D-5002 or D-4052


D-445
D-1160

1/D
1/W
1/D

3/D
3/W
1/D

D-189 or D4530
D-4007
UOP 864 or D-1552 or D-2622
UOP 384 or D-4629
UOP 389 or D-5708

1/D
1/W
1/D
1/W
1/W

1/D
1/W
1/D
1/W
1/D

D-97
UOP 269
UOP 614
UOP 375

1/W
Occas
Occas
1/D

1/W
Occas
Occas
1/D

Circulating Main Column Bottoms


Gravity
D-1298 or D-5002 or D-4052
BS & W
D-4007
Ash
D-482

Occas
Occas
Occas

1/D
Control
1/D

Main Column Bottoms Clarified Oil Product


Gravity
D-1298 or D-5002 or D-4052
Viscosity
D-445
Vacuum Distillation
D-1160
BS & W
D-4007
Sulfur
UOP 864 or D-1552
Ash
D-482

3/D
1/W
1/D
1/D
1/W
1/W

3/D
1/W
1/D
Control
1/D
1/D

157048
Analytical Methods
Page 13

STREAM AND TEST

TEST NUMBER

FREQUENCY
Normal Startup

Heavy Cycle Oil Product


Gravity
Distillation
Pour Point
Flash Point
Viscosity
Sulfur
Cetane Index

D-1298 or D-5002 or D-4052


D-86
D-97
D-93
D-445
UOP 864
D-976

1/D
1/D
1/D
1/D
1/D
1/D
1/D

3/D
3/D
1/D
1/D
1/W
1/D
1/D

Light Cycle Oil Product


Gravity
Distillation
Pour Point
Flash Point
Viscosity
Sulfur
Cetane Index

D-1298 or D-4052
D-86
D-97
D-93
D-445
UOP 864
D-976

1/D
1/D
1/D
1/D
1/D
1/D
1/D

3/D
3/D
1/D
1/D
1/W
1/D
1/D

Stripped Heavy Naphtha Product


Gravity
D-1298 or D-4052
Distillation
D-86
H2S and RSH
UOP 163
Sulfur
UOP 864
Composition (PONA)
UOP 777
Research Octane
D-2699
Motor Octane
D-2700
RVP
D-323

1/D
1/D
1/W
1/D
3/W
1/D
1/D
1/D

3/D
3/D
1/W
1/D
1/D
1/D
1/D
1/D

Blended Fuel Oil Product


Gravity
Distillation
Viscosity
Sulfur
Pour Point
Flash Point

D-1298 or D-4052
D-86
D-445
UOP 864 or D-1552
D-97
D-93

1/D
1/D
1/W
1/D
1/D
1/D

3/D
3/D
1/W
1/D
1/D
1/D

Main Column Receiver Gas


H2S
Composition

UOP 212
UOP 539

Occas
Occas

1/D
1/D

157048
Analytical Methods
Page 14

STREAM AND TEST

TEST NUMBER

FREQUENCY
Normal Startup

Main Column Receiver Liquid


Gravity
Distillation
GC (C4 and lighter)
H2S and RSH

D-1298 or D-4052
D-86
UOP 725
UOP 163

Occas
Occas
Occas
Occas

Occas
Occas
Occas
Occas

Regenerator Flue Gas


Composition (Orsat or GC)
SOx
NOx
Particulate

UOP 172 or UOP 539


EPA #6
EPA #7
EPA #5

1/D
Occas
Occas
Occas

3/D
Occas
Occas
Occas

Spent Catalyst
Percent Carbon

UOP 703

1/W

Regenerated Catalyst
Particle Size Distribution*
Surface Area*
Pore Volume*
Activity*
Metals by ICP*
Percent Carbon*

UOP 856
UOP 874
UOP 874
D-3907
UOP 546
UOP 703

1/W
1/W
1/W
1/W
1/W
1/D

2/W
2/W
2/W
2/W
2/W
Control

Flue Gas to Electrostatic Precipitator


Isokinetic Particle Determin.
EPA #5

Occas

Occas

Flue Gas from Electrostatic Precipitator


Isokinetic Particle Determin.
EPA #5

Occas

Occas

*Normally performed by catalyst vendors laboratory.

157048
Analytical Methods
Page 15

STREAM AND TEST

TEST NUMBER

Main Column Receiver Water


Iron, Copper
Phenols
Cyanides
Sulfides
Ammonia
Total Oils
pH
Total Dissolved Solids
Silica

UOP 314
UOP 262
UOP 682
UOP 683
UOP 740
D-3921
D-1293
D-1126
D-859

BFW and Continuous Blowdown


Sodium
D-4192
Total Alkalinity
D-1067
M Alkalinity
D-1067
P Alkalinity
D-1067
Chloride (as Cl-)
D-512
Silica (as SiO2)
D-859
Total Dissolved Solids
STD Method 2540C
Total Suspended Solids
STD Method 2540D
pH
D-1293
Specific Conductance
D-1125
Phosphates
D-4327
Oil
D-3921
Hydrazine
D-1385

FREQUENCY
Normal Startup
Occas
Occas
1/M
1/M
Occas
Occas
1/D
1/W
1/M

Occas
Occas
Occas
Occas
Occas
Occas
3/D
Occas
Occas

1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W

1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W

Saturated Steam from Catalyst Cooler, Flue Gas Cooler, and Main Column
Bottoms Steam Generator Steam Drums
Impurities
D-2186-C
Occas Occas
Silica
D-859
Occas Occas
Sodium
D-1428
Occas Occas
Lean Gas Product
H2S
Composition

UOP 212
UOP 539

1/D
1/D

3/D
3/D

Debutanizer Net Overhead Liquid


H2S & Mercaptan Sulfur
UOP 163
Composition
UOP 539
Total Sulfur
UOP 923

1/D
1/D
1/D

3/D
3/D
3/D

157048
Analytical Methods
Page 16

STREAM AND TEST

TEST NUMBER

FREQUENCY
Normal Startup

Debutanizer Bottoms Product


Gravity
Distillation
H2S & Mercaptan Sulfur
RVP
Research Octane
Motor Octane
C4 and lighter
Sulfur

D-1298 or D-4052
D-86
UOP 163
D-323
D-2699
D-2700
UOP 725
UOP 864 or UOP 836

1/D
1/D
1/D
1/D
1/D
1/D
1/D
1/D

3/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D

Naphtha Splitter Bottoms


Gravity
Distillation
Research Octane
Motor Octane
Sulfur

D-1298 or D-4052
D-86
D-2699
D-2700
UOP 864 or UOP 836

1/D
1/D
1/D
1/D
1/D

3/D
3/D
3/D
3/D
3/D

Naphtha Splitter Side Cut Product


Gravity
D-1298 or D-4052
Distillation
D-86
Research Octane
D-2699
Motor Octane
D-2700
Sulfur
UOP 864 or UOP 836

1/D
1/D
1/D
1/D
1/D

3/D
3/D
3/D
3/D
3/D

Naphtha Splitter Overhead Product


Gravity
D-1298 or D-4052
Distillation
D-86
RVP
D-323
Research Octane
D-2699
Motor Octane
D-2700
C4 and lighter
UOP 725
Sulfur
UOP 864 or UOP 836

1/D
1/D
1/D
1/D
1/D
1/D
1/D

3/D
3/D
3/D
3/D
3/D
3/D
3/D

Depentanizer Overhead Product


H2S & Mercaptan Sulfur
UOP 163
Composition
UOP 539

1/D
1/D

3/D
3/D

157048
Analytical Methods
Page 17

STREAM AND TEST

TEST NUMBER

FREQUENCY
Normal Startup

Depentanizer Bottoms Product


Gravity
Distillation
H2S & Mercaptan Sulfur
RVP
Research Octane
Motor Octane
C4 and lighter
Sulfur

D-1298 or D-4052
D-86
UOP 163
D-323
D-2699
D-2700
UOP 725
UOP 864 or UOP 836

1/D
1/D
1/D
1/D
1/D
1/D
1/D
1/D

High Pressure Receiver Water


Iron, Copper
Phenols
Cyanides
Sulfides
Ammonia
Total Oils
pH

UOP 314
UOP 262
UOP 682
UOP 683
UOP 740
D-3921
D-1293

Occas
Occas
1/M
1/M
Occas
Occas
1/D

3/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
Occas
Occas
Occas
Occas
Occas
Occas
3/D

LABORATORY TEST SCHEDULE FREQUENCY NOMENCLATURE


1/D
3/D
1/W
3/W
2/M
N
S
Occas
Control

One determination per day


Three determinations per day
One determination per week
Three determinations per week
Two determinations per month
During normal operation
During startup
Determination is done only occasionally
Determination is done as frequently as necessary for plant control during
startup

157048
Analytical Methods
Page 18

OUTLINE OF SELECTED ANALYTICAL METHODS


SUBJECT INDEX
Test Description
Activity Test for Catalyst
API Gravity
Apparent Bulk Density of Catalyst
Ammonia in Refinery Water
Ash from Petroleum Products
Boilaway (weathering Test)
Carbon on Catalyst
Carbonyl Sulfide (COS) in Gases
Catalyst Loading in Heavy Oil
Color ASTM
Saybolt
Conradson Carbon Residue
Copper in Water
Cyanide in Refinery Water
Distillation of Heavy Oil
of Petroleum
of Petroleum
of Petroleum
(Fractionation)
Vacuum
Vacuum
Doctor Test
Flash Point, Closed Cup
Flash Point, Open Cup
Fractionation of Petroleum

Number
D-3907
D 1298
UOP 254
UOP 740
D 482
UOP 155
UOP 703
UOP 212
UOP 233
D 1500
D 156
D 189
UOP 314
UOP 682
UOP 1
D 86
UOP 77
UOP 79
UOP 76
D 1160
UOP 41
D 93
D 92
UOP 79

157048
Analytical Methods
Page 19

Test Description
Flue Gas Analysis, (GC)
(Orsat)
Particulates, SOx, NOx
Gas Analysis GC
GC
- Pentenes and lighter in olefinic gasoline
Gravity API
Gum
Copper Dish
Existent (Steam Jet)
Hydrogen Sulfide (H2S)
in Gas Tutwiler
with Mercaptans
Induction Period of Gasoline
Iron in Water
Isokinetic Particle Determination in Flue Gas
Kinematic Viscosity
Loss of Ignition of Catalyst
Mercaptan Sulfur Gases
Liquid Hydrocarbons
Metals Trace, in Crackling Catalysts
Trace, in Oils
Trace, in Oils
Nitrogen in Heavy Distillate
Octane Motor
Research
Particle Size Distribution of Catalyst
pH, Iron and Copper in Refinery Water

Number
UOP 539
UOP 172
EPA #5,6,7
UOP 539
UOP 709
UOP 725
D 1298
UOP 11
UOP 277
UOP 9
UOP 212
UOP 6
UOP 314
D 3685
D 445
UOP 275
UOP 212
UOP 163
UOP 546
UOP 389
UOP 391
UOP 384
D 2700
D 2699
UOP 422
UOP 314

157048
Analytical Methods
Page 20

Test Description
Phenols in Petroleum Products
Pore Volume and Pore Diameter of Catalyst
Pour Point of Petroleum Oils
Reid Vapor Pressure
Sampling of Petroleum
Sediment and Water in Oil
Sintering Index of Catalyst
Sulfides in Refinery Waters
Sulfur in Heavy Oils
Sulfur Doctor Test (H2S and Mercaptans)
H2S in Gases (Tutwiler)
Mercaptan and H2S in Light Distillates
H2S, Mercaptans, and COS in Hydrocarbon Gases
in Heavy Distillates
Total, in Light Distillates
Total Sulfur Lamp
Quartz Tube
Surface area, Pore Volume, and Pore Diameter of Catalyst
UOP Characterization Factor K
Vacuum Distillation
Viscosity Kinematic
Water and Sediment in Oil
Weathering Test (Boilaway)

Number
UOP 262
UOP 425
D 97
D 323
UOP 516 or D 270
D 4007
UOP 424
UOP 683
D 1552
UOP 41
UOP 9
UOP 163
UOP 212
D 1552
D 1266
D 1266
D 1552
UOP 425
UOP 375
D-1160
D 445
D 4007
UOP 155

157048
Analytical Methods
Page 21

OUTLINE OF SELECTED
ANALYTICAL TEST METHODS NUMERICAL INDEX
Test Number

Description

UOP 1
UOP 6
UOP 9

Distillation Range of Heavy Oils


Induction Period of Gasoline
H2S in Gases (Tutwiler)

UOP 11
UOP 41

Gum, Copper Dish


Doctor Test (H2S and Mercaptans)

UOP 76
UOP 77
UOP 79
D 86
D 92
D 93
D 97
UOP 155
D 156
UOP 163

Vacuum Distillation
Distillation of Petroleum
Distillation of Petroleum
Distillation of Petroleum
Flash Point, Open Cup
Flash Point, Closed Cup
Pour Point of Petroleum Oil
Weathering Test (Boilaway)
Saybolt Color
Mercaptans and H2S in Liquid Hydrocarbons

UOP 172
D 189
UOP 212

Flue Gas Analysis (Orsat)


Conradson Carbon Residue
H2S, Mercaptans and COS in Hydrocarbon Gases

UOP 233
UOP 251
UOP 254
UOP 262
D 270

Catalyst Loading Test


Activity Test for Catalyst
Apparent Bulk Density of Catalyst
Phenols in Petroleum Products
Sampling Petroleum Products

157048
Analytical Methods
Page 22

Test Number

Description

UOP 275
UOP 277
D 287
UOP 314
D 323
UOP 375
UOP 384
UOP 389
UOP 391
UOP 422
UOP 424
UOP 425
D 445
D 482
UOP 516

Loss of Ignition of Catalyst


Existent Gum (Steam Jet)
API Gravity
pH, Iron, and Copper in Refinery Water
Reid Vapor Pressure
UOP Characterization Factor
Nitrogen in Heavy Distillate
Trace Metals in Oils
Trace Metals in Oils
Particle Size Distribution in Catalyst
Sintering Index of Equilibrium Catalyst
Surface Area, Pore Volume, and Pore Diameter of Catalyst
Kinematic Viscosity of Oils
Ash from Petroleum Products
Sampling of Gasoline, Distillates and C3-C4 Fractions

UOP 539
UOP 546
UOP 682
UOP 683
UOP 703
UOP 709
UOP 725
UOP 740
D 1160
D 1266
D 1500
D 1552
D 2699
D 2700
D 3685
D 4007

Gas Analysis (GC)


Metals in Cracking Catalyst
Cyanide in Refinery Water
Sulfide in Refinery Water
Carbon on Catalyst
Gas Analysis (GC)
Pentenes and lighter in olefinic gasoline
Ammonia in Water
Vacuum Distillation
Total Sulfur in Petroleum Products (Lamp)
ASTM Color (formerly ASTM Union)
Sulfur in Heavy Oils
Octane Rating, Research
Octane Rating, Motor
Isokinetic Particle Determination in Flue Gases
Water and Sediment in Oil

157048
Analytical Methods
Page 23

DISTILLATION RANGE OF HEAVY PETROLEUM OILS


UOP METHOD 1

Scope
This method is for determining the distillation range of heavy petroleum oils. It is
applicable to petroleum products whose boiling range extends above that of
kerosene; e.g., crude oils, gas oils and fuel oils. The method differs from ASTM
Method D 86 in that a 200 ml flask is used and the distillation is continued past the
thermal decomposition point to a dry or coke residue. The test is particularly useful
in estimating gasoline, kerosene and/or distillate contents and the coking
characteristics of these oils.
Outline of Method
A 100-ml sample is distilled under prescribed conditions. Systematic observations
of thermometer readings and volumes of condensate are made, and the weight of
coke or residue is determined. The results of the test are calculated and reported
from these data. No corrections are applied to the data.
Precautions
Oils containing more than traces of water are very difficult to distill. However, if the
heat is applied to the flask correctly, water can be distilled from the oil without
bumping. When water is present, heat the flask evenly over its top and bottom
surfaces; do not concentrate heat on the bottom of the flask. Keep the top of the
flask hot enough to prevent water vapor from condensing there and allow time for
the temperature to drop to ambient before continuing the distillation. Do not include
water in the percentages reported for the temperatures named. The IBP obtained in
this manner on samples containing water may, or may not, be a true IBP owing to
the possibility of superheating the vapors when the flame is applied to the top
surface of the flask. Note this on the distillation sheet.

157048
Analytical Methods
Page 24

Decomposition or cracking usually occurs when oils containing material boiling


above 625F (329C) are distilled at atmospheric pressure. When this decomposition takes place it will be impossible to maintain a uniform distillation rate without
causing a gradual drop in temperature. Therefore, disregard the 4-5 ml per minute
rate from the temperature at which cracking begins and continue the distillation at
such a rate that there is a steady rise in temperature.
Precision
See ASTM Method 86 for precision statement.

