Final Year Project

A Plant Design Project On
Production of 10,000 BPSD High Octane Gasoline

Form Hydro Isomerization of LSR Naphtha
By Penex Once Through Process
Submitted To
Institute of Chemical Engineering & Technology
University of The Punjab Lahore
B.Sc. Chemical Engineering

Batch 2011-2015
Submitted By
Muhammad Arslan E11-CE-37
M Salman Tahir E11-CE-41
M Zubair Zahid E11-PG-12
Zeeshan Pervaiz E11-PG-22
Supervised By
Prof Dr. Rafi-Ullah Khan
1
Dedication
We dedicate our work and utmost efforts to ALLAH Almighty, the creator of this universe
and most merciful and bounteous, You have always been by our side guiding us all the
way to this destiny & Holy Prophet (S.A.W.W.), the cause of the creation of this universe.
A special feeling of gratitude to our loving parents who taught us how to be persevere and
be patient in midst of trials. Our most respected Teachers who built our knowledge
foundations. Our friends who encouraged and strengthened us, our siblings who are our
supporters and well-wishers.
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Acknowledgement
We take immense pleasure in thanking our worthy teachers for their valuable help regarding our
plant design project. We all owe special thanks to our project supervisor Prof. Dr. Rafiullah Khan
and Dr. Muhammad Rashid Usman (Associate Professor) Institute of Chemical
Engineering and Technology, University of the Punjab, Lahore. Their motivation, guidance and
kind words always encouraged us to work with commitment. Whenever we found ourselves in any
sort of trouble, we always found them available to cater the issue. This sort of generosity and favor
is highly commendable.
We are also grateful to our worthy director Prof. Dr. Amir Ijaz, whose moral support, encouraged
us to work dedicatedly and diligently.
We are grateful to our parents for their special prayers that helped us achieve this tedious task
comprising calculations as well as the report writing.
We also express sincere thanks to all the staff of library for their kind and generous help during our
plant design project.
Authors
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Contents
Introduction ............................................................................................................................................. 10
1.1 Naphtha ............................................................................................................................................. 11

1.1.1 Heavy Naphtha .................................................................................................................................. 11
1.1.2 Light Naphtha ................................................................................................................................... 11
1.2 Gasoline ............................................................................................................................................. 12

1.2.1 Octane Number.................................................................................................................................. 13
1.2.2 Blending ............................................................................................................................................. 13
1.2.3 Octane Blending ................................................................................................................................ 13
1.3 Environmental Regulations to Improve Octane Number ................................................................. 14
1.4 Isomerization ..................................................................................................................................... 15

1.4.1 Hydroisomerization History of LSR Naphtha. ................................................................................. 15
1.4.2 Hydroisomerization Processes. ......................................................................................................... 15
1.4.2.1 UOP BenSat Process ................................................................................................................. 16
1.4.2.2 UOP Butamer Process .............................................................................................................. 16
1.4.2.3 UOP Penex Process ................................................................................................................... 16
1.4.3 Reason for Selection of Isomerization .............................................................................................. 17
Process description .................................................................................................................................. 19
2.1 Introduction ....................................................................................................................................... 20
2.2 Feed Stock Requirements .................................................................................................................. 20

2.2.1 Contaminants .................................................................................................................................... 20
2.2.1.1 Sulfur.......................................................................................................................................... 20
2.2.1.2 Water or other oxygenated compounds .................................................................................. 21
2.2.1.3 Nitrogen Compounds ................................................................................................................ 21
2.2.2 Undesirable Hydrocarbons ............................................................................................................... 21
2.2.2.1 Olefins ......................................................................................................................................... 21
2.2.2.2 Cyclic Compounds .................................................................................................................... 21
2.2.2.3 C7 Hydrocarbons ....................................................................................................................... 21
2.3 Process Flow ...................................................................................................................................... 22
2.4 Process chemistry .............................................................................................................................. 22

2.4.1 Hydrocracking ................................................................................................................................... 24
2.4.2 Benzene Saturation ........................................................................................................................... 24
2.4.3 Ring Opening..................................................................................................................................... 24
2.5 Process Variables ............................................................................................................................... 24

2.5.1 Reactor Temperature ......................................................................................................................... 24
4
2.5.2 Liquid Hourly Space Velocity (LSHV) ............................................................................................. 24
2.5.3 Hydrogen to Hydrocarbon mol Ratio (H2/HCBN) ........................................................................... 25
2.5.4 Pressure ............................................................................................................................................. 25
2.5.5 Catalyst Promoter .............................................................................................................................. 25
2.5.6 Hydroisomerization Reactor ............................................................................................................. 25
2.6 Catalysts for Light Naphtha Isomerization ....................................................................................... 26
2.7 Selection of Catalyst........................................................................................................................... 27
Material Balance ..................................................................................................................................... 28
3.1 Introduction ....................................................................................................................................... 29
3.2 Feed Streams...................................................................................................................................... 29

3.2.1 Feed 1: Light straight run naphtha .................................................................................................. 29
3.2.2 Feed 2: Hydrogen gas ....................................................................................................................... 30
3.2.3 Feed 3: Catalyst promoter ................................................................................................................. 30
3.2.4 Feed 4: Caustic alkali (10% NaOH + 90% water) ........................................................................... 31
3.3 Material balance around first reactor ............................................................................................... 32
3.4 Material Balance around Reactor 2 .................................................................................................. 38
3.5 Material balance around Stabilizer column ...................................................................................... 43
Energy Balance ........................................................................................................................................ 45
4.1 Introduction ....................................................................................................................................... 46
4.2 Energy balance around heat exchanger 1 ......................................................................................... 46
4.3 Energy Balance around heat exchanger 2 ......................................................................................... 47
4.4 Energy balance around isomerization reactor 1 ............................................................................... 48
4.5 Energy balance around Isomerization reactor 2 ............................................................................... 52
4.6 Energy balance around Stabilizer column ........................................................................................ 56

4.6.1 Fin fan Cooler ................................................................................................................................... 56
4.6.2 Reboiler .............................................................................................................................................. 56
Design of Process Equipment .................................................................................................................. 58
5.1 Heat exchanger design ....................................................................................................................... 59

5.1.1 Determination of Shell Diameter ...................................................................................................... 59
5.1.1.1 Provisional area ......................................................................................................................... 62
5.1.1.2 Bundle diameter ........................................................................................................................ 62
5.1.2 Determination of tube side heat transfer coefficient ........................................................................ 64
5
5.1.3 Determination of tube side pressure drop ......................................................................................... 64
5.1.4 Shell side heat transfer coefficient .................................................................................................... 66
5.1.4.1 Ideal cross flow coefficient (hoc) ............................................................................................... 66
5.1.4.2 Tube row friction factor (Fn) .................................................................................................... 68
5.1.4.3 Window correction factor (Fw)................................................................................................ 69
5.1.4.4 Bypass correction factor ........................................................................................................... 70
5.1.4.5 Leakage correction factor ........................................................................................................ 71
5.1.5 Pressure drop on shell side................................................................................................................ 72
5.1.5.1 Bypass correction factor for pressure drop ............................................................................ 73
5.1.5.2 Window zone ............................................................................................................................. 74
5.1.5.3 End zone..................................................................................................................................... 74
5.1.5.4 Total shell side pressure drop .................................................................................................. 75
5.2 Pump Design ...................................................................................................................................... 75

5.2.1Pressure drop due to Friction ............................................................................................................ 75
5.2.2 Work done by pump ........................................................................................................................... 77
5.2.3 Power requirement ............................................................................................................................ 77
5.3 Reactor Design ................................................................................................................................... 78
5.4 Mechanical Design of vessel ............................................................................................................... 80

5.4.1 Cylindrical section ............................................................................................................................. 81
5.4.2 Doomed Section ................................................................................................................................. 81
5.5 Distillation Column Design ................................................................................................................ 82

5.5.1 Number of Plates ............................................................................................................................... 82
5.5.2 Minimum reflux ratio ........................................................................................................................ 83
5.5.3 Plate efficiency .................................................................................................................................. 84
5.5.4 Actual number of plates .................................................................................................................... 84
5.5.5 Feed point location ............................................................................................................................ 84
5.5.6 Column diameter ............................................................................................................................... 86
5.5.7 Column height ................................................................................................................................... 89
5.6 Provisional plate design ....................................................................................................................... 89
5.6.1 Check weeping ................................................................................................................................... 90
5.6.2 Plate pressure drop............................................................................................................................ 91
5.6.3 Residence time ................................................................................................................................... 92
5.6.4 Check Entrainment ........................................................................................................................... 92
Process Flow Diagrams ........................................................................................................................... 93
6.1 Introduction ....................................................................................................................................... 94
6.2 Block flow diagram ............................................................................................................................ 94
6.3 Conventions and format .................................................................................................................... 94
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6.4 Process flow diagram ......................................................................................................................... 95
6.4.1 Process topology ................................................................................................................................ 95
6.4.2 Stream information ........................................................................................................................... 96
HAZOP .................................................................................................................................................... 98
7.1 What is HAZOP? ............................................................................................................................... 99

7.1.1 Objectives of HAZOP ........................................................................................................................ 99
7.1.2 How and Why HAZOP is used. ......................................................................................................... 99
7.1.3 Advantages of HAZOP .................................................................................................................... 100
7.1.4 Limitations of HAZOP .................................................................................................................... 100
7.2 Technical Approach to HAZOP ...................................................................................................... 100

7.2.1 Guidewords, Selection of parameters and Deviation ..................................................................... 100
7.3 The System for HAZOP Method. .................................................................................................... 101
7.4 HAZOP Study Procedure ............................................................................................................... 101
7.5 Hazards Identification Related To Naphtha ................................................................................... 101

7.5.1 Emergency Overview ....................................................................................................................... 101
7.5.2 Potential Acute Health Effects. ....................................................................................................... 102
7.5.3 Potential Chronic Health Effects .................................................................................................... 103
7.5.4 Fire-fighting measures .................................................................................................................... 103
7.6 Benzene Toxicological Overview ..................................................................................................... 104

7.6.1 Kinetics and metabolism.................................................................................................................. 104
7.6.2 Sources and route of human exposure ........................................................................................... 104
7.6.3 Health Effects of Acute / Single Exposure ..................................................................................... 104
7.6.5 Health Effects of Chronic / Repeated Exposure ............................................................................ 104
7.7 Recommendations for the Storage of Naphtha ............................................................................... 105
Cost Estimation ..................................................................................................................................... 106
8.1 Why Estimation? ............................................................................................................................. 107
8.2 Cost estimation of equipment .......................................................................................................... 107