157048
Analytical Methods
Page 25

INDUCTION PERIOD OF GASOLINES BY THE UOP OXYGEN BOMB


UOP METHOD 6

Scope
This method is for determining the induction period of gasolines. It is useful in
predicting the storage stability, in lieu of the more valuable storage tests and
accelerated gum determination. It is a valuable control test and an excellent
measure of inhibitor effectiveness.
This method does not give the same numerical induction periods as ASTM Method
D 525 because of differences in construction of the bombs and bath. However, the
results are parallel and this method is preferred for its speed and convenience.
Outline of Method
The sample is placed in a bomb at 60-70F (15-20C) and subjected to oxygen at
100 psig. The bomb is heated rapidly to 211.6F (99.7C). The pressure is recorded
continuously until the break point has been passed. The induction period is then
determined from the chart record.
Precautions
The bombs and bottles must be scrupulously clean to obtain reproducible results.
Precision
Repeatability should be considered suspect it results differ from the mean by more
than 5%.

157048
Analytical Methods
Page 26

HYDROGEN SULFIDE IN GASES BY THE TUTWILER METHOD


UOP METHOD 9

Scope
This method is for the determination of hydrogen sulfide in gas mixtures. Mercaptan
sulfur, if present, is determined as hydrogen sulfide. The accuracy of this method is
not sufficient to obtain reliable results below 5 grains of H2S per 100 cu. ft.
Outline of Method
The sample is admitted to a Tutwiler buret, displacing a starch solution. A known
volume of starch solution is retained in the buret and a standard iodine solution is
admitted and measured from the buret until the starch solution assumes a taint
permanent blue color. The concentration of hydrogen sulfide is calculated from the
volume of iodine used and its known normality.
Precautions
It is recommended that gases to be analyzed for hydrogen sulfide content be
sampled directly from the plant stream into the buret. If the sample is to be
transported, it should be done in a dry glass or stainless steel container.
Do not confuse the blue color of the iodine-starch complex with the opalescent
milky appearance resulting from the separation of free sulfur.

157048
Analytical Methods
Page 27

Precision
Duplicate results by the same operator should be considered suspect it they differ
by more than the following amounts, depending on the iodine solution used:
Iodine Solution A:

10 grains*

Iodine Solution B:

20 grains*

Iodine Solution C:

5 grains*

*To convert to weight ppm:


grain/100 SCF 542.1
= ppm (wt)
MW gas

157048
Analytical Methods
Page 28

COPPER DISH GUM CONTENT OF GASOLINE


UOP METHOD 11

Scope
This is a method for determining the weight of the residue obtained when a gasoline
or naphtha is evaporated in a copper dish. Considered in connection with the
induction period, it is an indication of the stability of the gasoline in storage.
Outline of Method
The sample is evaporated in a clean, copper dish under controlled conditions and
the weight of the residue is determined.
Report
Report the average weight of the residue as milligrams of copper dish gum per 100
ml of gasoline.

157048
Analytical Methods
Page 29

DOCTOR TEST FOR PETROLEUM DISTILLATES


UOP METHOD 41

Scope
This is a qualitative test for the presence of hydrogen sulfide and mercaptans in
gasoline, jet fuel, kerosene and similar petroleum products.
Outline of Method
The sample is shaken with a sodium plumbite solution in a test tube. If hydrogen
sulfide is present the following reaction occurs:

Na2PbO2 + H2S

PbS + 2NaOH

The lead sulfide is black and readily visible. If this reaction does not appear, sulfur
is added to the test tube and the mixture shaken again. If mercaptans are present,
on shaking they undergo a series of reactions, coloring the hydrocarbon layer first
orange, then red and brown, and finally a black precipitate of lead sulfide appears.
The overall reactions may be written:

Na2PbO2 + 2RSH
(RS) 2Pb + S

(RS) 2Pb + 2NaOH


RSSR + PbS

157048
Analytical Methods
Page 30

Report
(a)

Hydrogen sulfide present.


If hydrogen sulfide is detected, report it.

(b)

Sample sour.
If a brown or black precipitate forms, the sample contains a relatively high
concentration of mercaptans and is reported sour.

(c)

Sample borderline or sweet.


If the mercaptan content of the sample is low, observe the sulfur layer and
judge as follows:
Discoloration of Floating Sulfur

Report

Definitely discolored
Barely discolored
Not discolored

sour
borderline
sweet

Precaution
Use only sufficient sulfur to form a thin film floating on the interface between the
sample and the doctor solution.

157048
Analytical Methods
Page 31

HIGH VACUUM DISTILLATION OF


HIGH BOILING RANGE PETROLEUM PRODUCTS
UOP METHOD 76

Scope
The distillation apparatus described in this method was devised to provide a means
of determining the boiling range of heavy oils. It is intended for the determination, at
reduced pressures, of the boiling temperature ranges of petroleum products which
have an initial boiling point in excess of 460F (238C) and which decompose when
distilled at atmospheric pressure. The method is applicable to petroleum products
which can be partially or completely vaporized at a maximum liquid temperature of
750F (399C), at a pressure in the range of 0.2-0.3 mm of mercury absolute, and
which may be condensed as liquids at the pressure of the test.
Outline of Method
The sample is distilled at a pressure of 0.2-0.3 mm of mercury absolute under
conditions which provide approximately one theoretical plate fractionation. Data
obtained, converted to 760 mm mercury, allow the preparation of a distillation curve
relating volume distilled and boiling point.

157048
Analytical Methods
Page 32

CRUDE OIL EVALUATION BY HEMPEL DISTILLATION


UOP METHOD 77

Scope
This method is for determining the gasoline, naphtha and kerosene content of a
crude oil as a guide in operating crude oil topping facilities.
Outline of Method
The method employs a Hempel column to secure the desired precision in a manner
which simulates the results obtained from a commercial distillation. Directions are
given to obtain end point gasoline, or naphtha, and kerosene of either specified end
point or API gravity.

157048
Analytical Methods
Page 33

FRACTIONATION OF PETROLEUM DISTILLATES AND CRUDE OILS


UOP METHOD 79

Scope
This method describes laboratory fractionation equipment and procedures used in
obtaining true boiling point data for petroleum distillates and crude oils. Procedures
are also given for obtaining specific boiling range distillates for further analysis.
Outline of Method
A known volume of a petroleum distillate or a crude oil sample is fractionated in a
high efficiency laboratory column. The distillation may consist of: (1) the precision
fractionation of normally liquid hydrocarbons to collect fractions for further
identification: (2) the quantitative separation of normally gaseous hydrocarbons,
such as C3 and/or C4 hydrocarbons from C5 and heavier gasoline or crude oil
fractions, and/or (3) the determination of true boiling point (TBP) distillation curves
at atmospheric and reduced pressures.

157048
Analytical Methods
Page 34

DISTILLATION OF PETROLEUM PRODUCTS


ASTM D 86
Scope
This method covers the distillation of motor gasolines, aviation gasolines, aviation
turbine fuels, special boiling point spirits, naphthas, white spirit, kerosenes, gas oils,
distillate fuel oils, and similar petroleum products. A 100 ml sample is distilled under
prescribed conditions and systematic observations of thermometer readings and
volumes of condensate are made.
Definitions
1.

Initial boiling point (lBP) thermometer reading at instant first drop of


condensate falls from the lower end of the condenser tube.

2.

End point (EP) maximum thermometer reading obtained during the test.

3.

Dry point thermometer reading observed at instant last drop of liquid


evaporates from lowest point in flask. Any drops or film of liquid on side of flask
or on thermometer are disregarded.

Decomposition point thermometer reading that coincides with first


indication of thermal decomposition of the liquid in the flask, as evidenced by
fumes and erratic thermometer readings which usually show a decided
decrease after any attempt to adjust the heat.

5.

Percent recovery maximum percent recovered.

6.

Percent total recovery combined percent recovery and residue in the flask.

7.

Percent loss 100 minus percent total recovery.

8.

Percent residue percent total recovery minus percent recovery.

9.

Percent evaporated sum of percent recovered and percent loss.

157048
Analytical Methods
Page 35

FLASH AND FIRE POINTS BY CLEVELAND OPEN CUP


ASTM D 92

Scope
This method covers determination of the flash and fire points of all petroleum
products except fuel oils and those having an open cup flash below 175F (79C).
Summary of Method
The test cup is filled to a specified level with the sample. The temperature of the
sample is increased rapidly at first and then at a slow constant rate as the flash
point is approached. At specified intervals a small test flame is passed across the
cup. The lowest temperature at which application of the test flame causes the
vapors above the surface of the liquid to ignite is taken as the flash point. To
determine the fire point, the test is continued until the application of the test flame
causes the oil to ignite and burn for at least 5 sec.
Precision
The following data should be used in judging the acceptability of results (95 percent
confidence).
Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:

157048
Analytical Methods
Page 36

Repeatability
Flash point
Fire point

15F (8C)
15F (8C)

The results submitted by each of two laboratories should be considered suspect if


the results differ by more than the following amounts:
Reproducibility
Flash point
Fire point

30F (17C)
25F (14C)

157048
Analytical Methods
Page 37

FLASH POINT BY PENSKY-MARTENS CLOSED TESTER


ASTM D 93

Scope
These methods cover the determination of the flash point by Pensky-Martens
closed-cup tester of fuel oils, lube oils, suspensions of solids, liquids that tend to
form a surface film under test conditions, and other liquids.
Summary of Method
The sample is heated at a slow, constant rate with continual stirring. A small flame
is directed into the cup at regular intervals with simultaneous interruption of stirring.
The flash point is the lowest temperature at which application of the test flame
causes the vapor above the sample to ignite.

157048
Analytical Methods
Page 38

WATER AND SEDIMENT IN CRUDE OILS


ASTM D 4007

Scope
This standard defines a primary centrifuge method and two alternatives for
determining the amount of water and sediment in crude oil. It further specifies a
base method to be used when centrifuging is not suitable or when the accuracy of a
centrifuge method is to be confirmed.
Summary of Method
The three centrifuge methods involve selection of number of factors such as type of
solvent, type and amount of demulsifier, temperature of the sample during testing,
and the duration of centrifuging. With many types of oil, the results are not
dependent on the selected factors. Those factors which are not the most convenient
can be used with good results.

157048
Analytical Methods
Page 39

POUR POINT OF PETROLEUM OILS


ASTM D 97

Scope
The test for pour point is intended for use on any petroleum oil.
Summary of Method
After preliminary heating, the sample is cooled at a specified rate and examined at
intervals of 5F (or 3C) for flow characteristics. The lowest temperature at which
movement of the oil is observed is recorded as the pour point.
Definition
Pour point the lowest temperature, expressed as a multiple of 5F (or 3C) at
which the oil is observed to flow when cooled and examined under prescribed
conditions.
Calculation and Report
Add 5F (or 3C) to the temperature recorded and report the result as the Pour
Point, ASTM D 97.
Precision
Repeatability Duplicate results by the same operator should be considered
suspect if they differ by more than 5F (or 3C).
Reproducibility The results submitted by each of two laboratories should be
considered suspect only if the two results differ by more than 10F (or 6C).

157048
Analytical Methods
Page 40

WEATHERING TEST FOR GASES


UOP METHOD 155

Scope
This is a rapid procedure for the estimation of iso- and normal butane in liquefied
butane samples. Propane does not interfere with the analysis and is determined if
present in concentrations not exceeding 25%. Pentane and olefins will interfere in
the analysis, if present. The test is sufficiently accurate for routine control of plant
operations, the apparatus is inexpensive and the technique involved requires little
experience.
Outline of Method
A 94 ml sample of liquefied butanes is drawn into a precooled centrifuge tube. It is
then weathered in air to the 90 ml mark. The centrifuge tube and contents are then
transferred to a water bath maintained at 60-70F (15-20C). Temperature readings
are recorded when the liquid level has dropped to the 50- and 15-ml graduation
marks of the centrifuge tube. From these temperatures and weathering test curve,
the approximate concentrations of propane, isobutane and normal butane are
determined.

157048
Analytical Methods
Page 41

Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:
Hydrocarbons
Propane
i-butane
n-butane

Maximum Deviation, %
+ 2.5
+ 1.5
+ 1.0

157048
Analytical Methods
Page 42

SAYBOLT COLOR OF PETROLEUM PRODUCTS


(SAYBOLT CHROMOMETER METHOD)
ASTM D 156

Scope
This method covers the determination of the color of refined oils such as undyed
motor and aviation gasoline, jet fuels, naphthas and kerosene. A sample of the
liquid is added to a tubular column through which a light source is seen. The color is
compared with specified glass standards. The height of the liquid sample is
decreased by levels until the color of the sample is lighter than that of the standard.
The color number above this level is reported. The range of number is +30 (lightest)
to -16 (darkest color). Color standards correspond to sample depth and color
number.
Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than 1 color unit.
Results submitted by one laboratory should be considered suspect if they differ
from that of another laboratory by 2 color units.

157048
Analytical Methods
Page 43

HYDROGEN SULFIDE AND MERCAPTAN SULFUR IN LIQUID


HYDROCARBONS BY POTENTIOMETRIC TITRATION
UOP METHOD 163
Scope
This method is for the determination of hydrogen sulfide and mercaptan sulfur in
liquid hydrocarbons, such as gasoline, naphtha, light cycle oils and similar
distillates. It is applicable to samples containing as little as 1.0 ppm mercaptan
sulfur and 1.0 ppm hydrogen sulfide.
Attention is called to the fact that an earlier version of this method (163-62) included
determination of free sulfur. This has been deleted from the present method.
Outline of Method
The liquid hydrocarbon sample is titrated potentiometrically in ammoniacal isopropyl
alcohol using alcoholic silver nitrate as titrant. A glass reference electrode and a
silver-silver sulfide indicating electrode system are used. Estimation of the hydrogen
sulfide and mercaptan sulfur content is made from the titration curves. Either an
automatic recording titrator or a manually-operated instrument may be used.
Free sulfur is a possible interference and instructions are given for analysis of
samples containing it.
Calculations

Hydrogen sulfide, as S, wt -ppm =

Mercap tan, as S, wt - ppm =

3
16 10 A N
SV

32 103 (B - A) N
SV

157048
Analytical Methods
Page 44

where:
A = volume of silver nitrate solution used to reach the sulfide ion end point,
ml
B = volume of silver nitrate solution used to reach the mercaptide ion end
point, ml
N = normality of alcoholic silver nitrate solution
S = specific gravity of sample at the temperature at which the sample is
pipetted
V = volume of sample, ml
Precautions

Allow enough time for the titration cell to reach equilibrium before recording the
volume of silver nitrate solution and the emf when the manual titration is made.
When using a recording titrator, add the titrant at a rate of 3.0 ml per minute in the
vicinity of the end point, otherwise the end point will be overshot.

157048
Analytical Methods
Page 45

VOLATILE NITROGEN BASES AND AMMONIA IN


CATALYSTS, DEPOSITS, AND WATER SOLUTIONS
UOP METHOD 169

Scope

This is a method for the determination of ammonia and steam-volatile nitrogen


bases in catalysts, deposits, and water solutions. The procedure does not
distinguish between ammonia and volatile nitrogen bases. Ammonia in the parts per
million range can be determined with this method by using 0.005 N sulfuric acid and
large samples.
Outline of Method

A known quantity of sample is introduced into a Kjeldahl flask, diluted with distilled
water, and made alkaline with 50% sodium hydroxide. The volatile nitrogen bases
are distilled in a Kjeldahl apparatus and the condensate collected in a boric acid
adsorbing solution. This solution is then titrated with standardized sulfur acid using
methyl purple indicator.

157048
Analytical Methods
Page 46

FLUE GAS ANALYSIS (ORSAT)


UOP METHOD 172

Scope

This method is for the quantitative determination of carbon dioxide, oxygen and
carbon monoxide in flue gases.
Outline of Method

Systematically, the gas sample is admitted into a series of pipets, each containing a
reagent for the removal of an individual component. After contact with each reagent,
the gas is returned to the buret. The difference in residual volume indicates the
amount of component absorbed. In this manner, percentages of carbon dioxide,
oxygen and carbon monoxide are determined.
Precision

Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:
Carbon dioxide

+ 0.2%

Oxygen

+ 0.3%

Carbon monoxide

+ 0.3%

157048
Analytical Methods
Page 47

CONRADSON CARBON RESIDUE OF PETROLEUM PRODUCTS


ASTM D 189
Scope

This method covers the determination of the amount of carbon residue left after
evaporation and pyrolysis of an oil, and is intended to provide some indication of
relative coke-forming propensities. The method is generally applicable to relatively
nonvolatile petroleum products which partially decompose on distillation at
atmospheric pressure. Petroleum products containing ash-forming constituents as
determined by ASTM Method D 482, Test for Ash from Petroleum Products, will
have an erroneously high carbon residue, depending upon the amount of ash
formed.
Summary of Method

A weighed quantity of sample is placed in a crucible and subjected to destructive


distillation. The residue undergoes cracking and coking reactions during a fixed
period of severe heating. At the end of the specified heating period, the test crucible
containing the carbonaceous residue is cooled in a desiccator and weighed. The
residue remaining is calculated as a percentage of the original sample, and
reported as Conradson carbon residue.
Calculation

Calculate the carbon residue of the sample or of the 10 percent distillation residue
as follows:
Carbon residue = (A 100)/W
where:
A = weight of carbon residue, g
W = weight of sample, g

157048
Analytical Methods
Page 48

Report
Report the value obtained as "Conradson carbon residue, percent" or as
"Conradson carbon residue on 10 percent distillation residue, percent," ASTM
D 189.