8.2.1 Cost of Pump ................................................................................................................................... 107
8.2.2 Cost of Reactor 1 ............................................................................................................................. 108
8.2.3 Cost of Reactor 2 ............................................................................................................................. 108
8.2.4 Cost of Heat exchanger 1 ................................................................................................................ 108
8.2.5 Cost of heat exchanger 2 ................................................................................................................. 109
8.2.6 Cost of Distillation Column............................................................................................................. 109
7
8.3 Fixed Capital Investment................................................................................................................. 112
References.............................................................................................................................................. 116
List of Figures
Figure 1: Process Flow Sheet of Hydroisomerization of LSR Naphtha ............................................. 22
Figure 2: UOP Penex Hydroisomerization Reactor .......................................................................... 25
Figure 3: Material Balance around Steam Mixer ............................................................................. 31
Figure 4: Material balance around Reactor 1 .................................................................................. 32
Figure 5: Material Balance around Reactor 2 .................................................................................. 38
Figure 6: Material balance around Stabilizer Column ..................................................................... 43
Figure 7: Material Balance around Stabilizer Column ..................................................................... 44
Figure 8: Temperature correction factor Ft ..................................................................................... 61
Figure 9: Overall Heat Transfer Co-efficient .................................................................................... 61
Figure 10: Shell to Tube Bundle Clearence ...................................................................................... 63
Figure 11: Tube side Friction factor ................................................................................................. 65
Figure 12: Shell side heat transfer factor against Reynold number ................................................ 67
Figure 13: Tube row correction factor Fn ........................................................................................ 68
Figure 14: Baffle geometrical factors ............................................................................................... 69
Figure 15: Window correction factor ............................................................................................... 70
Figure 16: Coefficient for FL ............................................................................................................. 72
Figure 17: Coefficient for F'L , Pressure drop ................................................................................... 73
Figure 18: frication factor of pipes................................................................................................... 76
Figure 19: PFD of UOP Penex Once through process in Hysys ........................................................ 97
Figure 20: Hazop study flow chart……………………………………………………………………………………………..102
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List of Tables
Table 1: Classification of light and heavy naphtha on basis of initial and final boiling points ........ 12
Table 2: Typical Limits on Stream Impurities ................................................................................... 21
Table 3: Composition of Naphtha in feed ....................................................................................... 30
Table 4: Material Balance around Reactor 1 ................................................................................... 38
Table 5: Material Balance around Reactor 2 ................................................................................... 43
Table 6: Constant Values for dia of bundle determination ............................................................. 63
Table 7: Pipe roughness ................................................................................................................... 76
Table 8: Specification sheet for reactors ......................................................................................... 80
Table 9: Typical design stress for plate ............................................................................................ 81
Table 10: Possible number of plates according to reflux ratio ........................................................ 84
Table 11: Conventions for Process Equipment ................................................................................ 95
Table 12: Indication of utility streams ............................................................................................. 96
Table 13: Stream Information Table ................................................................................................ 96
Table 14: Summary of acute benzene vapor toxicity..................................................................... 104
Table 15: Total Purchased cost ...................................................................................................... 111
Table 16: Fixed capital Investment (Direct Cost) ........................................................................... 112
Table 17: Fixed Capital Investment ( Indirect Cost) ....................................................................... 112
Table 18: Variable Cost .................................................................................................................. 114
Table 19: Fixed Cost ....................................................................................................................... 114
Table 20: Plant Overhead............................................................................................................... 115
Table 21: General Expenses ........................................................................................................... 115
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Chapter 1
Introduction
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1.1 Naphtha
Naphtha is a liquid petroleum product that boils from about 30°C (86°F) to approximately
200°C (392°F), although there are different grades of naphtha within this extensive boiling
range that has different boiling ranges. On a chemical basis, naphtha is difficult to define
precisely because it can contain varying amounts of its constituents (paraffins, naphthenes,
aromatics, and olefins) in different proportions, in addition to the potential isomers of the
paraffins that exist in the naphtha boiling range. Naphtha is also represented as having a
boiling range and carbon number similar to those of gasoline being a precursor to gasoline.
The term petroleum solvent describes special liquid hydrocarbon fractions obtained from
naphtha and used in industrial processes and formulations. These fractions are also referred
to as industrial naphtha. Other solvents include white spirit, which is subdivided into
industrial spirit [distilling between 30°C and 200°C (86°F–392°F)] and white spirit [light
oil with a distillation range of 135°C -200°C (275°F–392°F)]. The special value of naphtha
as a solvent lies in its stability and purity.
There are usually two naphtha cuts produced from most crude distillation. These are light
naphtha and heavy naphtha. Both these streams are the bottom product of the debutanizer
unit. They are separated in a naphtha splitter fractionation tower. The light naphtha
contains most of the crude’s C5’s and much of the paraffin portion of the crude’s C6’s.
The purpose of making such a division is to produce satisfactory heavy naphtha which will
contain the heavier naphthenes and will be a suitable feed for a catalytic reformer.
Naphtha is used in fertilizer plant as fuel in reformer where high temperature is required. It
is also used as fuel in steam generation in the plant where reforming is done with the help
of steam. Some gas turbines for power generation have also been installed recently which
require naphtha as fuel.
1.1.1 Heavy Naphtha
The "heavier" or rather denser types are usually richer in naphthenes and aromatics and
therefore also referred to as N&As. These can also be used in the petrochemical industry
but more often are used as a feedstock for refinery catalytic reformers where they convert
the lower octane naphtha to a higher octane product called reformate. Alternative names
for these types are Straight Run Benzene (SRB) or Heavy Virgin Naphtha. Light and
heavy naphtha are classified on basis of initial and final boiling points.
1.1.2 Light Naphtha
Light naphtha being less dense ("lighter") will have a higher paraffinic content. These are
therefore also referred to as paraffinic naphtha. The main application for these type of
naphtha is as a feedstock in the petrochemical production of olefins. This is also the reason
they are sometimes referred to as "light distillate feedstock" or (These naphtha types can
also be called "straight run gasoline or "light virgin naphtha). When used as feedstock in
petrochemical steam crackers, naphtha is heated in the presence of water vapour and the
absence of oxygen or air until the hydrocarbon molecules break apart. The primary
products of the cracking process are olefins (ethylene / ethene, propylene / propene and
11
butadiene). When naphtha is used as a feedstock in catalytic reforming the primary
products are aromatics including benzene, xylene, and toluene.
Table 1: Classification of light and heavy naphtha on basis of initial and final boiling points
1.2 Gasoline
Gasoline is the most widely used fuel in the world. Although an API survey reports that 40
types of gasoline are made by refineries, about 90% of the total gasoline produced in the
United States is used as fuel in automobiles. Most refiners produce gasoline in two or three
grades, unleaded regular, premium, and super-premium, and in addition supply a regular
gasoline to meet the needs of farm equipment and pre-1972 automobiles. The principal
difference between the regular and premium fuels is the antiknock performance. In 1999
the posted method octane number (PON) of unleaded regular gasoline was about 87 and
that of premium gasoline ranged from 89 to 93. The non-leaded regular gasoline averaged
about 88 PON. For all gasoline, octane numbers average about two numbers lower for the
higher elevations of the Rocky Mountain States. Posted octane numbers are arithmetic
averages of the motor octane number (MON) and research octane number (RON) and
average four to six numbers below the RON. Gasoline is complex mixtures of
hydrocarbons having typical boiling ranges from 100 to 400oF (38 to 205oC).
Although there are several properties of gasoline. The three that have greater effect on the
engine performance are Reid Vapor Pressure, Boiling Range and Antiknock
Characteristics. The Reid vapor pressure and boiling range govern the starting engine,
warm up rate of the acceleration, loss of dilution mileage, economy and tendency to vapor
lock.
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1.2.1 Octane Number
Octane numbers are a measure of a gasoline’s resistance to knock or detonation in a
cylinder of a gasoline engine. The higher this resistance is the higher will be the efficiency
of the fuel to produce work. A relationship exists between the antiknock characteristic of
the gasoline (octane number) and the compression ratio of the engine in which it is to be
used. The higher the octane rating of the fuel then the higher the compression ratio of
engine in which it can be used.
By definition, an octane number is that percentage of isooctane in a blend of isooctane and

normal heptane that exactly matches the knock behavior of the gasoline. Thus, a 90 octane
gasoline matches the knock characteristic of a blend containing 90% isooctane and 10% n-
heptane. The knock characteristics are determined in the laboratory using a standard single
cylinder test engine equipped with a super sensitive knock meter. The reference fuel
(isooctane blend) is run and compared with a second run using the gasoline sample.
Details of this method are given in the ASTM standards.
Two octane numbers are usually determined. The first is the research octane number (ON
res or RON) and the second is the motor octane number (ON mm or MON). The same
basic equipment is used to determine both octane numbers, but the engine speed for the
motor method is much higher than that used to determine the research number. The actual
octane number obtained in a commercial vehicle would be somewhere between these two.
The significance of these two octane numbers is to evaluate the sensitivity of the gasoline
to the severity of operating conditions in the engine. The research octane number is usually
higher than the motor octane number, the difference between them is termed the
‘sensitivity of the gasoline.
1.2.2 Blending
Components are blended to promote high antiknock quality, ease of starting, quick warm-
up, low tendency to vapor lock, and low engine deposits. For Octane number improvement
highly branched iso-paraffins are added to the gasoline main stream. N-butane is added to
give desired Reid vapor pressure and vapor pressure.
Normal butane is blended into gasoline to give the desired vapor pressure. The vapor
pressure [expressed as the Reid vapor pressure (RVP)] of gasoline is a compromise
between a high RVP to improve economics and engine starting characteristics and a low
RVP to prevent vapor lock and reduce evaporation losses. As such, it changes with the
season of the year and varies between 7.2 psi (49.6 kPa) in the summer and 13.5 psi (93.1
kPa) in the winter. Butane has a high blending octane number and is a very desirable
component of gasoline; refiners put as much in their gasoline as vapor pressure limitations
permit. Iso-butane can be used for this purpose but it is not as desirable because its higher
vapor pressure permits a lesser amount to be incorporated into gasoline than n-butane.
1.2.3 Octane Blending
Octane numbers are blended on a volumetric basis using the blending octane numbers of
the components. True octane numbers do not blend linearly and it is necessary to use
blending octane numbers in making calculations. Blending octane numbers are based upon
experience and are those numbers which, when added on a volumetric average basis, will
13
give the true octane of the blend. True octane is defined as the octane number obtained
using a CFR test engine.
1.3 Environmental Regulations to Improve Octane Number