157048
Analytical Methods
Page 49

HYDROGEN SULFIDE, MERCAPTAN SULFUR


AND CARBONYL SULFIDE IN HYDROCARBON
GASES BY POTENTIOMETRIC TITRATION
UOP METHOD 212

Scope

This method is for determining hydrogen sulfide, mercaptan sulfur and carbonyl
sulfide in gaseous hydrocarbons and in liquefied petroleum gas (LPG) of ordinary
properties. Also covered is the determination of mercaptan in non-ordinary LPG
which may contain a wide range of hydrocarbon types from ethane to such gasoline
boiling range hydrocarbons as pentane and hexane. The hydrogen sulfide
concentration range which can be determined is from 0.3 to several thousand
wt-ppm. The method is also applicable to LPG samples containing as little as 1.0
ppm mercaptan sulfur.
Outline of Method

The sample, taken either from a sample bomb or directly from a refinery stream, is
scrubbed first through a potassium hydroxide solution and then through a
monoethanolamine solution. A potentiometric titration of the absorbed hydrogen
sulfide and mercaptan sulfur follows. The monoethanolamine solution, which
contains the absorbed carbonyl sulfide, is titrated potentiometrically with alcoholic
silver nitrate in an acidic titration solvent. The concentration of each item sought is
estimated from the titration curve.
Precision

Samples containing hydrogen sulfide mercaptan and carbonyl sulfide sulfur:


An estimated standard deviation (esd) is not reported since insufficient data are
available at present to permit this calculation with at least 4 degrees of freedom.

157048
Analytical Methods
Page 50

Samples containing mercaptan sulfur only and appreciable concentrations or


pentane and higher boiling materials:
The estimated standard deviation based on indicated replicates is shown below.
Duplicate results by the same operator should not be considered suspect unless
they differ by more than the amounts shown in the "allowable difference" column
(95% probability).

Type of Sample

LPG containing
appreciable concentrations
of pentane and higher
boiling materials

No. of
Pairs

Mercaptan
Level,
wt-ppm, S

esd,
wt-ppm,
S

6.0

0.28

Allowable
difference,
wt-ppm, S

1.1

157048
Analytical Methods
Page 51

FLUID CRACKING CATALYST LOADING TEST


UOP METHOD 233

Scope

This method is used to determine the proportion of silica-alumina type catalyst in


recycle stock from a fluid catalytic cracking plant.
Outline of Method

In this procedure the oil-catalyst mixture is washed free of oil with cold benzene,
dried and weighed.
Note: Toluene may be substituted for benzene.
Precautions

Do not conduct the analysis near an open flame. It is preferably carried out under a
hood.
Be sure the crucible is dry before placing it in the oven. It is advisable to leave the
oven door ajar for 5-10 minutes immediately after introducing the crucible.
If the catalyst persists in adhering to the Erlenmeyer flask, dry and weigh the flask
and add the increase in weight to the catalyst weight in the crucible.
Precision

Duplicate determinations by the same operator should agree within 5%.

157048
Analytical Methods
Page 52

ACTIVITY TEST FOR FLUID CRACKING CATALYST


UOP METHOD 251

Scope

This method is for evaluating the activity of fluid catalytic cracking catalysts relative
to a reference catalyst by measuring the conversion of a Mid-continent gas oil to
gas and gasoline. The procedure is applicable to both fresh and used catalyst.
Outline of Method

A standard gas oil charge stock is cracked over the test catalyst in a fixed-bed
operation under carefully controlled standard operating conditions. The conversion
to gasoline and gas is measured. The activity, expressed as a percentage, is the
ratio of the liquid hourly space velocity used with the test catalyst to the liquid hourly
space velocity required with a primary reference catalyst to give the same
conversion as that obtained with the test catalyst. The latter value is read from an
experimentally-obtained reference catalyst calibration curve showing conversion as
a function of space velocity.
Notes

1.

Fresh and equilibrium synthetic catalysts are calcined prior to activity testing
for 2 hours at 1112F +25F (600C) in a muffle furnace having a vent in the
door to permit slow circulation of air. The catalyst is loaded in 150-ml tall-form
porcelain crucibles (without covers) filled about one-half full. Fresh catalyst is
first dried at about 400F (204C) for 2 hours to remove moisture and avoid the
spattering of catalyst which otherwise may occur if placed directly in the muffle
furnace at 1112F. Regenerated equilibrium catalysts have substantially all of
the carbonaceous deposit (except embedded carbon) removed in calcining.
For normal carbon deposits of 0.3 to 0.5 wt-% or less, the activity rating is not

157048
Analytical Methods
Page 53

affected by the carbon removal. Abnormal carbon deposits, up to 1 and 1.5 wt%, usually will reduce the weight activity by 1 to 2 numbers.
In calcining fresh or used natural catalysts, the temperature employed is that
used when regenerating the catalyst in commercial practice.

157048
Analytical Methods
Page 54

APPARENT BULK DENSITY OF FLUID CRACKING CATALYST


UOP METHOD 254

Scope

This is a procedure for determining the apparent bulk density (ABD) of loosely
packed fluid cracking catalyst.
Outline of Method

The sample is poured into a weighed, 25 ml cylinder under carefully prescribed


conditions. Excess catalyst is scraped off and the full cylinder is weighed. The
weight of catalyst, in grams, divided by the volume of the container, in milliliters, is
reported as the ABD of the sample.
Definition

Apparent bulk density is defined as weight per unit volume. It is an empirical value
for the particular type of solid particles to which the determination applies; in this
case, fluid (powered) cracking catalyst in a size range of less than 200 m effective
diameter.
Calculations

Calculate the ABD as weight per unit volume.

where:
W = weight of the catalyst, g

157048
Analytical Methods
Page 55

PHENOLS AND THIOPHENOLS IN PETROLEUM


PRODUCTS BY SPECTROPHOTOMETRY
UOP METHOD 262

Scope

This method is intended primarily for the quantitative determination of phenols and
thiophenols in gasoline and in refinery caustics, but it also is applicable to crude
cresylic acids derived from these refinery caustics. "Phenols" consist of a mixture of
phenol, cresols and xylenols. "Thiophenols" denotes the analogous sulfur
compounds.
Outline of Method

Phenols and thiophenols are extracted from the petroleum fraction with 10% sodium
hydroxide solution. The ultraviolet absorption spectrum of the caustic extract is then
recorded. A base-line technique is used to compensate for background absorption
of the sample. Calibration in a similar manner with known solutions and the
application of Beer's Law permits calculation of weight-percent phenols and weightpercent thiophenols.
In the presence of excessive concentrations of mercaptans, only the sum of the
phenols and thiophenols can be determined directly. However, an accurate value
for thiophenols can be obtained from the modified procedure described, involving
adsorption of the sample on silica gel followed by selective elution of the
thiophenols.
The procedure for refinery caustics and crude cresylic acids is identical to that for
petroleum fractions except that the extraction step is omitted.

157048
Analytical Methods
Page 56

Precautions

Use clean glassware and CP reagents.


Shake vigorously in order to obtain quantitative extraction.
Since this method of sample preparation is employed chiefly to avoid the oxidation
of thiophenols during storage, the extraction must immediately follow sampling. An
inert atmosphere and the proper sample container are mandatory.
Do not use carbon dioxide as the inert gas.

157048
Analytical Methods
Page 57

SAMPLING PETROLEUM AND PETROLEUM PRODUCTS


ASTM D 270

Scope

This method covers procedures for obtaining representative samples of stocks or


shipments of crude petroleum and petroleum products, except electrical insulating
oils, and butane, propane, and other petroleum products that are gases at
atmospheric temperature and pressure.
Summary of Method

Samples of petroleum and petroleum products are examined by various methods of


test for the determination of physical and chemical characteristics. It is accordingly
necessary that the samples be truly representative of the petroleum or petroleum
products in question. The precautions required to ensure the representative
character of the samples are numerous and depend upon the type of material being
sampled, the tank, carrier, container or line from which the sample is being
obtained, the type and cleanliness of the sample container, and the sampling
procedure that is to be used. Each procedure is suitable for sampling a number of
specific materials under definite storage, transportation, or container conditions.
The basic principle of each procedure is to obtain a sample or a composite of
several samples in such manner and from such locations in the tank or other
container that the sample or composite will be truly representative of the petroleum
or petroleum product.

157048
Analytical Methods
Page 58

LOSS ON IGNITION OF CATALYST AT 900C


UOP METHOD 275

Scope

This method is for determining the loss on ignition of fresh or used catalyst or
catalyst bases of the various commercial shapes and sizes, when an ignition
temperature of 900C is specified. It is also applicable to other sample types, such
as catalyst fines.
A representative weighted sample is heated at 900C to constant weight and the
loss in weight calculated as percent loss on ignition.
Precision

Duplicate determinations should not differ by more than 0.2% absolute for values
below 3.0%, or more than 0.3% to 10.0%.
Based on 10 pairs at the 2% loss on ignition level, the standard deviation calculated
from the mean range was 0.072%.
Time for Analysis

Elapsed time per test is about 21/4 hours (5.0 hours when fines are being
analyzed).

157048
Analytical Methods
Page 59

EXISTENT GUM IN DIOLEFIN-CONTAINING GASOLINES


AND NAPHTHAS BY THE STEAM JET METHOD
UOP METHOD 277

Scope

Some gasolines and naphthas contain appreciable concentrations of diolefins or


other materials which are sensitive to oxidation. Examples are: (1) pyrolysis
naphtha (ethylene coproduct gasoline), (2) certain catalytically cracked gasolines,
and (3) certain thermally cracked gasolines. This method is used to determine the
existent gum in these types of materials. An inert gas, steam in this case, is used in
the evaporation step in order to prevent gum from forming in the test beaker during
the evaporation. It has been observed that the ASTM air-jet Method D 381, when
used on oxidation-sensitive samples, tends to give falsely high gum values because
of gum formation during the evaporation.
Outline of Method

The steam jet method is similar to ASTM Method D 381 for Existent Gum in Fuels
by Jet Evaporation. The sample in a tarred beaker is placed in a heated metal block
apparatus maintained at 325F (163C) and evaporated to dryness by a jet of steam
which has been superheated to 325F (163C). The residue is weighed and
reported as milligrams of gum per 100 ml of sample.
Precautions

The types of gasolines and naphthas for which this method is intended must be
sampled and handled carefully in order to prevent oxidation. For best results it is
recommended that: (1) the sample containers be purged with inert gas such as
nitrogen, carbon dioxide, or sweet refinery gas prior to taking the samples, (2) any
storage between time of sampling and analysis be in the dark (preferably

157048
Analytical Methods
Page 60

refrigerated storage), (3) the time lapse between sampling and analysis be as short
as possible.
Precision

Duplicate results by the same operator should not be considered suspect unless
they differ by more than approximately 25% of the result.

157048
Analytical Methods
Page 61

API GRAVITY OF CRUDE PETROLEUM AND PETROLEUM PRODUCTS


(HYDROMETER METHOD)
ASTM D-287

Scope

Using a glass hydrometer the API gravity of crude petroleum and petroleum
products which have Reid Vapor Pressures under 26 lbs. can be determined.
Gravities are determined at 60F (15C), or converted to 60F, by means of
standard tables. Conversion tables are not applicable to nonhydrocarbons or
essentially pure hydrocarbons such as the aromatics. Of interest: the ID of the
sample cylinder must be at least 25 mm greater than the OD of the hydrometer. The
height of the cylinder shall be such that the sample height is 25 mm more than the
submerged portion of the hydrometer.
Precision

Repeatability Duplicates should not differ by more than 0.2 degrees API.
Reproducibility Results should not differ by more than 0.5 degrees API when done
by different labs.
The above judgments are valid providing API gravities were obtained at a
temperature not differing from 60F by more than 18F (10C).

157048
Analytical Methods
Page 62

ANALYSIS OF REFINERY WATERS FOR pH, IRON, AND COPPER


UOP METHOD 314

Scope

This method is designed for measuring the extent of corrosion caused by refinery
waters. Copper and iron are determined at a level of 0.1 ppm and higher. The
metals may be present as simple dissolved ions, as complex ions with cyanide or
other complexing agents, or as part of the suspended solids that often are present.
Ammonia, hydrogen sulfide, hydrogen cyanide and organic matter do not interfere.
The pH of the water is determined because it usually correlates with the extent of
corrosion.
Outline of Method

The water sample, including any suspended solids, is concentrated in the presence
of sulfuric acid until sulfur trioxide fumes appear and then treated successively with
nitric acid and aqua regia.
Iron is determined colorimetrically. The lower limit of detection is 0.1 ppm iron.
Copper is determined colorimetrically. The lower limit of detection is 0.1 ppm copper
in the water sample.
The pH of the original water sample is determined with a pH meter using a glasscalomel electrode system. Samples drawn for determination of pH at the refinery
should be taken in glass bottles, leaving little or no air space above the liquid, and
should be stoppered immediately with rubber or neoprene. The pH should be
measured as soon thereafter as possible as it is often subject to fairly rapid change
with time. Draw samples to be sent out of the refinery in polyethylene bottles to
avoid breakage.

157048
Analytical Methods
Page 63

Precision

Insufficient data available to calculate an esd with at least 3.7 degrees of freedom.
Time for Analysis

The elapsed time is about 8 hours per sample.

157048
Analytical Methods
Page 64

VAPOR PRESSURE OF PETROLEUM PRODUCTS


(REID METHOD)
ASTM D 323
Scope

This method determines the absolute vapor pressure of volatile crude oil and
volatile nonviscous petroleum products, except LPG. The gasoline chamber of the
testing apparatus is filled with a chilled sample and connected to the air chamber
section which should be at 100F (37.8C). The container is then immersed in a
constant-temperature bath and shaken periodically until equilibrium is reached. A
manometer attached at the end of the cylinder like apparatus is read and corrected
if the air chamber temperature is initially at something other than 100F.
Precision

Repeatability Duplicate results by the same operators should be considered


suspect it they differ by more than the following:
Range

Repeatability

0-5 psi
5-16 psi
16-26 psi

0.1
0.2
0.3

Reproducibility Results by two laboratories should be considered suspect it they


differ by more than the following:
Range

0-5 psi
5-16 psi
16-26 psi

Repeatability

0.35
0.3
0.4

157048
Analytical Methods
Page 65

CALCULATION OF UOP CHARACTERIZATION FACTOR AND


ESTIMATION OF MOLECULAR WEIGHT OF PETROLEUM OILS
UOP METHOD 375

Scope

This method is for determining the UOP Characterization Factor, which is indicative
of the general origin and nature of a petroleum stock. Values of 12.5 or higher
indicate a material predominantly paraffinic in nature. Highly aromatic materials
have characterization factors of 10.0 or less.
This method also may be used to estimate the molecular weight of typical
petroleum fractions. It is not intended for estimating the molecular weight of a pure
hydrocarbon compound.
Outline of Method

This method gives directions for estimating:


1.

The UOP-Characterization Factor from API gravity and Engler distillation,

2.

The UOP Characterization Factor from API gravity and kinematic viscosity at a
temperature of 100, 122 or 210F (37.8, 50 or 98.9C), and

3.

The molecular weight from API gravity and Engler distillation.

Definitions

The UOP Characterization Factor, K, of a hydrocarbon is defined as the cube root


of its absolute boiling point, in degrees Rankine, divided by its specific gravity at
60F.

157048
Analytical Methods
Page 66

Molecular weight, as employed herein, is the average molecular weight of a


petroleum fraction and not that of a single, pure compound.
Cubic average boiling point is the cube of the sum of the products of the volume
fraction multiplied by the cube root of the boiling point of each component
expressed in degrees Rankine.
Mean average boiling point is the arithmetic average of the true molal boiling point
and the cubic average boiling point, expressed in degrees Fahrenheit.
True molal average boiling point is the sum of the products of the mol fraction
multiplied by the boiling point of each component.

157048
Analytical Methods
Page 67

NITROGEN IN PETROLEUM DISTILLATES AND HEAVY OILS


BY ACID EXTRACTION OR DIRECT KJELDAHL PROCEDURE
UOP METHOD 384

Scope

This acid extraction method is specifically intended for the determination of


combined nitrogen in petroleum distillates and heavy oils in concentrations ranging
from 0.2 to 20 ppm. Nonextractable samples, and samples containing nitrogen
concentrations ranging from 20 ppm to several percent, can be handled by a direct
Kjeldahl analysis.
The types of nitrogen compounds which can be determined are those which usually
are determined by a macro-Kjeldahl procedure and include amines, amides,
pyridines, pyroles and quinolines. The method does not apply to organic nitrocompounds nor to those containing a -N = N- linkage.
Precision

Duplicate determinations run in the same laboratory by the same operator on the
same equipment should not differ from the mean by more than the percent relative
in the table below:
Total
Nitrogen, ppm

Percent,
Relative

0.5
5
45
500

20
11
5
2

The estimated standard deviation was calculated to be 0.35 at the 16-ppm level,
based on 5 replicate samples; 1.38 at the 54-ppm level, based on 6 replicates.