Concern over the effects of hydrocarbon fuels usage on the environment has caused
changes in environmental regulations which impact gasoline and diesel fuel compositions.
The main restrictions on diesel fuels limit sulfur and total aromatics contents and gasoline
restrictions include not only sulfur and total aromatics contents but also specific compound
limits (e.g., benzene), limits on certain types of compounds (e.g., olefins), maximum Reid
vapor pressures, and also minimum oxygen contents for areas with carbon monoxide
problems. This has led to the concept of ‘‘reformulated gasoline.’’ A reformulated
gasoline specification is designed to produce a fuel for spark ignition engines which is at
least as clean burning as high methanol content fuels. As more is learned about the
relationship between fuels and the environment, fuel specifications are undergoing
changes.
One of the most important technical issues in automotive fuel regulatory regime that has
evolve in the United States since 1973 is the need to provide sufficient octane while at the
same time meeting the increasingly stringent fuel contents requirement designed to reduce
emissions and protect public health. There are several ways for refiners to provide octane
and all of them have the environmental consequences. Over all increasingly stringently
fuel regulation during past decades have contributed to decline in pollutants emission and
concurrent reductions in risks to the public health.
Producing motor fuels to reduce the environmental impact requires refinery equipments
addition as well as changes in catalysts and processing techniques. Of the gasoline
production 90% used in automobiles in USA and aviation gasoline market is relatively
small and accounts for about 3 % of the gasoline market. For this reason, it is not
considered in the preliminary design.
1.3.1 Sulfur and Aromatics in Gasoline
Tests indicate that it is desirable to have gasoline sulfur contents of less than 300 ppm
(0.03 wt %). The fluid catalytic cracker (FCC) naphtha is the main source of sulfur in the
refinery gasoline pool. For a given refinery crude oil charge, to meet the 300 ppm sulfur
specification, with no octane penalty, it is necessary to hydrotreat the FCC feedstock to
reduce the sulfur level sufficiently to produce FCC naphthas with acceptable sulfur
contents. The alternative is to hydrotreat the FCC naphtha, but this saturates the olefins in
the naphtha and results in a blending octane reduction of two to three numbers. Some
aromatics and most olefins react with components of the atmosphere to produce visual
pollutants. The activities of these gasoline components are expressed in terms of reactivity
with (OH) radicals in the atmosphere. The sources and reactivity of some of this gasoline
components .Specifically, xylenes and olefins are the most reactive and it may be
necessary to place limits on these materials.
14
1.4 Isomerization
The primary commercial use of the branched isomers of C4, C5, and C6 paraffins is in the
production of clean-burning, high-performance transportation fuels. The elimination of
tetraethyl lead over the last 30 years as a means of improving the antiknock properties of
gasoline and more recent regulations restricting motor fuel composition have led refiners
to select alternative means of producing high-quality gasoline. As a result of benzene
concentration restrictions, end-point and olefin content limitations, and potential
limitations on total aromatics concentration, the choices of high-quality gasoline blending
components available in the typical refinery are limited.
Isomerate, the gasoline blending component from light paraffin isomerization, is an ideal
choice. Another equally valuable blending component is alkylate resulting primarily from
the acid-catalyzed reaction of isobutene with an aliphatic olefin. Both isomerization and
alkylation yield highly branched, high-octane paraffinic components that by themselves
can satisfy the strictest environmental requirements.
1.4.1 Hydroisomerization History of LSR Naphtha.

The first successful efforts in the research and development of catalytic systems for the
isomerization of normal paraffins came in the early 1930s. The requirement for high-
octane aviation gasoline during World War II accelerated the application of early
isomerization research. Light olefinic hydrocarbons were available from the newly
developed fluid catalytic cracking (FCC) process and from other mainly thermal
operations. These olefinic hydrocarbons could be alkylated with isobutane (iC4) to
produce a high-octane gasoline blending component. However, the supply of isobutane
from straight-run sources and other refinery processing was insufficient, and a new source
of supply had to be found.
The first commercial butane isomerization unit went on-stream in late 1941. By the end of
the war, 38 plants were in operation in the United States and 5 in allied countries for a total
capacity of approximately 50,000 barrels per stream day (BPSD). Five principal
isomerization processes, including one developed by UOP, were used in the United States.
All were based on Friedel-Crafts chemistry and used aluminum chloride in some form.
The wartime units fulfilled the needs of the time. However, despite many improvements,
the units remained difficult and costly to operate. Corrosion rates were excessive, plugging
of catalyst beds and equipment was common, and catalyst consumption was high. The
units were characterized by high maintenance and operating costs and low on stream
efficiency.
1.4.2 Hydroisomerization Processes.

 UOP BenSat Process 
 UOP Butamer Process 
 UOP Penex Process 
 UOP Zeolitic Process 


15
UOP Penex process has further sub classes for Octane number improvement.
 Penex Once through Process 
 Penex-Molex Process 
 Penex with DIP Process 
 Penex with DIH Process 
1.4.2.1 UOP BenSat Process

The UOP BenSat process was developed to treat C5-C6 feed stocks with high benzene
levels. Because almost all the benzene is saturated to cyclohexane over a fixed bed of
catalyst, no measurable side reactions take place. Process conditions are moderate, and
only a slight excess of hydrogen above the stoichiometric level is required. The high heat
of reaction associated with benzene saturation is carefully managed to control the
temperature rise across the reactor. Product yield is greater than 100 liquid volume percent
(LV %), given the volumetric expansion associated with saturating benzene and the lack of
any yield losses from cracking to light ends. The product has a lower octane than the feed
as a result of the conversion of the high octane benzene into lower-octane cyclohexane.
However, the octane can be increased by further processing the BenSat product in an
isomerization unit, such as a UOP Penex unit.
1.4.2.2 UOP Butamer Process

Many research studies were conducted, and in 1959, UOP made available to the industry a
butane isomerization process, UOP’s Butamer process, that used a highly active, low-
temperature hydroisomerization catalyst capable of achieving butane conversion at
temperature levels equivalent to the wartime Friedel-Crafts systems without the attendant
corrosion or sludge formations. Industry acceptance of the UOP process was rapid, and in
late 1959, the first Butamer unit, the first commercial butane isomerization unit to use a
low-temperature, dual-functional catalyst system, was placed on-stream on the United
States West Coast.
1.4.2.3 UOP Penex Process

The UOP Penex Process is specifically designed for the continuous catalytic
Hydroisomerization of pentanes, hexanes, and mixtures thereof. The reactions take place
in a hydrogen atmosphere, over a fixed bed of catalyst, and at operating conditions which
promote Hydroisomerization and minimize hydrocracking. Operating conditions are not
severe as reflected by moderate operating pressure, low temperature, high catalyst space
velocity, and low hydrogen partial pressure requirements.
Ideally, this Hydroisomerization catalyst would convert all the feed paraffins to the high
octane-number branched structures: normal pentane (nC5) to iso-pentane (iC5) and normal
hexane (nC6) to 2, 2- and 2, 3-dimethyl butane. The reaction is controlled by a
thermodynamic equilibrium that is more favorable at low temperature. The reactor effluent
is cooled before entering the product stabilizer. The stabilized, isomerized liquid product
from the bottom of the column then passes to gasoline blending.
Alternatively, the stabilizer bottoms can be separated into normal and iso-paraffins
components by fractionation or molecular-sieve separation or a combination of the two
16
methods to obtain recycle of the normal paraffins and low-octane methyl pentane. Product
octanes in the range of 87 to 92 RON, clear, can be achieved by selecting one of the
various possible schemes. The least capital-intensive recycle flow scheme is achieved by
combining the Penex process with a (Penex DIH) deisohexanizer column.
An efficient recycle operation is obtained by combining the Penex process with UOP’s
Molex process, which uses molecular sieves to separate the stabilized Penex product into a
high-octane iso-paraffins stream and a low-octane normal paraffin stream. In this system,
fresh feed together with the recovered low-octane normal paraffin stream is charged to the
Penex unit. The isomerized product is denormalized in the Molex unit and recovered for
gasoline blending.
1.4.3 Reason for Selection of Isomerization

To comply with the regulations imposed by the environmental agencies. Refiners follow
the different catalysts and techniques, some of them are catalytic reforming, catalytic
cracking, hydrocracking, polymerized gasoline, Alkylation and n-butane blending and use
of additives like MTBE (methyl tertiary butyl ether), ETBE (ethyl tertiary butyl ether),
TAME (tertiary amyl methyl ether) and ethanol.Other additives, for example, antioxidants,
metal deactivators, and antistall agents.
Catalytic reformate is the C 5 gasoline product of the catalytic reformer. Heavy straight-
run (HSR) and coker gasoline are used as feed to the catalytic reformer, and when the
octane needs require, FCC and hydrocracked gasoline of the same boiling range may also
be processed by this unit to increase octane levels but reforming process is the most
expensive process of these methods.
The processing conditions of the catalytic reformer are controlled to give the desired
product antiknock properties in the range of 90 to 104 RON (85 to 98 PON) clear (lead-
free). The FCC and HC gasoline are generally used directly as gasoline blending stocks,
but in some cases are separated into light and heavy fractions with the heavy fractions
upgraded by catalytic reforming before being blended into motor gasoline, so some extra
processing involved obtaining for complying gasoline.
This has been true since motor gasoline is unleaded and the clear gasoline pool octane is
now several octane numbers higher than when lead was permitted. It is usual for the heavy
hydrocrackate to be sent to the reformer for octane improvement. The reformer increases
the octane by converting low-octane paraffins to high-octane aromatics. Some aromatics
have high rates of reaction with ozone to form visual pollutants in the air and some are
claimed to be potentially carcinogenic by EPA.
Restrictions on aromatic contents of motor fuels will have increasing impacts on refinery
processing as more severe restrictions are applied. This will restrict the severity of
catalytic reforming and will require refiners to use other ways to increase octane numbers
of the gasoline pool by incorporating more oxygenates in the blend.
Polymer gasoline is manufactured by polymerizing olefinic hydrocarbons to produce

higher molecular weight olefins in the gasoline boiling range. Refinery technology favors
17
alkylation processes rather than polymerization for two reasons: one is that larger
quantities of higher octane product can be made from the light olefins available, and the
other is that the alkylation product is paraffinic rather than olefinic, and olefins are highly
photo reactive and contribute to visual air pollution and ozone production.
Alkylate gasoline is the product of the reaction of iso-butane with propylene, butylene, or
pentylene to produce branched-chain hydrocarbons in the gasoline boiling range.
Alkylation of a given quantity of olefins produces twice the volume of high octane motor
fuel as can be produced by polymerization. In addition, the blending octane (PON) of
alkylate is higher and the sensitivity (RON MON) is significantly lower than that of
polymer gasoline.
Hydroisomerization is the best suited to abolish most of these limitations. This process
enhances the Octane number as well as removes the aromatics, lead and other undesirable
contents about completely. This process used the normal paraffin’s to produce the iso-
paraffins. The separation of iso and normal paraffin’s is carried out hence producing even
high octane gasoline, used to produce gasoline blending stock. For maximum octane
number without addition of lead, now refiners install isomerization unit to process the LSR
fraction and achieve the octane improvement of 13 to 20 numbers over that of LSR.
18
Chapter 2
Process description
19
2.1 Introduction
The UOP Penex Process is specifically designed for the continuous catalytic isomerization of
pentanes, hexanes, and mixtures thereof. The reactions take place in a hydrogen atmosphere,
over a fixed bed of catalyst, and at operating conditions which promote isomerization and
minimize hydrocracking. Operating conditions are not severe as reflected by moderate
operating pressure, low temperature, high catalyst space velocity, and low hydrogen partial
pressure requirements.
Ideally, this isomerization catalyst would convert all the feed paraffins to the high octane-
number branched structures: normal pentane (nC5) to i-pentane (iC5) and normal hexane
(nC6) to 2,2- and 2,3-dimethyl butane. The reaction is controlled by a thermodynamic
equilibrium that is more favorable at low temperature.
With C5 paraffins, inter conversion of normal pentane and i-pentane occurs. The C6-paraffin
isomerization is somewhat more complex. Because the formation of 2- and 3-methylpentane
and 2,3-dimethyl butane is limited by equilibrium, the net reaction involves mainly the
conversion of normal hexane to 2,2-dimethylbutane. All the feed benzene is hydrogenated to
cyclohexane, and a thermodynamic equilibrium is established between methylcyclopentane
and cyclohexane. Except for normal hydro treating, the Penex process requires neither special
feed pretreatment nor especially sharp or costly prefractionation for removal of C 6 cyclic or
C7+.
The hydroisomerization process is regarded as the one of the complex reaction network,
where such reaction takes place on metal and acid site catalyst. Therefore it is supposed that
the alkane is dehydrogenated on metal sites, the alkene is then protonated on acid site to a
carbonium ion, which is subsequently isomerized to branched chain carbonium ion. The
branched chain carbonium ion gives the proton back to the acid site. The resulting alkene is
then hydrogenated on metal site. Finally the branched chain is formed.
2.2 Feed Stock Requirements