157048
Analytical Methods
Page 68

TRACE METALS IN OILS BY WET ASH-SPECTROGRAPHIC METHOD


UOP METHOD 389

Scope

This method is applicable to the determination of iron, nickel, vanadium, lead,


copper, sodium and molybdenum, specifically, in crude petroleum and such
fractions as gas oils, fuel oils and let fuels. Additionally, manganese, chromium,
magnesium, tin, calcium, aluminum and zinc may be determined by this method.
Each of these elements can be determined over the concentration range of 0.02 to
1000 ppm if a 50-g sample of oil is ashed. Higher or lower concentrations can be
determined by ashing appropriately-sized samples.
Outline of Method

Cobalt and potassium are added to the oil sample as internal standards and
spectroscopic buffers. The oil sample is then coked with fuming sulfuric acid, ignited
and ashed at 1000F (538C), treated with aqua regia and the ash dissolved in
dilute hydrochloric acid. A spark spectrum of the solution is obtained by means of a
rotating-disk electrode technique. A microphotometer is used to measure the
densities of selected metal lines. Concentrations are determined from standard
calibration curves.
Precision

The estimated standard deviations (esd) for various concentration levels of the
metals determined by this method are shown below. Duplicate results by the same
operator should not be considered suspect unless they differ by more than the
amounts shown in the "allowable difference" column (95% probability).

157048
Analytical Methods
Page 69

Metal Level,
ppm

No. of
Pairs

esd,
ppm

1
10
50
200

5
5
5
5

0.09
0.59
3.2
13

Allowable
Difference, ppm

0.3
2.2
12
48

157048
Analytical Methods
Page 70

TRACE METALS IN PETROLEUM AND ORGANIC


PRODUCTS BY WET-ASHING; FLAME PHOTOMETER
AND SPECTROPHOTOMETRIC METHODS
UOP METHOD 391

Scope

This method is for determining trace concentrations (parts per million) of vanadium,
nickel, iron, copper and sodium in petroleum products such as crude oils and
residues, and varied organic compounds (including nitroanilines, amines,
chlorobenzenes, phenols and other related materials) produced or used in chemical
manufacturing. Other elements commonly found in these materials do not interfere.
Outline of Method

The sample is wet-ashed with fuming sulfuric acid and the coke is burned off in a
muffle furnace. The inorganic residue remaining is dissolved in acid and diluted to a
given volume. Vanadium, nickel, iron and copper are determined
spectrophotometrically, and sodium is determined by flame photometry, using
aliquots from the acid solution.
Precaution

The sulfuric acid concentration in the standard sodium solutions must be the same
as that in the sample solutions. If a different concentration of sulfuric acid is used for
the sample solution than that specified in this method, the calibration curve must be
prepared with sodium standard solutions containing this same sulfuric acid
concentration.

157048
Analytical Methods
Page 71

Precision

Duplicate determinations by the same operator should not be considered suspect


unless they differ by more than the following amounts:

Allowable
Difference for
Duplicates, ppm

Range, ppm

(Vanadium, Nickel, Iron, Copper)


0 to 2
>2

0.1 ppm of metal


5% of the mean

(Sodium)
0 to 2
>2

0.2 ppm
10% of the mean

Insufficient data are available to calculate a standard deviation for the metals listed.

157048
Analytical Methods
Page 72

PARTICLE SIZE DISTRIBUTION BY MICROMESH SIEVES


UOP METHOD 422

Scope

This method is for the determination of particle sizes of fluid cracking catalysts by
means of calibrated sieves having uniform precise square openings. It may also be
used for determining particle sizes of other powdered materials. The method
provides for the classification of particles in a range of sizes from about 20 to 149
microns.
The method is a modification of Shell Development Company, Method EMS 5Z2/61.
Outline of Method

A representative sample is appropriately humidified and then placed on the top


sieve of a calibrated set of precision sieves. The set is mounted on a specified
shaking apparatus and shaken for 20 minutes. The weight of catalyst retained on
each sieve and in the pan is determined, and the percentage of the sample retained
on each sieve and in the pan is calculated on the basis of the sum of weights of the
recovered fractions.

157048
Analytical Methods
Page 73

SINTERING INDEX OF USED FLUID CRACKING CATALYST


UOP METHOD 424

Scope

This method provides a means of separating and measuring a fraction of used fluid
cracking catalyst having a reduced apparent density resulting from the pores having
been sealed off by localized overheating.
Precision

Duplicate results by the same operator should be considered suspect if they differ
by more than 1% absolute. Duplicate results by different operators should be
considered suspect if they differ by more than 2% absolute.

157048
Analytical Methods
Page 74

SURFACE AREA, PORE VOLUME AND PORE DIAMETER


OF POROUS SUBSTANCES BY NITROGEN ADSORPTION
UOP METHOD 425

Scope

This method is for the determination of surface areas of porous substances by a


two-point system, using the basic Brunauer-Emmett-Teller (B.E.T.) theory of
multilayer adsorption, and pore volumes of the substances, using the capillary
condensation theory. Surface areas greater than 10 m2/g may be determined, as
well as the volume of pores up to a diameter of 600 Angstroms. Pore diameter is
calculated from surface area and pore volume.
Outline of Method

The surface area of a substance is determined by measuring the volume of nitrogen


gas adsorbed at liquid nitrogen temperature and relative pressures of 60/760 and
160/760, and applying the B.E.T. theory.
The pore volume is determined by measuring the amount of gaseous nitrogen
condensed in the pores at liquid nitrogen temperature and a relative pressure of
735/760. It can be shown by use of the Kelvin equation for capillary condensation
and the proper correction for multilayer adsorption that this volume is that required
to fill all pores of diameter less than 600 Angstroms.

157048
Analytical Methods
Page 75

Precision
Surface Area

Duplicate determinations should not differ by more than 8% from the mean.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 500-600
m2/g level was 12.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 100-200
m2/g level was 2.
Pore Volume

Duplicate determinations should not differ by more than 0.04 ml/g.


Based on 4 sets of 5 replicate determinations, the standard deviation in the range of
0.30 to 0.90 m2/g was 0.013.
Pore Diameter

Duplicate determinations should not differ by more than 5% from the mean.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 50-60
Angstrom level was 1.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 90-130
Angstrom level was 3.5.

157048
Analytical Methods
Page 76

Time for Test

The elapsed time for 1 sample is 9 hours.


The elapsed time for 6 samples is 10.5 hours.

157048
Analytical Methods
Page 77

KINEMATIC VISCOSITY OF TRANSPARENT AND OPAQUE LIQUIDS


(AND THE CALCULATION OF DYNAMIC VISCOSITY)
ASTM D 445

Scope

This method covers the determination of the kinematic viscosity of liquid petroleum
products, both transparent and opaque, by measuring the time for a volume of liquid
to flow under gravity through a calibrated glass capillary viscometer. The dynamic
viscosity can be obtained by multiplying the measured kinematic viscosity by the
density of the liquid.
Summary of Method

The time is measured in seconds for a fixed volume of liquid to flow under gravity
through the capillary of a calibrated viscometer under a reproducible driving head
and at a closely controlled temperature. The kinematic viscosity is the product of the
measured flow time and the calibration constant of the viscometer.
Precision

The following precision applies to clean, transparent oils tested between 60 and
212F (15 and 100C).
Repeatability Duplicate results by the same operator, using the same
viscometer, should be considered suspect if their difference is greater than 0.35
percent of their mean.
Reproducibility The results submitted by each of two laboratories should not be
considered suspect unless their difference is greater than 0.7 percent of their mean.
ASH FROM PETROLEUM PRODUCTS

157048
Analytical Methods
Page 78

ASTM D 482

Scope

This method covers the determination of ash from distillate and residual fuels, gas
turbine fuels, crude oils, lubricating oils, waxes, and other petroleum products, in
which any ash-forming materials present are normally considered to be undesirable
impurities or contaminants. The method is limited to petroleum products which are
free from added ash-forming additives, including certain phosphorus compounds.
Summary of Method

The sample contained in a suitable vessel is ignited and allowed to burn until only
ash and carbon remain. The carbonaceous residue is reduced to an ash by heating
in a muffle furnace at 1427F (775C), cooled and weighed.
Report

Report the result to two significant figures as the ash, ASTM D 482, stating the
weight of the sample taken.

157048
Analytical Methods
Page 79

SAMPLING OF GASOLINES, DISTILLATE FUELS


AND C3-C4 FRACTIONS
UOP METHOD 516

Scope

This is an outline of the sampling techniques necessary for obtaining, in a stainless


steel cylinder, an air-free sample of a liquid hydrocarbon. Samples may consist of
liquefied natural gases, high vapor pressure natural gasolines, various liquefied
petroleum gases, air unstable gasolines or other liquid hydrocarbon products which
require rigorous exclusion of air.
Outline of Method

Proper sampling techniques are specified to obtain an uncontaminated, air-free


sample in a suitable container; viz., a double-valved, stainless steel cylinder. The
cylinder is mounted vertically near the sampling point and connected to the plant
sample line by steel tubing or pipe. The connecting lines are flushed with the
sample, which is then allowed to flow upward through the cylinder. Several volumes
of sample are discarded before closing the sample cylinder valves of the cylinder.
Identification and Shipment

Properly identify each sample by attaching a tag to the cylinder giving company
name and location, time and date of sampling, identity of stream sampled, sample
pressure and tests required. Crate the cylinder to protect the valves from being
opened or damaged in shipment. Affix a "Red Label" or other proper shipping label
to the crate.

157048
Analytical Methods
Page 80

Notes and Precautions

Samples taken in containers found leaking either during or after sampling should be
discarded and new samples taken in leak-free cylinders.
Consult the current Interstate Commerce Commission or other appropriate
authorities for regulations for applicable specification for shipment. Consult ASTM
Methods D 270, D 1145 and D 1265, if necessary, for procedures for measurement
and sampling of petroleum and petroleum products.
For liquid samples taken in the above manner it is mandatory to immediately
provide a safe outage in the cylinder to prevent thermal expansion and cylinder
rupture. Follow the recommendations in this method to safely provide that outage.

157048
Analytical Methods
Page 81

GAS ANALYSIS BY GAS CHROMATOGRAPHY


UOP METHOD 539

Scope

This method is for determining the composition of a wide variety of gaseous


hydrocarbon mixtures obtained from refining processes or from natural sources,
including minor concentrations of the composite of C5 olefins and C6+
hydrocarbons. 1-Butene is not resolved from isobutylene and argon is determined
as a composite with oxygen. The lower limit of detection for a single component is
0.1 mol-%.
Outline of Method

All the constituents of a total gas sample cannot be resolved by a single


chromatographic column. Therefore in this procedure, 3 columns are connected in
series with appropriate coupling valves. Each column is used to separate a specific
portion of the total sample. The first column is able to resolve gases in the C3-C5
boiling range. The second column separates the components in the intermediate
boiling range carbon dioxide, ethylene, and ethane while the third resolves the
light gases hydrogen, oxygen + argon (composite), nitrogen, methane, and
carbon monoxide.
Precision

Based on 7 replicate determinations, the estimated standard deviations (esd) in


Table 1 were calculated for the components listed.

157048
Analytical Methods
Page 82

TABLE 1
GAS ANALYSIS BY GAS CHROMATOGRAPHY

LEVEL,
MOL-%

ESD,
MOL-%

ALLOWABLE
DIFFERENCE,
MOL-%

HYDROGEN
NITROGEN
METHANE
CARBON MONOXIDE

10
20
10
10

0.10
0.02
0.03
0.14

0.36
0.07
0.09
0.49

CARBON DIOXIDE
ETHANE
PROPYLENE
n-BUTANE

10
10
10
10

0.03
0.04
0.02
0.03

0.10
0.14
0.05
0.09

3
4

0.03
0.04

0.11
0.14

COMPONENT

ISOPENTANE
C5 OLEFINS/C6 PLUS

157048
Analytical Methods
Page 83

METALS IN CRACKING CATALYST BY EMISSION SPECTROSCOPY


UOP METHOD 546
Scope

This method is designed for the determination of metal impurities in silica-alumina


cracking catalyst containing 0 to 30% alumina and less than 1% Na. Impurities are
determined in the following ranges: Cu and Mo, 0.001 to 1.0%; Ni, V, Mn, Cr, Pb,
Sn, and Ti, 0.005 to 1.0%; Fe and Mg, 0.01 to 2.0%; Zn and Ca, 0.05 to 2.0%; Na,
0.05 to 1.0%.
Outline of Method

Samples of the unknown diluted in graphite are burned to completion using a 6-amp
dc arc. The photographed spectra are then examined to determine the elements
sought.
Iron, nickel, and vanadium concentrations are quantitatively determined by
densitometry, using an internal standard, while the concentrations of the remaining
metals are semi-quantitatively determined by visual comparison with spectra from
known samples.
Precision

Duplicate determinations for Fe, Ni, and V should not differ from the mean by more
than 10% in the 0.01 to 1.0% range.
Based on 10 replicates, the estimated standard deviation (esd) was calculated to
be:
Elemental

Level

esd

Fe
Ni
V

0.6
0.02
0.05

0.047
0.0017
0.0075

157048
Analytical Methods
Page 84

CYANIDE AND THIOCYANATE IN REFINERY WATERS AS CYANIDE


UOP METHOD 682

Scope

This method is for determining cyanide and thiocyanate in refinery water, both of
which are then calculated as weight-ppm cyanide. The lower limit of detection is
about 0.02 wt-ppm in samples containing no sulfur and 0.8 wt-ppm in those
containing 1% sulfide.
Outline of Method

A sample of refinery water is placed in a flask and hydrogen sulfide added. The
sample is then acidified with hydrochloric acid, bromine water is added and the
mixture allowed to stand until clear.
(1)

Reactions of bromine water with sample:

HCN + Br2

KCNS + 4 Br2 + 4 H2O

H2S + 4 Br2 + 4 H2O

CNBr + HBr

KBr + CNBr + H2SO4 + 6 HBr

8 HBr + H2SO4

The excess bromine is destroyed with arsenious acid and a pyridine-benzidine


mixture is added. The sample is then allowed to stand for 10 minutes.

157048
Analytical Methods
Page 85

(2)

Reaction of the pyridine and benzidine with sample:

(a)
+ CNBr
N

Br

CN

(b)
+ 2H 2 NC 6 H 4 -C 6 H 4 -NH
N
CN

Br

NHC 6 H 4 C 6 H 4 -NH

+ (Br)

+ H 2 N-CN

C 6 H 4 -C 6 H 4 NH 2

After standing the sample is diluted to volume. The absorbance is read on a


spectrophotometer at 525 m and calculated as weight-ppm cyanide.

157048
Analytical Methods
Page 86

SULFIDE IN REFINERY WASTE WATER USING CADMIUM CHLORIDE


UOP METHOD 683

Scope

This method is for determining sulfide in refinery waste water. It cannot be used on
caustic solutions. Good precision can be obtained when a titrant volume of 10 ml or
more is used. The estimated standard deviation of 0.013 was obtained on a sample
containing 0.8 wt-% S. However, with titrant volumes of less than 10 ml, the results
may be high by as much as 5% of the value found.
Outline of Method

The sample is pipetted into 100 ml of water containing a small amount of


ammonium hydroxide. It is then titrated potentiometrically with standard cadmium
chloride and the result calculated as weight-percent sulfur. The titration curve may
have 2 "breaks". The possible reactions are as follows:
To the first "break":

Cd++ + (NH4)2S

CdS + 2NH4+

Between the first and second "break":

either (a)

Cd++ + (NH4)2S S4

(b)

Cd++ + (NH4)2S S4

CdS + 4S + 2NH4+
CdS3 + 2NH4+

However, in this method the sulfide is calculated to the second "break" with the
equivalent weight of sulfur being 16.

157048
Analytical Methods
Page 87

Precision

The estimated standard deviation (esd) at the 0.8% sulfur level is shown below.
Duplicate results by the same operator are not considered suspect unless they
differ by more than the amount shown in the "allowable difference" column (95%
probability).

Type of
Sample

Sulfur
Level,
wt-%

No. of
Replicates

esd,
wt-% S

Allowable
Difference,
wt -%

Solution of
(NH4)2S

0.8

11

0.013

0.026

157048
Analytical Methods
Page 88

CARBON ON CATALYST BY "LECO" WR-12


WIDE RANGE CARBON DETERMINATOR
UOP METHOD 703

Scope

This method gives supplementary instructions for the determination of 0.01 to 80.0
wt-% carbon on catalysts.
It is necessary that the analyst be provided with the history of the sample so that the
proper sample preparation can be applied.
Outline of Method

The sample is weighed in a ceramic crucible, mixed with accelerators and burned in
an induction furnace using oxygen carrier gas. The products of combustion pass
through a purifying train consisting of a dust trap, antimony metal for chloride
removal, manganese dioxide for sulfur removal, and a heated catalyst lube for
conversion of carbon monoxide to carbon dioxide and hydrogen to water. The
carbon dioxide is adsorbed on molecular sieves at ambient temperature. After the
adsorption period is ended, the molecular sieve column is rapidly heated to 600F
(316C) and the carbon dioxide eluted and carried through the measuring thermistor
by an auxiliary flow of oxygen. The output of the thermistor bridge is integrated and
read on a digital voltmeter and converted to percent carbon by calculation.