The purpose of this section is to discuss and highlight the effects of the following
contaminants and undesirable components on the Penex Process.
2.2.1 Contaminants
Following contaminants are present in feed stream, as the Penex unit’s feed is hydrotreated
and dried, it is highly unlikely that any of these contaminants will manifest themselves to any
degree.
2.2.1.1 Sulfur
The presence of sulfur in the combined feed will decrease the activity of the catalyst. This
decrease in activity is temporary and recovery is normally rapid once the sulfur has been
removed.
20
2.2.1.2 Water or other oxygenated compounds
The oxygenated compounds react chemically with the active chloride on the catalyst. This
chloride is chemically bound into the alumina structure during manufacture. The water, once
it reacts with the catalyst and thereby splits out HC1, is chemically bound as hydroxyl to the
alumina.
2.2.1.3 Nitrogen Compounds
These compounds normally react with the chloride in the catalyst or the HCl to form salts
which can deactivate the catalyst permanently by coating the catalyst active sites, loss of
chloride due to salt deposits.
2.2.2 Undesirable Hydrocarbons

2.2.2.1 Olefins
The UOP Penex process has been operated with an olefin content of as much as 2%. The
amount and types of olefins present in, say, a C5/C6 fraction from a catalytic reformate are
acceptable. The adverse effect of appreciable quantities of olefins is thought to be due to
their physically coating the catalyst following polymerization.
2.2.2.2 Cyclic Compounds

Although this is not a cumulative effect, cyclic compounds are absorbed on the catalyst and
therefore reduce the active sites available for paraffin isomerization. Should the amount of
benzene in the charge stock exceed about 5%, additional catalyst inventory would be
required in the reactors.
2.2.2.3 C7 Hydrocarbons
It is preferable to restrict the C7+ content of the feedstock to the UOP Penex process using
catalyst to 2 or 3%. C7 paraffins hydrocrack quite readily to C3 and C4, and those which do
not hydrocrack will be isomerized to a mixture having a lower octane number than the C 5 or
C6.
Table 2: Typical Limits on Stream Impurities
Total sulfur 0.1 ppm

Total nitrogen 0.1 ppm
Total oxygenates 0.1 ppm
Water 0.5 ppm
Copper Nil
Lead Nil
Bromides Nil
Total chlorides 0.5 ppm
Arsenics Nil
Fluorides Nil
21
2.3 Process Flow
Light naphtha feed is charged to one of the two dryer vessels. These vessels are filled with
molecular sieves, which remove water and protect the catalyst. After mixing with makeup
hydrogen, the feed is heat-exchanged against reactor effluent. It then enters a charge heater
before entering the reactors. Two reactors normally operate in series. The reactor effluent is
cooled before entering the product stabilizer. In new Penex designs, both the recycle gas
compressor and the product separator have been eliminated. Only a slight excess of hydrogen
above chemical consumption is used. The makeup hydrogen, which can be of any reasonable
purity, is typically provided by a catalytic reformer. The stabilizer overhead vapors are
caustic scrubbed for removal of the HCl formed from organic chloride added to the reactor
feed to maintain catalyst activity. After scrubbing, the overhead gas then flows to fuel. The
stabilized, isomerized liquid product from the bottom of the column then passes to gasoline
blending.
Figure 1: Process Flow Sheet of Hydroisomerization of LSR Naphtha
2.4 Process chemistry

Paraffin isomerization catalysts fall mainly into either of two principal categories: those
based on Friedel-Crafts catalysts as classically typified by aluminum chloride and hydrogen
chloride and dual-functional hydroisomerization catalysts. The Friedel-Crafts catalysts
represented a first-generation system. Although they permitted operation at low temperature,
and thus more favorable isomerization equilibrium, they lost favor because these systems
were uneconomical and difficult to operate. High catalyst consumption and a relatively short
life resulted in high maintenance costs and a low on-stream efficiency.
Isomerization either by Friedel craft or dual-function catalysts is generally thought to entail

intramolecular rearrangements of carbonium ions as illustrated as follows
22
The equilibrium of paraffin is low isomerization condition is low, however sufficient olefin
must be present convert the carbonium by strong acid site.
Through the formation of the carbonium ion, the olefin product is removed, and equilibrium
is allowed to proceed. The carbonium ion in the second reaction undergoes skeletal
isomerization, probably through a cycloalkyl intermediate:
This reaction proceeds with difficulty because it requires the formation of a primary
carbonium ion at some point in the reaction. Nevertheless, the strong acidity of the
isomerization catalyst provides enough driving force for the reaction to proceed at high rates.
In the last step, the isoolefin intermediate is hydrogenated rapidly back to the analogous iso-
paraffin’s:
Equilibrium limits the maximum conversion possible at any given set of conditions. This
maximum is a strong function of the temperature at which the conversion takes place.
During isomerization of paraffins in the reactor, some other reaction also takes place such as
hydrocracking, ring opening and benzene saturation in the presence of hydrogen.
23
2.4.1 Hydrocracking
Hydrocracking occurs in the Penex reactor to a degree which depends on the feed quality and
severity of operation. Large molecules such as C7's tend to hydrocrack more easily than
smaller molecules.
C7H16 + H2 C4H10+C3H8
2.4.2 Benzene Saturation

Penex feeds can contain up to 5% benzene. The catalyst will saturate benzene to cyclohexane.
+ 3H2
2.4.3 Ring Opening
2.5 Process Variables

This section discusses the influence of various process variables on Penex process
performance.
2.5.1 Reactor Temperature

In general, reactor temperature is the main process control. A definite upper limit exists for
the amount of iso-paraffins which can exist in the reactor product at any given outlet
temperature. As reactor temperature is raised to increase the rate of isomerization, the
equilibrium composition will be approached more closely. At excessively high temperatures,
the concentration of iso-paraffins in the product will actually decrease because of the
downward shift in the equilibrium curve, even though the high temperature gives a higher
reaction rate. The use of temperatures higher than necessary to achieve a reasonably close
approach to equilibrium accomplishes nothing other than to increase the amount of
hydrocracking.
2.5.2 Liquid Hourly Space Velocity (LSHV)

This term, commonly shortened to LHSV, is defined as the volumetric hourly flow of reactor
charge divided by the volume of catalyst contained in the reactor, in consistent units. The
design LHSV for C5/C6 Penex operation is normally between 1 and 2. Increasing the LHSV
beyond this will lead to lower product isomer ratios.
24
2.5.3 Hydrogen to Hydrocarbon mol Ratio (H2/HCBN)
This ratio is defined as the number of moles hydrogen at the second reactor outlet per mol. of
reactor charge passing over the catalyst, and is specified at 0.05 (moles H2/mol HCBN). The
primary purpose of maintaining the ratio at or above the design is to avoid carbon deposition
on the catalyst and maintain enough H2 for the reactions to proceed. If necessary, the reactor
charge rate is to be reduced to maintain the design hydrogen to hydrocarbon ratio.
2.5.4 Pressure
Penex Unit is normally designed to operate at 31.5 barg at the reactor outlet. Methyl-
cyclopentane and cyclohexane appear to absorb on the catalyst and reduce the rate of
isomerization reactions. Higher pressure helps to offset this effect of the C6 cyclic
compounds. Lowering the unit pressure or operating at a slightly lower level would not affect
the catalyst life but the extent of isomerization would be influenced.
2.5.5 Catalyst Promoter

To sustain catalyst activity, the addition of chloride is necessary. Whenever there is a catalyst
chloride deficiency, the product isomer ratios will decrease (although not necessarily
instantaneously), other things being equal. Restarting the injection of chloride will tend to
return the activity of the catalyst to its previous level.
2.5.6 Hydroisomerization Reactor

The heart of the Penex system is the reactor section. The Penex system will normally employ
two reactors in a series flow configuration with the total required catalyst loading being
equally distributed between the vessels.
Reaction is exothermic and the temperature increase across the reactor. The reaction takes
place in a hydrogen atmosphere, over a fixed bed catalyst and at operating conditions which
promote Hydroisomerization and minimizing hydrocracking. The schematic diagram of the
Penex reactor is given below.
Figure 2: UOP Penex Hydroisomerization Reactor