157048
Analytical Methods
Page 89

Precision

The estimated standard deviation (esd) for carbon at different concentrations is


shown below.
For the 95% probability level, duplicate results by the same operator should not be
considered suspect unless they differ by more than the amounts shown in the
"allowable difference" column.

Carbon Level,
%C

Number of
Pairs Used

Number of
Replicates

esd,
%C

Allowable
Difference, % C

0.01-0.6
0.6-2
2-5
20

5
7
7
5

0.005
0.015
0.022
0.334

0.02
0.05
0.07
1.25

157048
Analytical Methods
Page 90

GAS ANALYSIS BY GAS CHROMATOGRAPHY


USING A TWO-INJECTION TECHNIQUE
UOP METHOD 709

Scope

This method is for determining most of the components, including low


concentrations of total C6+ hydrocarbons, normally found in a wide variety of
gaseous hydrocarbon mixtures obtained from refining processes or from natural
sources. Butene-1 is not resolved from isobutylene and argon is determined as a
composite with oxygen. The lower limit of detection for a single component is 0.1
mol-%.
Outline of Method

All the constituents of a total gas sample cannot be resolved by a single


chromatographic column. Therefore, in this procedure, 2 columns are connected in
series with appropriate coupling valves to a thermal conductivity detector. Each
column is used to separate a specific portion of the total sample. The first column is
able to resolve gases in the C2-C5 range. The second column separates the light
gases: H2, O2 + A (composite), N2, CH4 and CO.
Precision

Based on 6 replicate determinations, the estimated standard deviation (esd) in


Table 2 was calculated for the gases listed.
Duplicate results should not differ by more than the allowable difference indicated
(95% probability).

157048
Analytical Methods
Page 91

TABLE 2
GAS ANALYSIS BY GAS CHROMATOGRAPHY
USING A TWO-INJECTION TECHNIQUE

LEVEL,
MOL-%

ESD,
MOL-%

ALLOWABLE
DIFFERENCE,
MOL-%

HYDROGEN

21

0.186

0.68

NITROGEN

0.087

0.32

METHANE

12

0.180

0.66

CARBON MONOXIDE

0.266

0.97

PROPANE

0.077

0.28

PROPYLENE

0.203

0.74

ISOBUTANE

0.158

0.58

n-BUTANE

0.074

0.27

ISOBUTYLENE

0.264

0.96

COMPONENT

157048
Analytical Methods
Page 92

OILY MATERIAL IN REFINERY WATERS


BY INFRARED SPECTROPHOTOMETRY
UOP METHOD 726
Scope

This method is for determining oily material in refinery waters. It is especially


suitable for routine monitoring of effluent streams known to be relatively constant as
to the nature of the oily material present. The method has an advantage over
physical test methods in that volatile hydrocarbons can be determined and are not
lost.
Outline of Method

Oily material is extracted from water with carbon tetrachloride. The infrared
absorbances of the extract are determined at 2860 cm-1 (3.50 m) and 2930 cm-1
(3.42 m), and these are used to calculate the concentration of oily matter.
Definition

Oily material means any substance containing -CH, -CH2-, or -CH3 groups which
show infrared adsorption bands at 2860 cm-1 (3.50 m) and 2930 cm-1 (3.42 m)
and which is extractable from acidified water with carbon tetrachloride.
Sensitivity

The sensitivity of this method is about 1 ppm. The method can be extended to
include oil concentrations of less than 1 ppm by using cells of longer path length (5and 10-cm cells are common), larger samples of the water and smaller volumes of
carbon tetrachloride for the extraction.
Precision and Accuracy

Results are reported to the nearest part per million. Relative esd as reported in the
reference API method is 5%. Duplicate results should be considered suspect if they
differ by more than 20% of the average value.

157048
Analytical Methods
Page 93

DISTILLATION OF PETROLEUM PRODUCTS AT REDUCED PRESSURES


ASTM D 1160

Scope

This method covers the determination, at reduced pressures, of the boiling


temperature ranges of petroleum products which can be partially or completely
vaporized at a maximum liquid temperature of 750F (400C) at pressures down to
1 mm Hg, absolute.
Summary of Method

The sample is distilled, at some predetermined and accurately controlled pressure,


between 1 mm Hg, absolute, and atmospheric, under conditions which provide
approximately one theoretical plate fractionation. Data are obtained from which a
distillation curve relating volume distilled and boiling point at the controlled pressure
can be prepared.
Significance

Some petroleum products decompose when distilled at atmospheric pressure. This


distillation method is for determination of distillation characteristics of such products.
The apparatus and conditions of test provide approximately one theoretical plate
fractionation.
Results by this method are not comparable with those of other ASTM procedures
for the determination of boiling point ranges of petroleum products, such as ASTM
Method D 86 for Distillation of Petroleum Products.

157048
Analytical Methods
Page 94

SULFUR IN PETROLEUM PRODUCTS


(LAMP METHOD)
ASTM D 1266

Scope

This method determines the total sulfur in liquid petroleum products in


concentrations above 0.002 weight percent. The procedure involves burning the
sample in a closed system using a suitable lamp apparatus. An artificial atmosphere
composed of 70% CO, and 30% O2 is used to burn the sample to prevent formation
of nitrogen oxides. The oxides of sulfur are then oxidized to sulfuric acid. Sulfur as
sulfate is determined acidimetrically by titration or gravimetrically by precipitation as
barium sulfate.
Precision

Samples should contain in the range of 0.01% to 0.4% sulfur.


Repeatability Duplicate results by the same operator should not differ by more
than 0.005%.
Reproducibility Results by two laboratories should not differ by more than 0.010 +
0.025 S, where S = the total sulfur content, weight percent, of the sample.

157048
Analytical Methods
Page 95

ASTM COLOR OF PETROLEUM PRODUCTS


(ASTM COLOR SCALE)
ASTM D 1500

Introduction

This method has replaced the former ASTM Method D 155, Test for Color of
Lubricating Oil and Petrolatum by Means of ASTM Union Colorimeter. Method D
155 was withdrawn as an ASTM Tentative on July 1,1960. Method D 1500 is better
than the former Method D 155 in three respects: (1) the glass standards are
specified in fundamental terms; (2) the differences in chromaticity between
successive glass standards are uniform throughout the scale; and (3) the lighter
colored standards more nearly match the color of petroleum products.
Scope

This method covers the visual determination of the color of a wide variety of
petroleum products such as lubricating oils, heating oils, diesel fuel oils, and
petroleum waxes.
Report

Report as the color of the sample, the designation of the glass producing a
matching color, for example: 7.5 ASTM Color.
If the color of the sample is intermediate between those of two standard glasses
record the designation of the darker glass preceded by the letter "L", for example:
"L7.5 ASTM Color". Never report the color as being darker than a given standard
except those darker than 8, for example: ASTM Color.
If the sample has been diluted with kerosene, report the color of the mixture
followed by the abbreviation "Dil," for example: "L7.5 Dil ASTM Color".

157048
Analytical Methods
Page 96

Precision

The results obtained by different operators in the same laboratory should not vary
by more than 0.5 number, and the same variation should apply for determinations
between different laboratories at the 96 percent confidence level.

157048
Analytical Methods
Page 97

SULFUR IN PETROLEUM PRODUCTS


(HIGH-TEMPERATURE METHOD)
ASTM D 1552

Scope

This method covers two procedures for the determination of total sulfur in petroleum
products, including lubricating oils containing additives, and additive concentrates.
The method is applicable to samples boiling above 350F (177C) and containing
not less than 0.06 percent sulfur. Chlorine in concentrations less than 1 percent
does not interfere. Nitrogen when present in excess of 0.1 percent may interfere;
the extent of such interference may be dependent on the type of nitrogen
compound as well as the combustion conditions. The alkali and alkaline earth
metals, as well as zinc, phosphorus, and lead, do not interfere.
Summary of Method

The sample is burned in a stream of oxygen at a sufficiently high temperature to


convert about 97 percent of the sulfur to sulfur dioxide. A standardization factor is
employed to obtain accurate results. The combustion products are passed into an
absorber containing an acid solution of potassium iodide and starch indicator. A
slight blue color is developed in the absorber solution by the addition of standard
potassium iodate solution. As combustion proceeds, bleaching the blue color, more
iodate is added. The amount of standard iodate consumed during the combustion is
a measure of the sulfur content of the sample.
Report

Report the results of the test to the nearest 0.01 percent.

157048
Analytical Methods
Page 98

Precision

The following criteria should be used for judging the acceptability of results (95
percent confidence):
Repeatability Duplicate results by the same operator should be considered
suspect if they differ by more than the following amounts:
Sulfur, weight percent
(Range)

Repeatability

0 to 0.5
0.5 to 1.0
1.0 to 2.0
2.0 to 3.0
3.0 to 4.0
4.0 to 5.0

0.05
0.07
0.10
0.16
0.22
0.24

Reproducibility The result submitted by each of two laboratories should not be


considered suspect unless the two results differ by more than the following
amounts:
Sulfur, weight percent
(Range)

Reproducibility

0 to 0.5
0.5 to 1.0
1.0 to 2.0
2.0 to 3.0
3.0 to 4.0
4.0 to 5.0

0.05
0.11
0.17
0.26
0.40
0.54

157048
Analytical Methods
Page 99

KNOCK CHARACTERISTICS OF MOTOR FUELS


BY THE RESEARCH METHOD
ASTM D 2699
Scope

This method determines the knock characteristics of motor gasolines, intended for
use in spark-ignition engines. A Research octane number (RON) of 100 or lower is
the volume percent of iso-octane in a blend with n-heptane that matches the knock
intensity of the unknown sample. For numbers above 100, a comparison is made to
iso-octane and milliliters of tetraethyllead required to match knock intensity.
Summary of Method

The RON of a gasoline is determined by comparing its knocking tendency with


those for blends of reference fuels of known octane. Knock intensity is measured by
an electronic detonation meter on a testing unit consisting of a single cylinder
engine.
Repeatability

Data for limits on duplicate results by the same operator have not been developed.
Reproducibility

Results by different laboratories should be considered suspect if their difference is


greater than the limits shown below:
Ave. Research
Octane No. Level

Limits

80
85
90
95
100
105

1.2
0.9
0.7
0.6
0.7
1.1

157048
Analytical Methods
Page 100

KNOCK CHARACTERISTICS OF MOTOR FUELS


BY THE MOTOR METHOD
ASTM D 2700

Scope

This method covers the determination of the knock characteristics of motor and
aviation-type gasolines, intended for use in spark-ignition engines, in terms of
ASTM motor octane numbers.
Summary of Method
The ASTM Motor Octane Number of a fuel is determined by comparing its
knocking tendency with those for blends of ASTM reference fuels of known octane
number under standard operating conditions. This is done by varying the
compression ratio to obtain standard knock intensity, as measured by an electronic
detonation meter.
Definitions
ASTM Motor Octane Number of motor and aviation-type gasolines of 100 and
below The volume percent, to the nearest tenth, of iso-octane (equals 100.0) in a
blend with n-heptane (equals 0.0) that matches the knock intensity of the unknown
sample, when compared by this method.
ASTM Motor Octane Number of a motor gasoline above 100 The value, to the
nearest tenth, that corresponds to the equivalent engine rating in terms of milliliters
of tetraethyl lead in iso-octane.

157048
Analytical Methods
Page 101

Precision

Repeatability Data to determine acceptable limits for duplicate results obtained by


the same operator have not been developed.
Reproducibility The difference between two, single, and independent results,
obtained by different operators working in different laboratories on identical test
material would, in the long run, and in the normal and correct operation of the test
method, exceed the following values in only one case in 20 (see table).
Average Motor Octane
Number Level

Limits Octane Number

80
85
90
95
99
100.1
105

1.2
1.1
1.0
1.1
1.5
1.1
1.8

157048
Analytical Methods
Page 102

SAMPLING STACKS FOR PARTICULATE MATTER


ASTM D 3685

Scope

This method covers the sampling and determination of particulate matter in stack
gases.
Significance

The following procedure describes a method of sampling in stacks and flues which
has been standardized within the limits of the many conditions which are
encountered in the normal course of sampling stacks. No one procedure or set of
apparatus will apply to all problems. The recognition of one set of apparatus which
will satisfy a number of commonly encountered conditions will often leave many
other problems unanswered. The objective has been to select apparatus that will
give a reliable answer when applied to a variety of problems.
For compliance with regulations in the United States EPA method #5 is usually
required. Check with local authorities before using any lab method required for
compliance with environmental regulations.

157048
Procedures
Page 1

PROCEDURES
INTRODUCTION
The procedures given in this section are general instructions which may serve as a
guide for each unit. They cannot be specific because of the variations in the design
and construction of each Fluid Catalytic Cracking Unit. These methods should be
used by each refiner to develop a detailed set of operating instructions for his
particular unit.
Although basic procedures will be fairly consistent from unit to unit, the FCC is such
a flexible process that several different strategies exist for operating an FCC unit.
Individual refinery requirements and product markets should be carefully considered
to determine the most economic strategy to employ for the FCC unit. These
procedures will cover the basic operating steps for startup, shutdown and
emergency situations. Specific operating strategies for maximum economic benefit
will be left to the individual refiner.
This section is divided according to topic. These subsections are:
A.
B.
C.
D.
E.
F.
G.

Refractory Dryout -- Initial Startup


Normal Startup
Establish Normal Operating Conditions
Normal Shutdown
Emergency Procedures
Catalyst Handling
Special Operations

Throughout these procedures, references will be made to recirculation catalyst,


combustor and upper regenerator, which implies a high efficiency style combustor
regenerator, catalyst coolers, lift gas and alternate riser termination devices. Not all
units will have these features. Where not applicable to your specific unit, certain
steps in the procedures will not be followed. The basic principles for unit operation
are the same, however, regardless of the specific features of the unit. Refer to
Figures 1 through 3 for diagrams of the unit showing the key streams used in the
following procedures.

157048
Procedures
Page 2

A. REFRACTORY DRYOUT -- INITIAL STARTUP


The startup operations on the FCC Unit require careful coordination and planning.
The reactor-regenerator, main column, and Gas Concentration Unit must all be
inspected to verify proper construction and that the equipment is ready for use.
Utility systems should be commissioned and all catalyst and required chemicals on
site.
All instruments must be calibrated and control valves ready for service. Inspection
and precommissioning work is covered in depth in the UOP FCC Operations
Manual. The startup procedures that follow assume all equipment is ready for use.
The protective refractory lining in the regenerator, riser, and parts of the reactor
must be cured and dried before it is used. Failure to do this properly can result in
premature failure of this important protection. The dryout procedure is time
consuming, but once the refractory has been cured and dried, subsequent startups
will use a shorter procedure.
Minor repair work to the refractory will not necessarily require a full high
temperature dryout, but sufficient time must be allowed for curing and air drying. In
all cases the refractory manufacturer's guidelines should be consulted.
The initial dryout isolates the reactor and regenerator from the main column at the
vapor line blind. The vapor line vent opened upstream of the blind is opened to
allow air flow from the reactor to atmosphere. Any work remaining on the column,
gas compressor and Gas Concentration section can continue while the dryout is in
progress.
After application, the refractory lining contains three types of water: free, absorbed,
and chemically bonded. The curing step at ambient conditions allows time for the
chemical bonding to be completed. The free water must then be removed slowly to
prevent rapid expansion to steam that could damage the refractory. The absorbed
water is removed more slowly during a longer, high temperature step. AlI of the

157048
Procedures
Page 3

refractory must be cured and dried; be sure that air is directed to every part of the
reactor-regenerator system.
The dryout may be summarized as:
1.

Controlled heating of regenerator and reactor with hold steps for water
removal.

2.

Reactor-regenerator assembly field test for 24 hours.

3.

Controlled cooling of regenerator and reactor.

The source of heat for the dryout may be the air blower and direct fired air heater,
as in the following procedure, or it may be supplied with internal local heaters. The
choice may be dictated by the particular vendor preference and/or availability of
suitable equipment.
Procedure
The following procedure is intended to supplement the refractory vendor procedure.
During the dryout, several hold periods are maintained at a constant temperature.
The time period for the hold may vary depending on the type and thickness of the
refractory lining. Where the vendor procedure calls for more conservative steps,
those steps should be followed. Should the following steps be more conservative
than the vendor, further discussion is warranted to confirm that the dryout will be
adequate. In all cases, the procedure of the vendor responsible for the
application/performance of the refractory shall govern.
1.

Refractory Curing Step


a.

The curing procedure shall begin immediately after installation and shall
last a minimum of 24 hours. For the 4" low density gunned lining in the
regenerator, water or membrane curing steps may also be included.

157048
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b.

2.

3.

During the curing procedure, the temperature of the shell and lining shall
be kept above 60F (16C).

Refractory Air Drying


a.

After curing, the refractory lining shall be tested by tapping with a one
pound hammer at one foot intervals over the entire lining surface. Any
voids or dry filled spaces will emit a dull sound and these areas shall be
removed and replaced.

b.

After the 24 hour curing period, the refractory lining shall be air dried for
at least another 24 hours by natural or forced ventilation.

Preparation Steps for Dryout


a.

Isolate the structure with blinds in the feed, torch oil, fuel or gas to the CO
boiler and air heater, steam to the riser and stripper, and reactor vapor
line.

b.

Double block and bleed the riser blast points, flue gas quench nozzles
and all steam purge points.

c.

Remove the blankoffs on the catalyst loading lines and the drain points in
the flue gas system.

d.

Remove the blankoff on the vent nozzle on top of the reactor shell and
install a gate valve. Attach a pipe stack approximately six feet (two
meters) long to the valve for personnel protection.
This valve will only be used if the reactor vapor line vent does not pass
enough hot air to adequately heat up the reactor or if the riser termination
device is highly contained so that there is little or no air flow through the
reactor shell. Open the vapor line vent valve upstream of the vapor line
blind.

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4.

5.

e.

Connect the reactor skin thermocouples to a recorder for temperature


monitoring.

f.

Open air purges to all instrument DA points and slide valve packing
glands.

g.

Commission the steam systems of the flue gas cooler and catalyst cooler,
if present. Steam drum boilout procedures can be combined with the
dryout as long as the dryout procedure governs. The cooler tubes must
have circulating water flow for protection during the dryout.

h.

Close the spent and regenerated catalyst slide valves. Check the blast
and sample connections on the catalyst standpipes and drain any free
water.

i.

Open the snort valve on the main air blower discharge.

j.

Prepare the direct fired air heater for firing. Prepare alternate internal
heaters if they are to be used.

Start the Main Air Blower


a.

Follow the manufacturer's instructions for the air blower startup.

b.

Begin closing the discharge snort valve, forcing air into the regenerator.
As the pressure of the regenerator rises, the power required to drive the
blower increases. Check the air blower's performance curve and keep the
machine out of the surge condition.

Refractory Dryout
a.

Open the blast and sample connections on the catalyst standpipes and
drain any free water.

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b.

Follow the vendor's instructions for dryout or the following instructions, if a


suitable alternate is not available. Values given are approximate and to
be used as guidelines. Good judgment should be used for any situations
which deviate from the described steps.

c.

Raise the temperature in the regenerator at a rate of 50F (30C) per


hour to 250F (120C). Adjust the regenerator pressure to control the air
blower discharge temperature. Hold at this temperature for a minimum of
12 hours. Open the recirculation catalyst slide valve and cooled catalyst
slide valve (if present), to ensure air circulates to all parts of the
regenerator.

d.

As the regenerator is heating up, open the regenerated catalyst slide


valve to circulate air up the riser into the reactor. Vent at the reactor vapor
line vent and reactor shell if required. Raise the reactor temperature at
50F (30C) per hour to 250F (120C). Open the spent catalyst slide
valve to circulate air through the standpipe into the stripper. Air flow
should be primarily through the regenerated catalyst slide valve so that
the insulating refractory in the riser is heated thoroughly.
NOTE:

e.

It is important that the air blower is used only for initial dryout in
the reactor. For later startups, only steam should be used to
heat up the reactor. During operation, coke will form on the
reactor internals and walls. There is a real danger of damaging
oxidation or fire if this material is exposed to air at high
temperature.

For the cold wall regenerated catalyst standpipe, wye section and riser
with 5" high density vibracast refractory lining, the minimum hold period at
250F (120C) is 8 hours. It may be that some of this cold wall lining has
already been installed and dried out in the shop. In that case, the
remaining reactor lining will dictate the hold period required. For the 3/4"
abrasion lining in the upper riser and reactor vessel, the minimum hold
period at 250F (120C) is 4 hours.

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f.

After the 250F (120C) hold period, light the direct fired air heater and
raise the temperature in the regenerator and reactor at 50F (30C) per
hour to 650F (350C) and hold for 12 hours for 4" gunned lining, 8 hours
for 5" vibracast lining, or 4 hours for 3/4" abrasion lining. An operator
should be stationed by the air heater any time it is in service.

g.

When the regenerator temperature reaches 500F (260C), start the


purge steam flows to the torch oil guns and nozzles, and any quench
nozzles, to keep them cool. The spent catalyst standpipe expansion joint
steam purge can also be started at this time.

h.

While the reactor and regenerator are heating up, the equipment should
be checked for expansion problems. Completely inspect the vessels,
standpipes and structure every hour until the regenerator plenum has
reached its maximum, generally ~1200F (650C), and every two hours
thereafter. Check:
(1)

That the equipment is free to expand and is not contacting any


structural members.

(2)

That expansion joint tie rods are loose and not binding.

(3)

That catalyst lines and standpipes are free to move.

(4)

That small piping, especially instrument lines and electrical cables, is


not under strain.

i.

During the 650F (350C) hold period is a convenient time to perform the
first hot bolting step. Systematically hot bolt the entire reactor-regenerator
section.

j.

All slide valves should be hot stroked at all hold temperatures. Position
indicators should be checked with board readings and the valves checked

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Page 8

locally for free movement. Manual and handwheel operation should be


checked and any problems corrected.

6.

k.

Raise the regenerator temperature at 100F (55C) per hour to 1300F


(700C) or the highest temperature permitted by the air heater (may be
1200F (650C)). Raise the reactor temperature at 100F (55C) per hour
to 950F (510C).

l.

Hold the regenerator temperature at 1250F (680C) or the highest


achievable for 12 hours for 4" gunned lining or 8 hours for 5" vibracast
lining.

m.

When the regenerator temperature reaches 1000F (540C), begin hot


bolting the entire reactor-regenerator section again. Check for any
expansion related problems.

High Temperature Field Test of Reactor-Regenerator


At the end of the final refractory dryout hold period, a high temperature test is
conducted on the reactor, regenerator and interconnecting piping under
simulated low pressure operating conditions. The integrity of field welded and
bolted joints under the strains developed by the expansion of lines and vessels
is checked before putting catalyst and oil into the system. This test is only
conducted during the initial start of the unit.
a.

Follow the procedure as described in the UOP Schedule A, Project


Specification 314, Reactor-Regenerator Assembly Field Testing
Procedure. The test can only be conducted after:
(1)

The refractory linings in the regenerator, reactor and associated


piping have been fully cured and dried.

(2)

The direct fired air heater lining has been cured and dried.

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(3)

7.

Any expansion related problems discovered in the dryout have been


resolved.

b.

The reactor should be held at 950F (510C) and the regenerator at


1200-1250F (650-680C) for a 24 hour period before the system
pressure is raised.

c.

Begin closing the reactor vapor line vent valve and flue gas slide valve
and raise the reactor and regenerator pressure to approximately 28 psig
(2 kg/cm2) or to the value specified in the 314 Specification.

d.

Hold the reactor and regenerator at these conditions for a minimum of 30


minutes. Check all flanges and joints in the system for leaks. Check the
entire structure for any expansion related problems.

Cooldown and Inspection


a.

After the high temperature field test is completed, reduce the reactor
regenerator pressure back to the previous level.

b.

Begin reducing the air heater outlet temperature at 100F (55C) per
hour. When the regenerator temperature reaches 500F (260C), stop the
steam purges to the torch oil guns and nozzles.

c.

Shutdown the DFAH when the temperature control becomes erratic due
to low fuel gas flow.

d.

Continue air flow through the vessels until the temperature is within 50F
(30C) of the blower discharge temperature and then shut down the main
air blower.

e.

Open all manways and vents. Use fans or other air moving equipment to
cool the vessel internals to ambient conditions.

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f.

Remove the distributor flange at the bottom of the wye section to allow
inspection of the wye section.

g.

Inspect all refractory linings in the catalyst system, including the reactor,
regenerator, riser, standpipes, cyclones, air heater, flue gas line and
orifice chamber. Lock each slide valve in position to prevent accidental
movement during inspection. Small hairline cracks will be present in the
refractory and do not present a problem. Large cracks greater than 3/8"
(10 mm) that extend all the way to the shell should be repaired.

h.

For the final flange assembly before startup, glue of ceramic blanket to
the refractory retaining collars on all cold wall manways or blind flanges
before they are closed (see UOP standard specification 3-24-2 Figure 4).

B. NORMAL STARTUP
The normal startup of the unit can be divided into the following steps:
1.

Steam out the reactor and main column, and heat up the catalyst section.

2.

Heat up the fractionation section.

3.

Load catalyst to the regenerator and heat catalyst.

4.

Start the wet gas compressor.

5.

Circulate catalyst between the reactor and regenerator.

6.

Start oil to the riser.

7.

Establish normal operating conditions.

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It is assumed that the unit is cold and empty, and that all precommissioning
activities and refractory dryout have been completed. General guidelines are
given in these procedures and each refiner should develop specific startup
procedures for their particular unit. Variations from the steps given here are
acceptable as long as the basic intent is followed and safety matters are not
compromised.
1.

Steam Out Reactor and Main Column


a.

The following procedure starts from the condition that all equipment and
vessels are full of air. Steaming of the reactor and fractionation section is
used to free the unit of oxygen. The following items should be completed
before the steam out is begun:
(1)

The unit must be completely flushed, all vessels and piping closed
up, all orifice plates and instrumentation installed, and all equipment
ready for startup.

(2)

The reactor vapor line blind should be removed at this time (refer to
Figure 4). Some refiners prefer to leave this blind in place until later
in the startup sequence. This is acceptable but it is generally more
convenient to remove the blind now. The procedure following is
designed to use the reactor containing steam as a protection buffer
between the regenerator with air and the main column with
hydrocarbon.

(3)

If the vapor line blind is out, the vapor line vent should be blocked
and blinded.

(4)

Remove the blankoff from the main column high point vent and open
the valve a couple turns.

(5)

Isolate the wet gas compressor at the suction and discharge lines.
Steam should not be allowed to enter the compressor.

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(6)

Line up backup nitrogen to the DG purge gas header and start purge
gas to the reactor instrumentation DG points.

(7)

Make sure the regenerated and spent catalyst slide valves are fully
shut. All slide valves should be operational with hydraulic systems
commissioned.

(8)

Low points from various equipment and piping should be prepared to


drain condensate as the steam out progresses.

b.

Start steam to the base of the riser, to the feed distributors, to the reactor
stripper, and to the spent catalyst standpipe blast point. As the reactor is
purged and heated, steam will flow through the vapor line into the main
column. Continually drain condensate at the riser, reactor, stripper, and
main column low point drains. The spent catalyst standpipe blast point will
have to be used as a drain after the initial steaming is completed.

c.

Start steam into the bottom of the main column and into the sidecut
strippers. Vent at the top of the main column and at the overhead
receiver. Do not run the condenser fans or water to the trim cooler during
this procedure.

d.

Steam through the overhead receiver to the wet gas compressor suction
drum. Vent at the drum and drain condensate from low points. Steam
through the spillback lines and the interstage receiver but make sure the
compressor remains isolated. Connect steam hoses as needed if there is
trouble achieving a good steam plume from vents.

e.

Continually drain condensate from all low points. As the vessels and
piping heat up, less steam will condense and the low points can be
throttled to match the condensate drain rate. Condensate collecting in the
overhead receiver water boot can be pumped out with the sour water
pumps.

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f.

When there is a good steam plume out the top of the main column, main
column receiver, compressor suction drum and interstage receiver for at
least two hours, the system should be free of air and the steamout is
complete.

g.

A quick leak check should be conducted on the system. Throttle all vent
and drain valves to raise the pressure in the system to 10-12 psig (0.7-0.8
kg/cm2). Check all flanges, valve packings, etc. for leaks. It may be that
too much steam is condensed in the main column condenser to permit
building pressure for this leak test.

h.

Check all low points to ensure that all water is drained. Verify that the
spent catalyst standpipe is being drained from the blast and sample
connection.

i.

Start injecting fuel gas at the LCO stripper vapor return line. Raise the
reactor and main column pressure to 10-12 psig (0.7-0.8kg/cm2) before
reducing the steam injection. This will ensure that air is not drawn into the
unit as the steam condenses.

j.

Close all vents and continue draining water from all low points. Never
leave a drain point unattended with fuel gas in the system.
NOTE: Fuel gas injection to the LCO stripper should be enough that the
pressure transmitter on the main column receiver will keep the
overpressure control valve to the flare open a small amount at all
times. This will ensure that any air that might enter the system
will be purged out to the flare. On older units which used air as
the purge gas to the reactor instrument taps, air from the DA
points in the reactor is carried by the steam flows to the main
column and receiver. If this air is not purged out, the
concentration of oxygen can build up in the receiver to a high
level.

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2.

k.

The main column overhead condenser can be put in service to condense


the steam and build a concentration of fuel gas in the overhead receiver.
Fuel gas pressure must be adequate to ensure that a vacuum cannot
develop in any of the vessels. This is done in preparation for starting the
wet gas compressor.

l.

The Gas Concentration Unit should be air-freed by steamout in parallel


with the reactor-regenerator-main column sections. The columns and
absorbers should be pressured with fuel gas at the conclusion of the
steamout. Drain any free water from all low points.

Start the Main Air Blower


a.

Be sure all DA and DG purges and all instrumentation in the reactorregenerator section are in service.

b.

Start the main air blower after the fractionation section is pressured up
with fuel gas. Refer to the manufacturer's instruction manual for the
blower startup procedure.

c.

The differential pressure between the reactor and regenerator should be


maintained at a negative (reactor higher) 1.5 psig (0.1 kg/cm2). This will
ensure that any leakage through the slide valves will put steam into the
regenerator rather than air into the reactor.
NOTE: The steam in the reactor acts as a buffer between the
regenerator containing air and the main column which
contains some fuel gas. As long as the reactor pressure is
maintained as the highest level in the system, no
contamination of air and fuel gas can occur.

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3.

4.

d.

Open the recirculating catalyst slide valve and catalyst cooler slide valve
(if present) to allow heated air to flow up the standpipes to the upper
regenerator.

e.

If the unit is equipped with a power recovery unit, follow the


manufacturer's instructions for starting flue gas to the expander turbine

f.

Begin water circulation through the catalyst cooler tubes (if present) and
flue gas cooler tubes.

Light the Direct Fired Air Heater


a.

When the flow from the main air blower has stabilized, light the direct fired
air heater according to the manufacturer's instructions.

b.

Heat up the regenerator at a maximum rate of 200F (110C) per hour to


a target temperature of 1000F (540C).

c.

Start fluidizing air to the upper regenerator fluffing rings and to the
catalyst cooler fluidizing lances (if present) at minimum flow.

Inventory the Fractionation Section with Oil


a.

As the regenerator is being heated, the fractionation section can be


inventoried with oil to begin circulation and pumparound flows. During this
process the main column overhead should be maintained above 230F
(110C) to minimize steam condensation in the column. Fuel gas flow
should be maintained to the LCO stripper vapor return line so that a small
purge flow is maintained through the overhead receiver overpressure line
to flare.

b.

Since LCO and HCO will be unavailable for flushing oil to the instruments
and the main column bottoms pump flushes (gland seal, wear rings and
throat bushing), the flush header should be commissioned with raw oil or

157048
Procedures
Page 16

a light gas oil from outside the battery limits if the raw oil is very heavy.
When the LCO and HCO products become available, the flush systems
will be changed back to the proper stream.
c.

Start raw oil feed through the startup filling line to the bottom of the main
column. The addition of cold feed into the column will condense some
steam since it passes countercurrent with steam over the disk and donut
trays. Therefore, add raw oil to the column slowly until the column is hot.
Pay special care to removing free water from the low points in all vessels,
exchangers and piping because sudden water vaporization can damage
equipment.

d.

Slowly warm up the main column bottoms steam generators by backing in


steam through the bypass around the non-return valves. These steam
generators will be used to heat the raw oil in the main column.

e.

Start the main column bottoms pump and send oil through one of the
steam generators. This circulation must be done slowly at first to avoid
cooling the bottom of the main column. Raise the raw oil outlet
temperature as high as possible, then start flow through the second
steam generator. Try to maintain the column overhead temperature high
enough to drive water overhead.

f.

When the column bottom temperature has stabilized at its highest level
from the steam heating, slowly start bottoms circulation through the other
bottoms circulation loops. Circulate through the cold sections of the
system slowly until they are heated to avoid cooling the column bottom
excessively. Watch the bottoms level and bring in more raw oil as the
total bottoms circuit is inventoried. Start flow from the net bottoms pumps
through the startup line back to the raw oil charge pumps to complete the
loop. Check for water at the low points throughout the bottoms system.
This circulation and heatup will slowly dry out the bottoms system.

157048
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g.

After the bottoms circuit is hot and dry with good circulation flows, check
for free water in the LCO and HCO system low points. Check that the
sidecut strippers inlet level control valves are fully closed. Start a small
flow of hot raw oil from the main column bottoms up to the LCO circuit
return line via the startup filling line. This will put hot oil into the upper part
of the column. When the LCO draw tray is full, it will overflow to inventory
to HCO section and then overflow back to the bottom of the column. Add
raw oil as necessary to maintain the bottoms level as the LCO and HCO
sections are inventoried. Keep the bottoms temperature as hot as
possible with the steam generators.

h.