25
2.6 Catalysts for Light Naphtha Isomerization
The first hydroisomerization unit was introduced in 1953 by UOP, followed in 1965 by the
first BP unit, while in 1970 the first Shell Co. hydro-isomerization (HYSOMER) unit was
started up. All these processes take place in the gas phase on a fixed bed catalyst containing
platinum on a solid carrier. In the late 1950s and early 1960s, chlorinated platinum loaded
alumina was used as a catalyst. The major advantage of this catalyst was its low temperature
activity (T< 200°C) due to its high acidity. However the catalyst was sensitive towards water
and oxygenates and in addition had corrosive properties. Furthermore, chlorine addition
during the reaction is necessary to guarantee catalyst stability.
The isomerization of hydrocarbons < C6 is currently carried out very successfully using
bifunctional supported platinum catalysts. However, difficulties are encountered with
hydrocarbons larger than hexane since the cracking reactions become more significant over
platinum catalysts as the chain length increases.
There are three main types of Catalyst being used commercially for isomerization of paraffins
which are as follows.
1) Chlorinated Alumina
2) Sulfated zirconia
3) Zeolites
Comparison of different Hydroisomerization Catalyst
Chlorinated Alumina High activity/Performance
Sensitive to Contaminants
Regeneration not required
Sulfated Zirconia Good activity/Performance
Tolerant to contaminate
Regenerable
Zeolites Lower Activity/Performance
More Tolerant to Contaminates
Regenerate
26
2.7 Selection of Catalyst
The catalyst used in this process is Platinum Chloride impregnated on Alumina and reason
for selection is as follows.
The desire to operate at lower temperatures, at which the thermodynamic equilibrium is more
favorable, dictated the development of third-generation catalysts. The advantage of these
low-temperature [below 200°C (392°F)] catalysts contributed to the relative nonuse of the
high-temperature versions. Typically, these noble-metal, fixed-bed catalysts contain a
component to provide high catalytic activity. They operate in a hydrogen environment and
employ a promoter. Because hydrocracking of light gases is slight, liquid yields are high. The
first of these catalysts was commercialized in 1959 in the UOP Butamer process for butane
isomerization.
Low temperature is considered rather arbitrarily for catalyst classification purposes as

anything below 390 F (199 C) operating temperature. Typically these are fixed bed
catalysts containing a supported noble metal and a component to provide acidity in the
catalytic sense. They operate in a hydrogen atmosphere and may employ a catalyst promoter
whose concentration in the reactor may range from parts per million to substantially higher
levels. They generally all require a dry, low sulfur feedstock; however, they may differ
importantly in their tolerance of certain types and molecular weights of hydrocarbons.
The chlorinated Alumina, highest activity paraffin isomerization catalyst is available,

increases the octane number of typical naphtha stream from 70 to as high as 85 RON in once
through process. Up to 93 RON can be obtained by recycling the low octane paraffins. The
C5+ yield, from the chlorinated alumina catalyst is highest from other commercial catalyst
available because of high catalytic activity and low operating temperature.
Because Chlorinated Alumina systems are not economical regenerable, eventual reloading of
catalyst must be considered. Nevertheless, the Chlorinated Alumina system is often the most
economics choice because of its inherent activity.
As a result of intensive research and development in the field of isomerization of paraffins

technology, UOP’s I-80 catalyst is one of the high activity catalysts available currently. The
I-80 is significantly more active than I-8 catalysts, it is based on unique formulation and
manufacturing technique.
27
Chapter 3
Material Balance
28
3.1 Introduction
Material balances are the basis of process design. A material balance taken over the complete
process will determine the quantities of raw materials required and products produced.
Balances over individual process units set the process stream flows and compositions.
Material balances are also useful tools for the study of plant operation and trouble shooting.
They can be used to check performance against design; to extend the often limited data
available from the plant instrumentation; to check instrument calibrations; and to locate
sources of material loss. In this chapter we applied material balance calculations on heat
exchanger, reactors and distillation column.
3.2 Feed Streams

There are four feed streams that are entering in our system. We will direct these feed streams
in a mixer to combine them. Individual feed stream is explained below.
3.2.1 Feed 1: Light straight run naphtha

The project capacity of processing light naphtha is 10,000 barrels per stream day (BPSD).
Volumetric flow rate is calculated as follows:
As 1 barrel = 42 US gallon
And 1 m3 = 264.2 US gallon
Volumetric flow rate = 66.5 m3/h
Density of feed = ρ = 662.62kg/m3

Specific gravity = 0.663
Mass flow rate of feed = Volumetric flow × density
= 66.5 m3/h × 662.62 kg/ m3

= 43898.575 kg/h
To convert it into molar flow rate, divide mass flow rate with average molecular mass
Molar flow rate = 43898.575 kg/h × 1kgmol/79.027kg

= 555.48kgmol/h
29
The composition of Naphtha Feed is as under
Table 3: Composition of Naphtha in feed
Component Mole fraction Molar flow Molecular Mass flow Average

rate weight rate molar mass
i-butane 0.00116 0.644357 58.1 37.43713 0.067379855
n-butane 0.02043 11.34846 58.1 659.3453 1.186977318
i-pentane 0.176147 97.84614 72.1 7054.706 12.70016884
n-pentane 0.247826 137.6624 72.1 9925.458 17.86823245
cyclopentane 0.022063 12.25556 70 857.8889 1.544420984
2,2-dimethybutane 0.009233 5.128747 86.2 442.098 0.795915558
2,3-dimethybutane 0.01819 10.10418 86.2 870.9804 1.56795365
2-methylpentane 0.114557 63.63412 86.2 5485.261 9.87478354
3-methypentane 0.08151 45.27717 86.2 3902.892 7.026124176
n-hexane 0.189609 105.324 86.2 9078.929 16.34425529
methylcyclopentane 0.035146 19.5229 84.2 1643.828 2.95931174
cyclohexane 0.031048 17.24654 84 1448.71 2.608045758
benzene 0.037551 20.85883 78 1626.989 2.928969255
n-heptane 0.015532 8.627715 100 862.7715 1.553184675
1 555.4811 43897.3 79.025
3.2.2 Feed 2: Hydrogen gas

Hydrogen gas needed for the reaction is taken from the semi regenerative plat former unit.
Hydrogen to Hydrocarbon Ratio (H2/HC)
This ratio is defined as the number of moles hydrogen at the second reactor outlet per mol. of
reactor charge passing over the catalyst, and is specified at 0.056 (moles H2/moles HCBN).
= 0.056×555.48
= 31.10 kgmol/h
Hydrogen required according to chemical reaction
= 100.11 kgmol/h
So total flow rate of hydrogen stream
= 100.11+31.10
= 131.20 kgmol/h
3.2.3 Feed 3: Catalyst promoter
Catalyst promoter used in this process is percholoroethylene. For 90 days consumption is
= 18200 kg
So for 1 hour
= 18200/90×24
30
= 8.42 kg/h
Molecular weight of percholoroethylene is
= 166
= 0.0507 kgmol/h
3.2.4 Feed 4: Caustic alkali (10% NaOH + 90% water)

HCL formed
= 0.0507×4
= 0.2028 kgmol/h
Caustic required using acid
= 0.2028 kgmol/h
Weight of caustic alkali required
= 8.112 kg/h
Water required to form 10% solution
= 8.112×0.9/0.1
= 73
Total weight of solution
= 73+8.112
= 81.112 Kg/h
Hydrogen = 131kgmol/hr
Naphtha = 555.48 kgmol/hr
Feed = 679.531 kgmol/ hr
Perchloroethylene = .0507 kgmol/hr

Figure 3: Material Balance around Steam Mixer
31
3.3 Material balance around first reactor
The plug flow reactor (PFR, sometimes called continuous tubular reactor, CTR, or piston
flow reactors) is a model used to describe chemical reactions in continuous, flowing systems
of cylindrical geometry. The PFR model is used to predict the behaviour of chemical reactors
of such design, so that key reactor variables, such as the dimensions of the reactor, can be
estimated.
Fluid going through a PFR may be modeled as flowing through the reactor as a series of
infinitely thin coherent "plugs", each with a uniform composition, traveling in the axial
direction of the reactor, with each plug having a different composition from the ones before
and after it. The key assumption is that as a plug flows through a PFR, the fluid is perfectly
mixed in the radial direction but not in the axial direction (forwards or backwards). Each plug
of differential volume is considered as a separate entity, effectively an infinitesimally small
continuous stirred tank reactor, limiting to zero volume. As it flows down the tubular PFR,
the residence time (\tau) of the plug is a function of its position in the reactor. In the ideal
PFR, the residence time distribution is therefore a Dirac delta function with a value equal to
\tau.
The isomerization reactor used in UOP Penex process is a fixed bed plug flow reactor
operating in adiabatic mode. The catalyst used is platinum chloride impregnated in alumina.
There are nine main reactions taking place with different conversions. The reactions
occurring in the reactor are as follows:
Figure 4: Material balance around Reactor 1
32
Reaction 1
n-pentane i-pentane
CH3-CH2--CH2--CH2-CH3
CH3-CH2—CH-CH3
CH3
Moles of n-pentane in feed = 137.66 kgmol/h
1 kgmol/h of n-pentane is forming = 1 kgmol/h of i-pentane
Equilibrium conversion of n-pentane = 37 %
So i-pentane formed = 137.66 ×0 .37
= 50.93 kgmol/h
Unconverted n- pentane = 137.66-50.93
= 87.72 kgmol/h
Reaction 2
CH3
CH3-CH2-CH2-CH2--CH2-CH3 CH2-C-CH2-CH3
CH3
1 kgmol/h of n-hexane is forming = 1 kgmol/h of 2,2-dimethyl butane
Moles of n-hexane in feed = 105.324 kgmol/h
Equilibrium conversion of n-hexane = 52%
Fractional conversion of n-hexane = 84%
to 2,2- dimethyl butane
So 2,2- dimethyl butane formed = 105.324 ×0.52×0.84
= 46.005 kgmol/h
33
Reaction 3
n-hexane 2,3-dimethylbutane
CH3
CH3-CH2-CH2-CH2-CH2-CH3 CH3-CH-CH-CH3
CH3
to 2,3-dimethyl butane
So 2,3-dimethyl butane formed = 105.324 ×0.52×0.16
= 8.763 kgmol/h
Unconverted n-hexane after these reactions will be
= 105.324-46.005-8.763
= 50.56 kgmol/h
Reaction 4
Methyl pentane to 2,2-dimethybutane

CH3
CH3- CH-CH2-CH2-CH3 CH3-CH2-C-CH3
CH3 CH3
Moles of methyl pentane in feed = 108.717 kgmol/h
Equilibrium conversion of n-hexane = 1.2%
So 2,2-dimethylbutane formed = 108.717 ×0.012
= 1.30 kgmol/h
Unconverted methyl pentane after these reactions will be
= 108.717-1.30
34
= 107.417 kgmol/h
Reaction 5
Methylcyclopentane 2,2-dimethylbutane
Moles of methylpentane in feed = 19.523 kgmol/h
So 2,2-dimethylbutane formed = 19.523×0.046
= 0.8981 kgmol/h
Unconverted methylcyclopentane after these reactions will be
= 19.523-0.8981
= 18.625 kgmol/h
1kgmol/hr of methylcyclopentane is consuming = 1kgmol/h of hydrogen
So total hydrogen consumed will be
= 0.8981 kgmol/h
Reaction 6
Benzene + 3 H2 Cyclohexane
3H2
Moles of Benzene in feed = 20.58kgmol/h

35
Equilibrium conversion of benzene = 100%
So cyclohexane formed = 20.58kgmol/h
1kgmol/h of benzene is consuming = 3kgmol/h of hydrogen
So total hydrogen consumed will be = 20.853 × 3
= 62.576 kgmol/h
Reaction 7
Cyclohexane + Hydrogen 2,2-dimethy butane
Moles of cyclohexane in feed = 17.246 kgmol/h

Moles of cyclohexane being formed = 20.858 kgmol/h
Total moles to be reacted = 38.11 kgmol/h
1kgmol/h of cyclohexane is forming = 1kgmol/h of 2,2-dimethyl butane
Equilibrium conversion of cyclohexane = 55%
Fractional conversion of cyclohexane
To 2,2-dimethy butane = 84%
So 2,2-dimethy butane formed = 38.11 × .55 × .84
= 17.60 kgmol/h
1kgmol/hr of cyclohexane is consuming = 1kgmol/h of hydrogen
So hydrogen consumed in this reaction = 17.60 kgmol/h
Reaction 8
Cyclone + Hydrogen 2,3-dimethylbutane