Drain all free water in the LCO and HCO circuits and slowly start oil flow
through the heat exchange circuits in the Gas Concentration Unit,
bypassing the exchangers. Check that the main column overhead
temperature is high enough to avoid steam condensation in the column.
Do not place the sidecut strippers into operation at this time.

i.

Circulate oil flow through the LCO and HCO circuits until the lines are hot
and all free water has been removed. Maintain a small flow from the hot
bottoms circuit up to the LCO section to keep these sections hot and
overflow the draw trays back to the bottoms.

j.

Inventory the main column receiver with startup naphtha. Don't start reflux
at this time as it will cool off the top of the column and cause additional
steam condensation.

k.

This method of starting oil circulation tries to minimize water accumulation


in the fractionation section. It is very important to avoid circulating free
water back to hot sections of the column as the rapid water vaporization
could cause damage to the trays. All changes in operation and flows
should be made slowly and only after first draining any free water from
low points. Spare pumps should be drained and switched occasionally to
prevent water accumulation.

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5.

Prepare the Regenerator for Catalyst Inventory


a.

The heating of the main column and the regenerator can be taking place
at the same time. The regenerator is being heated with the direct fired air
heater and steam is flowing through the reactor. Completely inspect the
reactor-regenerator structure every hour until the maximum air heater
outlet has been reached, around 1200F (650C), and once every two
hours thereafter. Check:
(1)

That the equipment is free to expand and is not contacting any


structural members.

(2)

That expansion joint tie rods are loose and not binding.

(3)

That catalyst lines and standpipes are free to move.

(4)

That small piping, especially instrument lines and electrical cables, is


not under strain.

b.

When the regenerator temperatures reach 500F (260C), start purge


steam to the torch oil guns and nozzles, and any quench nozzles in the
upper regenerator. Commission the flue gas steam generator before the
temperature exceeds 500F (260C). Change air purges to packing
glands and expansion joints over to steam at 500F (260C).

c.

As soon as the regenerator temperatures are above 450F (230C), the


differential pressure transmitter across the spent catalyst slide valve can
be placed in service. This transmitter should read the same as the
reactor-regenerator differential pressure transmitter as it is measuring the
same two pressures. If it does not, this is an indication that there may be
condensate in the spent catalyst standpipe. The water can either be
drained from the blast and sample point, or preferably, it can be slowly
drained into the regenerator where it will vaporize and exit with the flue
gas. Manually open the spent slide valve a small amount to continually

157048
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drain the standpipe so that water does not accumulate. The desired
situation is that all of the condensate is kept drained, and if drained into
the regenerator, it is done slowly so that when the water vaporizes, it will
not cause a large pressure surge in the regenerator which could push air
into the reactor.
d.

When the air heater temperature reaches 600F (315C), start hot bolting
flanges and manways and systematically hot bolt the entire regenerator
and flue gas system. Repeat this procedure when the air heater
temperature exceeds 1000F (540C).

e.

When the temperature in regenerator has reached 1000F (540C),


catalyst can be loaded. A certain temperature is not required to load
catalyst, but since the catalyst is cold and must be heated, it is best to
have the regenerator already hot when loading is started. The main air
blower should be set at the design rate or at the maximum firing limit of
the air heater and the air heater should be adjusted to the maximum
outlet temperature, typcially around 1200 1350 F (650 - 730C). Since
heating the catalyst inventory is very time consuming, a high rate of hot
air flow is needed to help minimize this period. Close the recirculating
catalyst slide valve and the catalyst cooler slide valve (if present) before
loading catalyst.

f.

Check that all instrument purges have been started and contain the
proper RO throughout the reactor-regenerator section. Check that all
regenerator level and density transmitters are functioning. Ensure that air
flow is going to the upper regenerator fluffing rings and catalyst cooler air
lances (if present).

g.

Note that as catalyst is loaded into a high efficiency, combustor style


regenerator and the combustor density increases, the pressure in the
bottom of the combustor will increase. This will reduce the spent catalyst
slide valve P and it may be possible for air to flow back into the reactor.
If this P approaches zero reduce the regenerator pressure (with the

157048
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Page 20

reactor-regenerator PDIC) to ensure the spent catalyst slide valve P


remains positive.
6.

Loading Catalyst to the Regenerator


The initial load of catalyst into the regenerator should ideally be enough to
provide the total unit inventory. However, due to the size of the reactor and
stripper, this is usually not the case. The regenerator should be loaded with as
much catalyst as possible to high levels, then after catalyst circulation is
started and the reactor inventoried, additional catalyst will need to be loaded
into the regenerator.

The cyclone inlet velocities in the regenerator should be maintained greater than 35
ft/sec (11 m/sec) as much as possible to ensure good catalyst separation efficiency.
Lower pressure during heatup and catalyst loading can help increase the velocity
when the regenerator is cool. For bubbling bed and RFCC regenerators the
superficial bed velocity should not exceed 3 ft/sec (0.9 m/sec) during startup to
minimize catalyst loading to the cyclones.
a.

Ensure that the following items have been accomplished before loading
catalyst into the regenerator:
(1)

All slide valve P transmitters should be in service and the low P


override controller operable.

(2)

Check that all instrument purges, slide valve packing purges, and
expansion joint purges are commissioned.

(3)

Check that steam is not being used in the regenerated catalyst


standpipe, as any condensate will make mud when the catalyst is
loaded. Check the blast and sample point to make sure no
condensate is present.

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(4)

Make sure the catalyst cooler, regenerated catalyst and spent


catalyst slide valves are fully closed.

(5)

Ensure that fluffing air is on to the upper regenerator rings and to the
catalyst cooler (if present). Water must be circulating through the
cooler tubes to keep them cool.

(6)

Raise the feed atomizing steam to 150% of design rates to ensure


that any catalyst passing through to the riser can not plug the
distributors.

b.

Prepare the catalyst hoppers for transferring catalyst. Refer to the specific
procedures outlined in the Catalyst Handling section. Gauge the hoppers
before starting to establish the initial catalyst inventory.

c.

Start catalyst loading to the upper regenerator. Observe the level


instruments for signs that catalyst is accumulating. For a high efficiency
regenerator, open the recirculation slide valve a small amount to begin
circulation of catalyst to the combustor when a level is established and a
differential pressure appears across the recirculation slide valve. The
regenerator will begin to cool as cold catalyst is added. Keep the air
heater firing at its maximum temperature to help heat the catalyst.

d.

For a high efficiency style regenerator, open the recirculation slide valve
further to increase the density in the combustor as the level increases in
the upper regenerator. The combustor density will remain low even with
the recirculation valve full open since there is no catalyst circulating
through the spent standpipe yet. If possible, try to establish a combustor
density of 4-7 lb/ft3 (65-110 kg/m3).

e.

Near the end of the catalyst loading step, when a high level exists in the
regenerator and the combustor density is as high as possible with the
recirculation slide valve open, it is advisable to reduce the main air blower
rate to around 50% of design. This will cause the combustor density to

157048
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Page 22

increase, thereby increasing the combustor catalyst inventory. The upper


regenerator level will drop, which allows additional catalyst to be loaded,
increasing the total catalyst inventory. Adjust the air heater firing when the
air rate is reduced so the maximum temperature is not exceeded.
f.

7.

At the completion of the catalyst loading step, gauge the hopper again to
determine the quantity of catalyst loaded.

Heat Up the Catalyst Inventory


a.

As the cold catalyst is being loaded, it will cool the regenerator. Keep the
air heater firing at its maximum temperature to heat the catalyst. The rate
of heating the catalyst is not critical; the size of the catalyst inventory, the
speed of catalyst loading and the duty of the air heater will affect how fast
the temperature can be raised. A rate of 200-300F (110-170C) per hour
is a good target.

b.

For a high efficiency regenerator, adjust the catalyst recirculation rate to


obtain a density of at least 4-7 lb/ft3 (65-110 kg/m3) in the combustor
during the heatup. Torch oil should not be fired if the combustor density is
less than 4 lb/ft3 (65 kg/m3). Excessive particle temperatures or
afterburning can result if sufficient catalyst is not available to absorb the
heat from torch oil firing.
For a bubbling bed regenerator or 2 stage, RFCC regenerator the catalyst
level should be a minimum of 1 ft (0.3 m) over the torch oil guns before
starting torch oil.

c.

If torch oil is to be used to heat up the catalyst, the minimum temperature


at which it should be fired is 800-850F (425-450C). If an increase in the
combustor temperature is observed, the torch oil has ignited. If no
temperature change is observed, the torch oil has not ignited, and its use
should be discontinued until the catalyst temperature has been raised a
further 50F (30C). When using torch oil, adjust the torch oil atomizing

157048
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steam pressure to a minimum of 50 psig (3.5 kg/cm2). Control the


amount of torch oil to give a smooth even rise in temperature.

8.

d.

If a catalyst cooler is present on the regenerator, heating the catalyst will


take additional time, as the cooler will be taking some heat out as the
entire system is being heated. This is because water is circulating through
the tubes and the fluffing air is on. Water circulation is required to protect
the tubes and some air flow is recommended to keep the air lances clear
of catalyst. The minimum amount of fluffing air should be used throughout
the startup to minimize this heat removal effect.

e.

When the regenerator circulating catalyst inventory has been heated to


900F (480C), catalyst circulation to the reactor can be started. Continue
heating the regenerator catalyst to a target value around 1250F (675C)
in preparation for cutting in feed.

Start the Gas Concentration Unit Wet Gas Compressor


In order to control catalyst circulation between the reactor and regenerator, it is
necessary to have a constant pressure on the main column. Starting the wet
gas compressor at this time allows a better control over the pressure and
removes this task from the very busy time when feed is cut in. However, it may
not be possible to start the compressor now if fuel gas supply is insufficient or
molecular weight is too low. In that case, pressure control is maintained as
before, with a fuel gas purge to the LCO stripper and venting to flare at the
overpressure control valve. The wet gas compressor can be started after feed
is started to the riser.
a.

It is advisable to start the wet gas compressor early and have it operating
smoothly before circulating catalyst. Set the process controls in
preparation for compressor startup as follows:
(1)

Set the main column overpressure control to hold the system


pressure at 10 psig (0.7 kg/cm2).

157048
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9.

(2)

Manually open both compressor spillback control valves and their


bypasses.

(3)

Set the compressor speed control on manual at minimum speed or


open the suction valve fully.

b.

Start the compressor interstage cooler fans and open the cooling water to
the trim cooler.

c.

Increase the fuel gas makeup to the LCO stripper to provide an operating
cushion before starting the compressor.

d.

Start the compressor auxiliaries and the compressor according to the


manufacturer's instructions.

e.

Keep the compressor operating on total spillback until feed is charged to


the reactor. The discharge valve can be cracked open slowly to help
pressure up the gas concentration unit at this time but be careful to do
this very slowly so that the main column pressure is not sucked down
quickly.

Start Catalyst Circulation


The following procedure is general in nature and the specific arrangement of
the reactor and regenerator system needs to be carefully considered. The
velocity in the lift zone, upper riser and cyclones needs to be considered at all
times to ensure smooth catalyst circulation and to minimize catalyst losses.
For all types of riser terminations the velocity throughout the riser should
always be greater than 10 ft/sec (3 m/sec) when circulating catalyst. 15 ft/sec
(4.5 m/sec) is preferred. This will ensure smooth catalyst flow. When heating
up or circulating with steam only the heat demand and therefore the catalyst
circulation and cyclone loading is very low so that the cyclone efficiency is not
critical.

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Once startup naphtha (if used) or feed is introduced to the unit the additional
heat required to vaporize the hydrocarbon increases the catalyst circulation
and therefore the cyclone loading quickly. Before starting these streams the
catalyst separation efficiency of the riser termination device and cyclones must
be increased to minimize losses to the main column.
For a direct connect, SCSS, VSS or VDS riser termination systems the cyclone
inlet velocity should be increased to 35 ft/sec (11 m/sec) or greater with the
startup steam to the wye before starting raw oil or startup naphtha to the riser.
Note that this velocity includes the stripping steam vapor flow. This is very
important for direct connect or SCSS systems. The vortex chamber on VSS
and VDS riser termination systems is less sensitive to changes in velocity than
other types of termination devices so that this is not as critical but it is still
recommended.
For vented risers the velocity out of the riser is critical for catalyst separation.
Catalyst should not be circulated with startup naphtha or feed with less than 35
ft/sec (11 m/sec) riser exit velocity. This velocity does not include the stripping
steam vapor flow.
a.

When the regenerator has reached 900F (480C), the unit is ready to
start catalyst circulation. Temporarily stop the flow of oil from the MCB
circulation up to the LCO and HCO sections of the main column.
Shutdown the HCO and LCO circulation pumps if the inventory in these
sections is lost. When catalyst circulation is first started, it is possible that
catalyst can be carried into the main column. It is best to contain these
fines in the bottoms rather than having them spread through the LCO and
HCO circuits.

b.

Check the spent catalyst standpipe for any condensate. Crack open the
spent slide valve occasionally to drain condensate into the regenerator.
The P controller for the reactor and regenerator should be set at a
negative (reactor higher) 1.5 psig (0.1 kg/cm2) or more if required to keep
the spent catalyst slide valve P positive to provide a steam buffer

157048
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(reactor) between the air in the regenerator and hydrocarbon in the main
column.
c.

Set the lift and/or startup steam to the wye to maintain a velocity of 15
ft/sec (4.5 m/sec) throughout the riser. If sufficient fuel or natural gas is
available, lift gas flow can be started to help reduce the steam
requirement. This flow can come from the normal lift gas source (sponge
absorber) as recycle if the wet gas compressor is operating, or can be
piped in externally and vented at the main column overhead receiver if
the compressor is not operating.

d.

Feed steam to the Optimix feed distributors should be set at 150% of


design to ensure that catalyst can not plug the nozzles.

e.

Adjust the stripping steam and fluffing steam flows to design rates.

f.

Check the P across the regenerated catalyst slide valve and blast the
standpipe with air if there is low or no P. Slide valve differential
pressures will be erratic at low catalyst circulation rates.

g.

Start opening the regenerated catalyst slide valve with the reactor
temperature controller in manual. Closely watch the reactor temperature
which will rise as soon as catalyst begins to circulate. If no response is
observed after several minutes, blast the regenerated catalyst standpipe
again.

h.

The catalyst circulation from the reactor back to the regenerator should
be started as soon as possible to minimize any potential mud formation
(catalyst + condensate) in the spent catalyst standpipe. Do not wait until
the reactor level is fully established to start catalyst flow to the
regenerator. As soon as catalyst creates an increasing P across the
spent slide valve, open the valve on manual to start returning catalyst to
the regenerator. If the P does not increase across the valve, blast the
standpipe with steam.

157048
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i.

The reactor level should be increased without delay, particularly if the


cyclone diplegs are to be submerged in the catalyst bed. It is possible that
some catalyst can be lost to the main column before the diplegs are
submerged, but if the stripper level is raised smoothly and quickly,
catalyst losses will be minimized. It is important that a good flow of
catalyst is leaving the stripper back to the regenerator during this period.
On units without submerged diplegs the level may be increased more
slowly.
j.

As the reactor stripper level is increased, it may be necessary to bring in


more catalyst from storage to maintain levels in the regenerator. On units
with submerged diplegs this should be done before the stripper level
approaches the bottom of the diplegs. The catalyst level should never be
held just below the diplegs for any reason as it is possible to create a
vacuuming action through the cyclones if the seal is lost and draw
catalyst up the diplegs and out to the main column. Once the catalyst
level approaches the diplegs, they should be submerged as quickly as
possible.

k.

Place the reactor level controller on automatic as soon as possible. The


reactor temperature controller should be maintained in manual.

10. Raise Reactor Temperature


a.

As catalyst circulation is started, raise the reactor temperature smoothly


at a rate of 200-300F (110-170C) per hour. For certain reactor
configurations, it may be important how fast the skin temperatures are
increased. In some cases, special guidelines will be specified. It is useful
to record the reactor skin temperatures during the heatup for future
reference and analysis of developed stresses during the thermal
expansion.

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b.

When the reactor temperature has reached 600F (315C), startup


naphtha flow can be started to the riser. Startup naphtha may be used to
increase the catalyst flow and open the slide valves further for better
control. It smoothes the transition when feed is cut into the riser. It also
aids in wetting the main column trays with hydrocarbon and helps
displace water in the main column. Startup naphtha is an optional step in
the procedure. Any type of light naphtha, straight run or cracked, can be
used.
Increase the startup steam to achieve a cyclone inlet velocity of 35 ft/sec
(riser outlet velocity for vented riser terminations) before starting naphtha
flow to ensure that the separation efficiency is good as the catalyst
circulation rate and cyclone loading will increase significantly with the
heat required to vaporize the naphtha. As the naphtha is vaporized and
the cyclone (or riser outlet) velocity increases the startup steam may be
reduced.
Add additional naphtha to the main column overhead receiver as needed.
This naphtha will be recycled through the main column, to the overhead
receiver, back to the riser. Keep raising the reactor temperature at the
specified rate when naphtha is added.

c.

It is important that the bottom of the main column be maintained as hot as


possible during the reactor heatup to prepare for eventual cracked
product flows. The steam generators should be used to heat the bottoms
and maintain at least 350F (175C) in the bottom of the column. A high
temperature will ensure that all water and much of the naphtha is driven
overhead to minimize the accumulation in the column.

d.

Continue to heat up the regenerator catalyst inventory to 1250F (675C)


as the reactor temperature is increased. Torch oil can be used to maintain
this temperature while the reactor is being prepared for starting feed.
Make sure the combustor density is maintained above 4 lb/ft3 (65 kg/m3)

157048
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when torch oil is fired (or the level is maintained above the torch oil guns
in a bubbling bed or RFCC regenerator).
e.

At some point after stable catalyst circulation has been established, and
both spent and regenerated catalyst slide valves have good P across
them, the reactor-regenerator P controller can be adjusted to a positive
value (regenerator pressure higher) to help balance the two slide valve
P's. Make sure the slide valve low P override controllers are
commissioned.

f.

Increase the reactor temperature to a target point around 980F (525C)


and the regenerator temperature to ~1250 1300 F (675 - 705C).
Maintain stable catalyst flow and levels before starting feed to the riser.

11. Charge Oil to the Reactor Riser


Feed can be started to the riser as soon as the preceding operations have
been stabilized.
a.

Stop backing steam into the main column steam generators and fill them
with boiler feed water to prepare for eventual heat removal/steam
production. This should be done slowly to avoid excessive thermal shock
when the tubes are changed from hot steam to cooler BFW.

b.

Set the feed flow through the bypass valve to the main column at
approximately 10% of design charge rate. The flow may be lined up
through the main column bottoms recycle flow meter. The bottoms
recycle meter is convenient to use for starting feed to the riser because
the normal feed control valve is too large to accurately control such small
flows.

c.

Feed steam should be set at 150% of design. Stripping steam and fluffing
steam flows should be at design.

157048
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Page 30

If startup naphtha is in service the cyclone inlet velocity (riser outlet


velocity for vented risers) should already be greater than 35 ft/sec (11
m/sec).
If startup naphtha is not used then the startup steam rate should be
increased to achieve a cyclone inlet velocity (riser outlet velocity for
vented risers) of 35 ft/sec (11 m/sec) or greater.
d.

Prior to starting feed to the riser, be sure to drain all free water from the
feed line between the diverter valve and the feed nozzle block valves.
Start feed to the riser by switching the feed bypass switch to the normal
position. This will close the valve on the line to the main column and open
the line to the riser. Begin opening the regenerated catalyst slide valve
further at the same time to provide the additional heat required to
maintain riser temperature and velocity.
NOTE: Start feed very slowly at first to avoid thermal shock to the feed
distributor tips. The feed distributor tips can be cracked if
subjected to excessive thermal shock.
When cutting in oil, catalyst circulation must be increased to
maintain the reactor temperature. Do not allow the temperature
to drop below 930F (500C). Should the reactor temperature
drop too low, feed can be reduced until the temperature is
increased again. Initially, the regenerator temperature may drop
until catalyst containing coke enters the regenerator. Try to
maintain the combustor temperature around 1250F (675C).

e.

Begin increasing the feed rate smoothly in increments of 10-20% through


the normal feed control valve. As the feed rate is increased, startup
naphtha can be smoothly backed out. The lift steam rate can also be
reduced. It is best to wait until the feed rate is up to 40-50% before
beginning to reduce the startup naphtha and startup and feed steam

157048
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Page 31

rates. The reduction should be done gradually so that riser velocity does
not suddenly drop.
f.

As the circulation of relatively cool catalyst from the reactor to the


regenerator increases the regenerator temperatures will decrease
temporarily until spent catalyst with coke has displaced the clean catalyst
in the stripper. Additional torch oil will be required to keep the regenerator
temperature at 1250 1300 F (675-705 C)
When spent catalyst starts entering the regenerator and the coke starts
burning the regenerator temperatures will increase. Torch oil flow can be
reduced and eventually stopped. The air heater firing can also be reduced
and eventually stopped. The combustor temperature should be
maintained around 1275-1300F (690-705C). The regenerator upper
dense bed temperature should be slightly higher than the combustor.

g.

Continue increasing the feed rate smoothly in 5-10% increments to the


design value. During this time, gradually increase the air rate to the
regenerator as necessary. Adjust the reactor-regenerator P controller as
needed to balance the spent and regenerated catalyst slide valve P's.

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C. ESTABLISH NORMAL OPERATING CONDITIONS


At the completion of the unit startup, stabilize the unit operation using the following
process control guidelines:
Reactor Variables

Control

Raw Oil Charge Rate

As desired.

Raw Oil Preheat Temperature

Set to balance coke yield, conversion, and


gasoline RON requirements.

Lift Steam

Total flow set to achieve optimum lift zone


velocity, typically 10-20 ft/sec (3-6 m/sec).
Flows may be used in any ratio depending on
wet gas compressor, main column overhead
or sour water stripping constraints. Lift gas is
beneficial for metals passivation in units with
high nickel on Ecat (>3000 wppm)

And
Lift Gas

Feed Steam

Typically 1-2 wt% of design feed rate. Should


be adjusted to optimize yields. May be used
at high flow rates during startup and
emergencies.

Reactor Temperature

Adjust to obtain desired conversion, yield


pattern, coke yield and gasoline RON.

Reactor Pressure

Indirectly set
pressure.

Reactor Catalyst Level

Set to cover the top stripping grid or to seal


the diplegs in units with submerged primary
cyclone diplegs.

by

main

column

receiver

157048
Procedures
Page 33

Reactor Variables

Control

Stripping Steam

Use just enough to strip the catalyst of


residual hydrocarbons. Typical rate is 1.7-2.5
lb (kg) per 1000 lb (kg) of catalyst circulation.
Adjust by observing effect of changes on
regenerator temperature.

Main Column Bottoms Recycle

Normally zero. During turndown or when light


feeds are processed, some recycle may be
necessary to increase coke and help the unit
heat balance.

Naphtha to Riser

Used to assist catalyst circulation during


startup and to help control the regenerator
temperature when the unit is behind in
burning (old style unit partial combustion
operation).

HCO Recycle

For units operating in maximum distillate


production, used to increase coke yield or
improve LCO yield.

157048
Procedures
Page 34

Regenerator Variables

Control

Combustion Air Rate

Adjust for sufficient air to burn all coke off


spent catalyst. Maintain 1-2% excess oxygen
in the flue gas for full combustion units.
Typical value for full combustion is 14 lb (kg)
air per lb (kg) coke. The air/coke ratio on
partial combustion units is lower and is
adjusted to control the heat of combustion.

Combustor Temperature

Adjust for proper coke and CO combustion


and minimize afterburning. Typical value
1275F (690C) minimum.

Combustor Density

Adjust to optimize coke and CO combustion.


Normal value between 5-10 lb/ft3 (80-160
kg/m3).

Regenerated Catalyst
Temperature

Function of coke operation. May be


influenced by catalyst cooler if present.
Dense bed normally 20-50F (10-30C)
above combustor temperature. Dilute phase
normally 10-20F (5-10C) above dense.

Reactor-Regenerator
Differential Pressure

Adjust to obtain stable and balanced spent


and regenerated catalyst slide valve P's.

Slide Valve P's

Dependent on reactor-regenerator pressure


and catalyst levels. Normal values between 512 psi (Low pressure over-ride typically set
about 2 psi (0.14 kg/cm2).

157048
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Regenerator Variables

Control

Upper Regenerator Catalyst


Level

Adjusted by additions and withdrawals to


maintain a suitable catalyst surge capacity for
the unit.

Torch Oil Rate

Used during startup to aid in catalyst


inventory heatup. The use of torch oil should
be minimized for the protection of the
catalyst.

Air to Catalyst Cooler

Used to control the catalyst cooler duty and


therefore
the
regenerated
catalyst
temperature. A minimum air rate of 10-20% of
design should be maintained at all times. The
maximum air rate specified for the cooler
should never be exceeded. On flow through
catalyst coolers the air rate can be adjusted
to keep the cooled catalyst slide valve in a
good operating range.

Catalyst Cooler Slide Valve

A secondary control for adjusting heat


removal. Can be used to limit T across
cooler to about 200F (100C).

157048
Procedures
Page 36

Fractionation Section Variables

Control

Main Column Receiver Press

Adjust as required by the reactor-regenerator


P, and the relative main air blower discharge
pressure and wet gas compressor suction
pressure.

Overhead Receiver Temp

Generally maintained around 110-120F (4050C).

Main Column Top Temperature

Set to control the endpoint of the unstabilized


gasoline.

Main Column Reflux Rate

Controlled on cascade by the overhead


temperature controller. Reflux rate is set by
the overhead condenser duty required to heat
balance the column after the duty of the lower
pumparound streams are set. Primary
adjustment is with the MCB steam
generators.
Set to control the draw temperature and
endpoint of the heavy gasoline product.

Heavy Naphtha Product Draw


Rate
LCO Product Draw Rate

Set to control the LCO draw and LCO product


endpoint or to control the MCB temperature.

Cycle Oil Circulation Rates

Set by the process requirements of the


associated heat exchangers.

157048
Procedures
Page 37

Fractionation Section Variables

Control

Main Column Bottoms Circulation Adjust flow to steam generators to balance


Rate
the main column heat removal and set
overhead reflux flow. Minimum total flow back
to column must satisfy disc and donut liquid
rate of 6 gpm per ft2 (15m3 per m2) of column
area..
Main Column Bottoms Temp

Controlled primarily by the LCO product draw


rate. Quench from the steam generators may
be used to subcool the liquid in the bottom of
the column. Maximum bottoms temperature is
generally ~680F (360C) but is dependant on
feed type and reactor severity.

Unstabilized Gasoline Yield

Depends on charge rate and conversion.


Controlled by the level in the overhead
receiver.

Main Column Bottoms Product


Rate

Adjust to control the main column bottoms


level.

Cycle Oil Stripping Steam Rate

Adjust for product flash point specification.

Net Overhead Gas Flow

Depends on charge rate, reactor severity and


catalyst condition. Controlled by the wet gas
compressor speed or spillbacks to control the
main column overhead receiver pressure.

Flush Oil

Adjust as required to keep catalyst out of


instruments, and flush the main column
bottoms pump packing gland and wear rings.

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D. NORMAL SHUTDOWN
The shutdown of the FCC Unit is essentially the reverse of the startup steps. It
should be carried out in an orderly and planned sequence. Some main points to
remember are:
1.

Maintain good catalyst fluidization and circulation through the reactor and
regenerator throughout the shutdown. Increase riser steam to ensure
smooth catalyst circulation.

2.

Always decrease the charge rate before decreasing the air rate. Maintain
excess oxygen in the flue gas at all times and keep the regenerator hot to
ensure the catalyst is fully regenerated.

3.

Make sure all pumparound circuits are flushed out to eliminate problems
with heavy oils or catalyst fines.

During scheduled shutdowns, the catalyst section and the main column exchanger
circuits will usually be inspected and cleaned. Depending on the work to be done,
the main column might have to be water washed for entry. The Gas Concentration
Unit will be pumped out and purged with steam. If columns are to be entered, they
will need to be water washed.
Precautions must be taken to cool the reactor sufficiently before allowing air to enter
the vessel. This is done to guard against the possibility of auto-ignition of hot coke
deposits in the reactor or vapor line. The reactor should be cooled below 350F
(175C) before any manways or nozzles are opened. Riser and stripping steam
should be used to assist cooling the vessel as required.
The following procedure describes a full shutdown for maintenance entry to vessels.
Depending on the reason for the shutdown, the full procedure may not be followed,
and catalyst may or may not be left in the regenerator. In most cases, catalyst will
be transferred from the reactor to the regenerator during a shutdown. These

157048
Procedures
Page 39

procedures should be considered only guidelines. Detailed shutdown instructions


should be prepared by the refiner for his specific unit.
If the shutdown is temporary, the unit may be maintained in an operating mode and
catalyst circulation continued. However, circulating hot catalyst on steam for long
periods of time will damage the catalyst. Therefore, if the shutdown will be for
several days, it is usually best to stop catalyst circulation.
Procedure
1.

Notify offsites and utility systems well in advance that the FCC Unit will be
shutting down. Prepare the regenerator by withdrawing catalyst to drop
the upper regenerator level to a low value. This will make room for the
eventual transfer of the catalyst in the reactor and reduce the time
needed to unload the unit catalyst inventory.

2.

Slowly begin reducing the reactor temperature to 900F (480C). At the


same time, begin reducing the naphtha and LCO product flows. This will
make the main column bottoms material lighter, aiding in flushing out the
bottoms circuits.

3.

The regenerator temperatures will begin to drop when the reactor


changes are made. Adjust the recirculation catalyst and catalyst cooler to
keep the combustor hot, around 1250F (675C), to ensure all coke is
burned off the catalyst.

4.

Maintain the main column bottoms level low around 30%. Control the
level by drawing more or less bottoms product to storage.

5.

Begin decreasing the raw oil charge rate in increments of 5 to 10% to


50% of design. For full combustion units decrease the combustion air rate
as the charge is reduced, but always maintain excess oxygen in the flue
gas (2-5% provides a good safety margin) and good cyclone velocities.
On partial combustion units reduce the air rate to control the heat of

157048
Procedures
Page 40

combustion and move towards full combustion as the regenerator


temperature drops. Control the regenerator temperature at 1250-1300F
(675-705C). Maintain balanced main column heat removal and product
draw temperatures by decreasing pumparound circulations and product
flows as required.
6.

As the raw oil charge rate is reduced, increase the lift steam and the feed
steam to assist catalyst circulation. Begin reducing the reactor pressure to
increase vapor velocity in the riser and the cyclones. Lift gas flow to the
riser may need to be reduced as the gas production is decreased. When
control of the lift gas becomes difficult or unstable, shutdown the flow and
block in the control valve.

7.

As the coke make decreases, the regenerator will cool off. Reduce the
catalyst cooler air rate and begin closing the cooled catalyst slide valve.
The slide valve may be closed completely but do not stop the fluidizing air
until catalyst is removed from the regenerator. Fire the air heater when
needed to hold the combustor temperature at 1225-1250F (665-675C).
Torch oil may be used but should be avoided if possible due to its harmful
effect on the catalyst.

8.

The main column overhead gas production will decrease as the reactor
temperature and charge rate are decreased. Check that the spillback
valves for the wet gas compressor remain in a controlling range. Start fuel
gas flow into the LCO stripper vapor return line if needed to maintain main
column pressure control as the unit is shut down.

9.

Slowly decrease the reactor-regenerator P controller to a negative value


(reactor pressure higher than the regenerator) in preparation for cutting
feed. This is intended to create a higher pressure buffer of steam in the
reactor between the air in the regenerator and hydrocarbon in the main
column.

157048
Procedures
Page 41

10. Prepare to bypass feed from the riser. Make sure the main column has a
low level in the bottom. Keep the regenerator at a lower pressure than the
reactor and put the regenerated catalyst slide valve on manual control.
Increase riser steam to maintain catalyst circulation, bypass raw oil to the
main column, and reduce the flow of oil. Keep raw oil flowing in and out of
the main column until it is verified that any catalyst carried over to the
column during shutdown has been flushed out.
11. With the catalyst circulating on steam, begin dropping the reactor level to
transfer catalyst into the regenerator. Begin withdrawing catalyst from the
regenerator to the hopper to make room for the reactor inventory. Start
decreasing the air heater outlet temperature at 100-200F (50-100C) per
hour. When the regenerator temperatures have dropped below 1000F
(540C) close the regenerated catalyst slide valve and stop circulating
catalyst to the reactor. Maintain steam flow to the riser.
12. When oil is bypassed from the reactor, the gas make will decrease very
rapidly. Shutdown the wet gas compressor according to the
manufacturer's instructions and block it in. Nitrogen purge the compressor
casing.
13. After the wet gas compressor is shut down, block in the pressure
controller on the sponge absorber overhead line. Pressure as much liquid
as possible back to the main column or to the debutanizer from the other
gas concentration columns. After all the liquid is pumped out, depressure
the columns to the fuel gas system. When the fuel gas header pressure is
reached, depressure the remaining gas to flare.
14. As the main column starts to cool, stop the withdrawal of naphtha and
LCO to the sidecut strippers. The naphtha and cycle oils will then
overflow their accumulators, wash down the column, and dilute the
bottoms material. Open the bypass on the net bottoms product to the raw
oil line and start bottoms circulation as during startup. Switch the flushing
header source from LCO/HCO to the raw oil line. When the column and

157048
Procedures
Page 42

bottoms circuit is adequately flushed, pump out all circuits, the sidecut
strippers, and the column bottoms. Shut down the flushing headers.
When the column is empty, depressure it to flare. Pump out the overhead
receiver to the primary absorber column. Steam out the raw oil charge
line, the heat exchange train, and the reactor bypass line to the main
column from the raw oil pump discharge.
15. When all the catalyst has been transferred from the reactor into the
regenerator, close the spent cat