Moles of cyclohexane being formed = 20.858 kgmol/h
Total moles to be reacted = 38.11 kgmol/h
36
Equilibrium conversion of cyclohexane = 55%
Fractional conversion of cyclohexane to
2,3-dimethylbutane = 16%
So 2,3-dimethybutane formed = 38.11 ×0.55×0.16
= 3.353 kgmol/h
1kgmol/h of cyclohexane is consuming = 1kgmol/h of hydrogen
Unconverted cyclohexane after these reactions
= 38.11 – 17.60 – 3.353
= 17.15 kgmol/h
Reaction 9
Perchloroethylene + 5 Hydrogen 4 Hydrogen Chloride + Ethane
+ 5H2 4HCl + C2H6
Catalyst promoter used in this process is perchloroethylene. For 90 days consumption is
= 18200 kg
So for 1 hour
= 18200/9×024
= 8.42 kg/h
Molecular weight of perchloroethylene is = 166
Moles of catalyst entering = 0.0507 kgmol/h
1kgmol/h of perchloroethylene is consuming = 5 kgmol/h of hydrogen
So hydrogen consumed in this reaction = 0.0507 × 5
= .2535 kgmol/h of hydrogen
Total hydrogen consumption in Reactor 1
= .891+62.576+17.60+3.353+.2537+4.79
= 84.47 kgmol/h
37
Table 4: Material Balance around Reactor 1
Component Feed to ISO R-1 Product of ISO R-1

(kgmol/h) (kgmol/h)
Hydrogen 131.20 41.72
Methane 0 0.721
Ethane 0 0.366
Propane 0 8.494
i-butane 0.64130185 5.054
n-butane 11.2973047 6.324
i-pentane 97.845 148.775
n-pentane 137.66 86.72
2,2-dimethybutane 5.192 66.132
2,3-dimethylbutane 10.10 21.21
methylpentane 108.717 107.417
n-hexane 105.324 50.56
methylcyclopentane 19.523 18.625
Cyclohexane 17.246 22.88
Benzene 20.858 0
n-heptane 8.59 7.41
HCl 0 0.2028
perchoroethylene 0.0507 0
Total 667.044 595.94
3.4 Material Balance around Reactor 2

The isomerization reactor used in uop penex process is a fixed bed plug flow reactor
operating in adiabatic mode. The catalyst used is platinum chloride impregnated in alumina.
There are nine main reactions taking place with different conversions. The reactions
occurring in the reactor are as follows:
Figure 5: Material Balance around Reactor 2
38
Reaction 1
n-pentane i-pentane
CH3-CH2—CH-CH3
CH3
Moles of n-pentane in feed = 86.72 kgmol/h
1 kgmol/h of n-pentane is forming = 1 kgmol/h of i-pentane
Equilibrium conversion of n-pentane = 36.5 %
So i-pentane formed = 86.72 ×0 .365
= 31.65 kgmol/h
Unconverted n- pentane = 86.72-31.65
= 55.06 kgmol/h
Reaction 2
CH3
CH3-CH2-CH2-CH2--CH2-CH3 CH2-C-CH2-CH3
CH3
to 2,2- dimethyl butane
So 2,2- dimethyl butane formed = 50.56 ×0.50×0.84
= 21.23 kgmol/h
39
Reaction 3
n-hexane 2,3-dimethylbutane
CH3
CH3-CH2-CH2-CH2-CH2-CH3 CH3-CH-CH-CH3
CH3
to 2,3-dimethyl butane
So 2,3-dimethyl butane formed = 50.56 ×0.50×0.16
= 4.044 kgmol/h
Unconverted n-hexane after these reactions will be
= 50.56-21.23-4.044
= 25.286 kgmol/h
Reaction 4
Methylpentane to 2,2-dimethybutane
CH3
CH3- CH-CH2-CH2-CH3 CH3-CH2-C-CH3

CH3 CH3
40
So 2,2-dimethylbutane formed = 107.417 ×0.0182
= 1.95 kgmol/h
Unconverted methylpentane after these reactions will be
= 107.417-1.95
= 105.521 kgmol/h
Reaction 5
Methylcyclopentane 2,2-dimethylbutane
So 2,2-dimethylbutane formed = 18.625 × 0.0461
= 0.86 kgmol/h
Unconverted methylcyclopentane after these reactions will be
= 18.625-0.86
= 17.75 kgmol/h
1kgmol/hr of methylcyclopentane is consuming = 1kgmol/h of hydrogen
So total hydrogen consumed will be
= 0.86 kgmol/h
41
Reaction 6
Cyclohexane + Hydrogen 2,2-dimethy butane

1kgmol/h of cyclohexane is forming = 1kgmol/h of 2,2-dimethyl butane
Equilibrium conversion of cyclohexane = 55.56%
Fractional conversion of cyclohexane
To 2,2-dimethy butane = 84%
So 2,2-dimethy butane formed = 17.60 × .5556 × .84
= 8.21 kgmol/h
1kgmol/hr of cyclohexane is consuming = 1kgmol/h of hydrogen
Reaction 7
Cyclone + Hydrogen 2,3-dimethylbutane

Equilibrium conversion of cyclohexane = 55.56%
Fractional conversion of cyclohexane to
2,3-dimethylbutane = 16%
So 2,3-dimethybutane formed = 17.6 ×0.5556×0.16
= 1.56 kgmol/h
1kgmol/h of cyclohexane is consuming = 1kgmol/h of hydrogen
Total hydrogen consumed in these reaction = .86+1.56+8.21
42
= 10.63 kgmol/h
Total hydrogen consumed in both reactors = 84.47 + 10.63
= 100.11 kgmol/h
Table 5: Material Balance around Reactor 2
Component Inlet to ISO R-2 Outlet of ISO R-2

(kgmol/h) (kgmol/h)
hydrogen 41.72 31.10
methane 0.721 0.721
ethane 0.366 0.416
propane 8.494 8.494
i-butane 5.054 6.10
n-butane 6.324 5.72
i-pentane 148.775 180.43
n-pentane 86.72 55.06
2,2-dimethybutane 66.132 98.382
2,3-dimethyl butane 21.21 26.814
methylpentane 107.417 105.462
n-hexane 50.56 25.07
methylcyclopentane 18.625 17.75
cyclohexane 17.60 7.83
n-heptane 7.41 7.12
HCl 0.2028 0.2028
Total 595.94 576.67
3.5 Material balance around Stabilizer column

The purpose of this column is to separate any dissolved hydrogen and cracked gases (C1, C2
and C3's).
Figure 6: Material balance around Stabilizer Column

43
Figure 7: Material Balance around Stabilizer Column
Component Feed Mole Top Mole Bottom Mole

(Kmol/hr) fraction (Xf) product fraction product fraction
(Kmol/hr) (Xd) (Kmol/ (Xb)
hr)
Hydrogen 31.1 0.05393 31.1 0.596302
HCl 0.2028 0.000352 0.2028 0.003888
Methane 0.721 0.00125 0.721 0.013824
Ethane 0.416 0.000721 0.416 0.007976
Propane 8.494 0.014729 8.494 0.162861
i-butane 6.1 0.010578 6.1 0.11696
n-butane 5.72 0.009919 5.1 0.097786 0.62 0.001182
i-pentane 180.43 0.312882 0.021 0.000403 180.4 0.343941
n-pentane 55.06 0.095479 55.06 0.104975
2,2-dimethybutane 98.382 0.170603 98.382 0.18757
2,3-dimethylbutane
26.814 26.814
0.046498 0.051122
Methylpentane 105.462 0.18288 105.462 0.201068
n-hexane 25.07 0.043474 25.07 0.047797
Methylcyclopentane 17.75 0.03078 17.75 0.033841
Cyclohexane 7.83 0.013578 7.83 0.014928
n-heptane 7.12 0.012347 7.12 0.013575
Total 576.6718 1 52.1548 1 524.508 1
44
Chapter 4
Energy Balance
45
4.1 Introduction
As with mass, energy can be considered to be separately conserved in all but nuclear
processes. The conservation of energy, however, differs from that of mass in that energy can
be generated (or consumed) in a chemical process. Material can change form, new molecular
species can be formed by chemical reaction, but the total mass flow into a process unit must
be equal to the flow out at the steady state. The same is not true of energy. The total enthalpy
of the outlet streams will not equal that of the inlet streams if energy is generated or
consumed in the processes; such as that due to heat of reaction. Energy can exist in several
forms: heat, mechanical energy, electrical energy, and it is the total energy that is conserved.
In process design, energy balances are made to determine the energy requirements of the
process: the heating, cooling and power required. In plant operation, an energy balance
(energy audit) on the plant will show the pattern of energy usage, and suggest areas for
conservation and savings. In our project we will energy balance calculations on heat
exchangers, reactors and distillation column.
4.2 Energy balance around heat exchanger 1

For hot stream (tube side)
Pressure of feed stream = 480 psig
Temperature of hot stream in (T1) = 467 K
Temperature of hot stream out(T2) = 395 K
Cp of stream at mean temperature = 4375.20 J/kg.k
Molar flow rate = 667.044 kgmol/h
= 12.267 kg/s
Heat rate Q = m×Cp×ΔT
= 3984937.625 Watt
For cold stream (shell Side)
Q = 3984937.625 Watt
Temperature of cold stream in T1 = 339 K

By iteration temperature of cold stream at out of shell comes out to be 401 K
So mean temperature will be = 369.5 K
Cp at mean temperature = 3536.17 J/kg.K
Mass flow rate = 12.267 kg/s
46
Temperature of cold fluid into shell side
T2 = T1 + Q/m×Cp
= 400 K
4.3 Energy Balance around heat exchanger 2

For hot stream (tube side)
Pressure of feed stream = 480 psig
Temperature of hot stream in (T1) = 475 K
Temperature of hot stream out(T2) = 394 K
Cp of stream at mean temperature = 3534.14 J/kg.k
Molar flow rate = 667.044 kgmol/h
= 12.267 kg/s
Heat rate Q = m×Cp×ΔT
= 1340569.9 Watt
For cold stream (shell Side)
Q = 1340569.9 Watt
Temperature of cold stream in T1 = 400 K

By iteration temperature of cold stream at out of shell comes out to be 448 K
So mean temperature will be = 424.5 K
Cp at mean temperature = 3499.66 J/kg.K
Mass flow rate = 12.267 kg/s
Temperature of cold fluid into shell side

T2 = T1 + Q/m×Cp
= 449 K
47
4.4 Energy balance around isomerization reactor 1
The isomerization reactor is an adiabatic reactor operating at 480 psig and 350 oF (450K or
177oC). There are many reactions occurring parallel in the reactor releasing different
amounts of heat. The isomerization process is exothermic in overall and the heat liberated is
calculated separately for all the reactions.
Reaction 1
n-pentane iso-pentane
CH3-CH2—CH-CH3
CH3
ΔHf of n-pentane = -173.01 kj/mol

ΔHf of iso-pentane = -179.3 kj/mol
1 kgmol/h of n-pentane forming 1 kgmol/h of iso-pentane
So heat of reaction at 298K = -6.29 kj/mol.k
Mean heat capacity of reaction = 237 kJ/mol.K
Temperature difference = 152K
ΔHt = ΔH + Cp×ΔT
= 29.8 kj/mol
Reaction 2
n-Hexane 2,2-dimethylutane
ΔHf of n-hexane = -198.8 kj/mol

ΔHf of 2,2-dimethylbutane = -185.68 kj/mol
1 kgmol/h of n-hexane forming 1 kgmol/h of 2,2-dimethylbutane
So heat of reaction at 298K = ΔH = 13.1 kj/mol.k
Mean heat capacity of reaction = -107 kJ/mol.K
= -3.24 kj/mol
48
Reaction 3

= 6.30 kj/mol
Reaction 4
2-Methylpentane 2,2-dimethylbutane
ΔHf of 2-methylpentane = -174.74 kj/mol
1 kgmol/h of 2-methylpentane forming 1 kgmol/h of 2,2-dimethylbutane
So heat of reaction at 298K = ΔH = -10.9 kj/mol.k
= -97.8 kj/mol
Reaction 5
2-methylpentane 2,3-dimethylbutane

49
= -52.2 kj/mol
Reaction 6
methylcyclopentane + Hydrogen 2,2-dimethylbutane
ΔHf of methylcyclopentane = -105.93 kj/mol

ΔHf of hydrogen = 0
= -290 kj/mol
Reaction 7
Benzene + Hydrogen Cyclohexane
ΔHf of Benzene = 48.66 kj/mol

ΔHf of Cyclohexane = -156.2 kj/mol
1 kgmol/h of benzene forming 1 kgmol/h of cyclohexane
= -292 kj/mol
Reaction 8
Cyclohexane + Hydrogen 2,2-dimethylbutane

50
1 kgmol/h of cyclohexane forming 1 kgmol/h of 2,2-dimethylbutane
= -159 kj/mol
Reaction 9

= -92.7 kj/mol
Reaction 10
n-Butane Iso-butane
ΔHf of n-Butane = -147 kj/mol

ΔHf of Iso-Butane = -158.4 kj/mol
1 kgmol/h of n-butane forming 1 kgmol/h of iso-butane
= -307 kj/mol
Thus
51
Total heat generated in all 10 reactions = -1200 kj/mol
Total moles leaving from reactor 1 = 595.94 kgmol/h
Total weight of products = 609884 kg/h
Therefore Tout = Tin + Q/m×Cp
Cp of stream = 1382.57 kj/mol.k
So Tout = 475 K
4.5 Energy balance around Isomerization reactor 2

The product leaving isomerization reactor 1 is passed through heat exchanger 2 where it
exchanges some heat with feed stream. The final temperature of the stream being introduced
to 2nd reactor is maintained at 446k. This isomerization reactor is also an adiabatic reactor
operating at 446k and pressure of 465 psig. The same reactions are occurring parallel in the
reactor releasing different amounts of heats. Which are calculated as following:
Reaction 1
n-pentane iso-pentane
CH3-CH2—CH-CH3
CH3
ΔHf of n-pentane = -173.01 kj/mol

ΔHf of iso-pentane = -179.3 kj/mol
1 kgmol/h of n-pentane forming 1 kgmol/h of iso-pentane
So heat of reaction at 298K = -6.29 kj/mol.k
Temperature difference = 446-298 K
= 148 K
= 28.1 kj/mol
52
Reaction 2

= -2.77 kj/mol
Reaction 3

= 6.10 kj/mol
Reaction 4
2-Methylpentane 2,2-dimethylbutane
Temperature difference = 148 K
53
= -94.1 kj/mol
Reaction 5
2-methylpentane 2,3-dimethylbutane

= -50.3 kj/mol
Reaction 6
methylcyclopentane + Hydrogen 2,2-dimethylbutane
ΔHf of methylcyclopentane = -105.93 kj/mol

= -282 kj/mol
Reaction 7

54
= -156 kj/mol
Reaction 8

= -91 kj/mol
Reaction 9
n-Butane Iso-butane
ΔHf of n-Butane = -147 kj/mol

ΔHf of Iso-Butane = -158.4 kj/mol
1 kgmol/h of n-butane forming 1 kgmol/h of iso-butane
55
= -297 kj/mol
Thus
Total heat generated in all 9 reactions = -1170 kj/mol
Total moles leaving from reactor 1 = 576.67 kgmol/h
Total weight of products = 590164.078 kg/h
Therefore Tout = Tin + Q/m×Cp
Cp of stream = 1360 kj/mol.k
So Tout = 467 K
4.6 Energy balance around Stabilizer column

The product leaving isomerization reactor-2 at 467k is passed through heat exchanger 1 and
leaves at 395 k where it is introduces to stabilizer. The stabilizer, at the end of UOP PENEX
UNIT helps to separate the gaseous components where light components H2 CH4 HCL will
go out as top product and remaining components will condense due to the expansion from
450 psig to 350 psig approximately. This is a type of distillation column having a fin fan
cooler instead of total condenser after top plate. The gaseous stream leaves the column at
350k which is further cooled by fin fan cooler to about 310 k. the bottoms are heated up to
boiling point and leaves the column at 380k. The energy changes involved in reboiler and
cooler are accounted as follow.
By the design calculations, temperature at the top and bottom plate is given as:
Top plate temperature = 350 k

Bottom plate temperature = 372 k
4.6.1 Fin fan Cooler

Inlet temperature = 350 k
Outlet temperature = 310 k
Moles leaving as top product = 46.901 kgmoles/hr
Cp of top stream at mean temperature = 1210 kj/mol.k
Thus Heat removed as Qrem = m×Cp×ΔT
=2270008.4 kj/hr
4.6.2 Reboiler
Inlet temperature = 372 k
Outlet temperature = 380 k
56
Moles leaving as bottom product = 535.668 kgmoles/hr
Cp of bottom stream at mean temperature = 155 kj/mol.k
Thus Heat removed as Qrem = m×Cp×ΔT
= 664228.32.4 kj/hr
57
Chapter 5
Design of Process Equipment
58
5.1 Heat exchanger design
The complex flow pattern on the shell-side, and the great number of variables involved, make
it difficult to predict the shell-side coefficient and pressure drop with complete assurance. In
methods used for the design of exchangers prior to about 1960 no attempt was made to
account for the leakage and bypass streams. Typical of these “bulk-flow” methods are those
of Kern (1950) and Donohue (1955). Tinker
(1951, 1958) published the first detailed stream-analysis method for predicting shell-side
heat-transfer coefficients and pressure drop. Tinker’s presentation is difficult to follow, and
his method difficult and tedious to apply in manual calculations. It has been simplified by
Devore (1961, 1962). Mueller (1973) has further simplified Devore’s method. Bell (1960,
1963) developed a semi-analytical method based on work done in the cooperative research
programme on shell and tube exchangers at the University of Delaware. His method accounts
for the major bypass and leakage streams and is suitable for a manual calculation.
5.1.1 Determination of Shell Diameter

Temperature of hot fluid in to tube side T1 = 467 K
Temperature of hot fluid out from tube side T2 = 395 K
Temperature of cold fluid in to shell side t1 = 339 K
Temperature of Fluid out from Shell Side t2 = 390 K
Mean Temperature on tube side = 431 K
Mean Temperature on shell side = 364.5 K
Heat capacity of fluid on shell side in = 150 KJ/Kgmol- C
Heat capacity of fluid out from shell side = 153.5 KJ/Kgmol- C
Heat capacity of hot fluid in to tube side = 235.2 KJ/Kgmol- C
Heat capacity of hot fluid out from tube side = 230.6 K Kgmol- C
Mean heat capacity on shell side = 151.75 K Kgmol-C
Mean heat capacity on tube side = 232.9 KJ/Kgmol- C
Mass flow rate of cold fluid to shell side = 43898.575 kg/h
= 12.104 kg/s
Mass flow rate of hot fluid in tube side = 41790 kg/h
= 11.6 kg/s
59
Density of hot fluid to tube side = 488.7 kg/m3
Density of cold fluid to shell side = 264.9 kg/m3
Heat load Q = m × Cp × ΔT
Q = 18505 KW
Log mean temperature difference
So putting values we have
ΔTlm = 57.33 K
Ft correction factor
We select 2 shell passes and 4 tube passes
We know that
S = 0.1065
And
𝑻𝟏 − 𝑻𝟐
𝑹=
𝒕𝟏 − 𝒕𝟐
R = 1.2254
So from fig 8, Ft = 0.95
Now
ΔTm = 0.95 × 57.33
= 54.472 K
From fig 9, Let overall heat transfer coefficient

= 800 W/m2- C
60
Figure 8: Temperature correction factor Ft
Figure 9: Overall Heat Transfer Co-efficient

61
5.1.1.1 Provisional area
We know that
Heat Load Q = U × A × ΔTm
Area A = Q/(U × ΔTm)
= 424.63 m2
We choose following type of tubes
Outer diameter do = 20 mm = 0.02 m

Inner diameter di = 16 mm = 0.016 m
Tube length L = 4.88 m
Thus Area of a single tube is,
At = L×do×π
= 0.306464 m2
Number of tubes Nt = Provisional area/tube area
= 424.63/0.306464
= 1386
5.1.1.2 Bundle diameter
We have following formulae
As shell side fluid is relatively clean so we take 1.25 triangular pitch, and values of constants
n1 and K1 can be taken from table “6” using 2 tube passes
Putting values we have
Dia. of Bundle Db = 796.513 mm
62
Table 6: Constant Values for dia. of bundle determination
.
Using split ring floating head, from Figure 10
We have shell to bundle diametrical clearance = 68 mm
Therefore Diameter of shell Ds = 68 + 796.513 mm
= 864.5 mm
Figure 10: Shell to Tube Bundle Clearence
63
5.1.2 Determination of tube side heat transfer coefficient
Tube cross sectional area = π/4 × di = 200.6 mm2
Tubes per pass = Nt/4 = 346

Total flow area
= tubes per pass × tube cross sectional area
= 0.06961 m2
Mass velocity of hot fluid = mass flow/ tube flow area
= 166.765 kg/s-m2
Linear velocity of fluid Ut = mass velocity of fluid/density of fluid
= 0.34122 m/s
We know that
So,
Tube side heat transfer coefficient, hi = 11912.9 W/m2- C
5.1.3 Determination of tube side pressure drop
Tube side pressure drop can be calculated using following correlation
Where,
Np = Number of tube passes
64
Jf = Friction factor
L = Length of tube
Ut = Linear velocity of fluid
µ = Viscosity of fluid in tube

Reynold Number calculated as
𝜌𝑢𝑑𝑖
𝑅𝑒 =
µ
= 31396.7
And from Figure 11, Jf factor can b taken as = 3.7×10-3
Figure 11: Tube side Friction factor
Thus Putting values in above mentioned correlation and neglecting viscosity terms we
calculate tube side pressure drop as,
ΔPt = 1.311 kPa
65
5.1.4 Shell side heat transfer coefficient
Shell side coefficient is given by
Where
hoc = heat transfer coefficient calculated for cross over an ideal tube bank with no
leakage or by passing.
Fn = correction factor to allow for the effect of number of vertical tubes

Fw = window effect correction factor
Fb = bypass stream correction factor
FL = leakage correction factor
5.1.4.1 Ideal cross flow coefficient (hoc)
Where,
μ = Viscosity of cold fluid
kf = Thermal conductivity
Jh = Heat correction factor
Re = Reynold number
Pr = Prandtel number
The heat-transfer coefficient for an ideal cross-flow tube bank can be calculated using the
heat transfer factors jh given in Figure 12.
Area for cross flow
66
Where
lb = Baffle spacing
pt = Tube pitch
Taking baffle spacing as 1/5 of shell diameter
So
lb = Ds/5 = 172.903 mm
pt = 25 mm
So , As = 0.0605 m2
Gs = mass flow on shell side/ cross flow area

Gs = 201.502 kg/s-m2
Re = (𝐺𝑠 × 𝑑𝑜)/µ
= 33583
𝐶𝑝×𝜇
Pr =
𝐾𝑓
here
Cp = Mean heat capacity of cold fluid = 151.75 KJ/Kgmol- C
μ = Viscosity of cold fluid = 0.12×10-3 kg/m.s
kf = Thermal conductivity = 0.05982 W/m-K
So Pr = 0.30441
Figure 12: Shell side heat transfer factor against Reynold number
67
So putting values in given correlation we have,
Ideal cross flow coefficient hoc = 2501.29 W/m2.K
5.1.4.2 Tube row friction factor (Fn)
The mean heat-transfer coefficient will depend on the number of tubes crossed. Figure 13 is
based on data for ten rows of tubes. For turbulent flow the correction factor Fn is close to 1.0.
In laminar flow the heat-transfer coefficient may decrease with increasing rows of tubes
crossed, due to the build-up of the temperature boundary layer. The factors given below can
be used for the various flow regimes,
Ncv is number of constrictions crossed = number of tube rows between the baffle tips
1) Re >2000, turbulent;
2) Re >100 to 2000, transition region,
3) Re <100, laminar region,
Ncv = height between baffle tips (Hc)/tube vertical pitch(pt)
Where, Hc = Bc × Ds
and Bc is a the baffle cut as a fraction which is = 0.25
Hc = 0.2161 mm = 216.1 m
Height between baffle tips = (Ds−4) × Hc = 432.25
Tube vertical pitch = pt = 0.87 × 25 = 21.75 mm
Thus Ncv = 19.87
Figure 13: Tube row correction factor Fn
So
Fn = 1.02
68
5.1.4.3 Window correction factor (Fw)
This factor corrects for the effect of flow through the baffle window, and is a function of the
heat-transfer area in the window zones and the total heat-transfer area. The correction factor
is shown in Figure 15 plotted versus Rw, the ratio of the number of tubes in the window
zones to the total number in the bundle, determined from the tube layout diagram and we
calculate Ra/ Figure 14.
Where,
Hb = Height from baffle chord to top of tube bundle
Db = Bundle diameter
Bc = Bundle cut as a fraction
So
Hb = 182.128 mm, Baffle cut = Hb/Ds = 0.2106
Figure 14: Baffle geometrical factors
From Figure 14 we have
Ra/ = .12
69
Now tubes in one window area = Nw = Nt × Ra/ = 166.22
Tubes in cross flow area = Nt – (2×Nw) = 1054
Rw = 2×Nw/Nt
Rw = 0.24
From Figure 15, we have Fw = 1.12
Figure 15: Window correction factor
5.1.4.4 Bypass correction factor

This factor corrects for the main bypass stream, the flow between the tube bundle and the
shell wall, and is a function of the shell to bundle clearance, and whether sealing strips are
used.
Where
α = 1.5 for laminar flow, Re <100, and 1.35 for transitional and turbulent flow, Re>100,
Ab = clearance area between the bundle and the shell
As = maximum area for cross-flow
Ns = number of sealing strips encountered by the bypass stream in the cross-flow zone,
Ncv = number of constrictions, tube rows, encountered in the cross-flow section.
70
Ab = 0.01176 mm2
Ab/As = 0.194
So Fb = 0.769
Very low sealing strips needed so we try one strip for each five vertical rows
Ns/Ncv = 1/5
Now Fb becomes = 0.6761

5.1.4.5 Leakage correction factor
Using clearances as specified in the Standards
Using following equation,
Where,
Atb = Total area between baffles and tube

ct = diametrical tube to baffle clearance
So Asb = 0.008672
AL = Atb + Asb = 0.0393
AL/As = 0.6494
From Figure 16
β = 0.64
Thus, FL = 0.6979
71
So Shell side heat transfer coefficient
hs = 1632.05 W/m2- C
Figure 16: Coefficient for FL
5.1.5 Pressure drop on shell side

From Error! Reference source not found. for
Re = 33588.7
Jh factor = 4 × 10-2
Us = Gs/ ρ
Us = 0.7606 m/s
We have following relation
Neglecting viscosity term and putting values we have
72
∆Pi = 487.394 N/m2 = 0.487 kPa
5.1.5.1 Bypass correction factor for pressure drop

Bypassing will affect the pressure drop only in the cross-flow zones. The correction factor is
calculated from the equation used to calculate the bypass correction factor for heat transfer,
equation 12.30, but with the following values for the constant [6]
-Laminar region, Re<100, α = 5.0
-Transition and turbulent region, Re>100, α = 4.0
We have following relation
Putting values
Fb` = 0.65
From Figure 17
= 0.57
Now
FL` = 0.2675
So
∆Pc = FL` × Fb` × ∆Pi
∆Pc = 188.464 N/m2 = 0.188 kPa
Figure 17: Coefficient for F'L , Pressure drop

73
5.1.5.2 Window zone
From Figure 14 for baffle cut at 25%
Ra = 0.19
Putting values
Aw = 0.05926 m2
Now
Uw = Mass flow/Aw× ρ
Uw = 0.7767 m/s
Where
So
Uz = 0.7686
Now
Nwv = 8.373
Relation for this
∆Pw = 164.914 N/m2 = 0.165 kPa
5.1.5.3 End zone

Relation for end zone is
∆Pe = 1001.02 N/m2
74
5.1.5.4 Total shell side pressure drop
Where
Nb = Number of baffles
Nb = [(L/lb) – 1 ]
Nb = 27.22
∆Ps = 11433.965 N/m2 = 11.43 kPa
5.2 Pump Design

5.2.1Pressure drop due to Friction
We take the pipe of 40 schedule having 6 inches diameter and following dimensions. [9] [10]
Outer dia = 168.3 mm
Thickness = 7.11 mm
Internal Dia = 154.08 mm
Length of pipe used = 150 ft = 46 m,
Flow rate of feed, Qo = 10,000 BPSD
= 66.5 m3/h
= 292.82 GPM [1 m3 =264.2 US Gallon]
Now calculating cross sectional area of pipe
𝜋
Area of pipe A = 𝑑2 = 0.02832 m2
4
Velocity of feed at inlet of the pump

Velocity = Qo/A
66.5 𝑚3/ℎ
= = 0.6522 m/s
0.02832 𝑚
Density of feed = 662.62 kg/m3

Viscosity of feed = 0.2799 centipoise = 1.0074 kg/m.hr
Now calculating Reynold number at inlet of pipe
𝜌𝑢𝑑
Reynold number, Re = = 259878.5
𝜇
From table 7, for commercial steel pipe taking absolute roughness as

75
e = 0.046
Table 7: Pipe roughness
Relative roughness = e/d0 = 0.046/168.3 = 2.7×10-4
From figure 18, taking friction factor as f = 0.0025
Figure 18: frication factor of pipes
So pressure drop in pipe due to friction is
𝐿 𝜌𝑢2
∆𝑃𝑓 = 8𝑓( )
𝐷𝑖 2
Where,
ΔPf = pressure drop due to friction, N/m2
L = length of pipe, m
Di = inside diameter of pipe, m
Ρ = density of feed kg/m3
76
µ = Viscosity of feed, kg/m.h
f = friction factor of pipe
Therefore pressure drop due to friction is
ΔPf = 841.33 N/m2
5.2.2 Work done by pump

∆𝑃 ∆𝑝𝑓
Work done = W = 𝑔∆𝑍 + −
𝜌 𝜌
Where,
w = work to be done by the pump, J/Kg
Δz = difference in elevation (Z1-Z2), m
ΔP = difference in system pressures (P1-P2), N/m2
ΔPf = pressure drop due to friction, N/m2
ρ = liquid density, kg/m3
g = acceleration due to gravity, m/s2
So taking elevation as 10 ft,
Δz = -10 ft
ΔP = 14.7 psi ˗ 480 psi = - 465.3 psi = ˗ 33008571.42 N/m2
So
W = -5092 J/kg
5.2.3 Power requirement

Power can be calculated by using following equation
w×m
P=
η
Where
W = Work done by pump, Watt
m = mass flow rate of feed, kg/s
η = pump efficiency
Thus, power required
77
j
5092 ×12.19 kg/s
kg
P = = 88673.5 watt = 88.673 Kw
0.70
5.3 Reactor Design

The heart of the Penex system is the reactor section. The Penex system will normally employ
two reactors in a series flow configuration with the total required catalyst loading being
equally distributed between the vessels.
Calculations
Inlet temperature of the stream = 422 k
Outlet temperature of the stream = 477 k
Pressure in the reactor = 480 Psig
LHSV (Liquid hour space velocity) = 1.43 hr-1
Space Time, T = 1/S
= 1/1.43
Space Time, T = 0.699 hr
We know the equation
T = V/Vo
Where,
V = Volume of reactor
Vo = Volumetric flow rate
Mass flow rate of Naphtha = 44160.576 Kg/h
Specific gravity of Naphtha S.G = 0.6633
Volumetric flow rate of feed, Vo = 10000 BPSD = 66.5 m3/hr
V = T * Vo
= 0.699 × 66.5
Volume of reactor = 46.50 m3
Since reactor is packed with catalyst. So, we will have to consider a fraction void which is Ɛ.
78
ƐA = 0.4
Vf = VƐ
Where,
Vf = Volume of reactor + Catalyst
Vf = 46.50×1.4
Vf = 65.1 m3
Suppose 30% space is provided at top and bottom of reactor. i.e.
Vf = 65.1× 1.3
Vf = 84.63 m3
So
Volume occupied by catalyst = 84.63 – 46.50
= 38.13 m3
Empty Space = 65.1 – 38.13
= 26.98 m3
Empty space at top = Empty space at bottom
So, Empty space at top = 13.49 m3
And, Empty space at bottom = 13.49 m3
Assuming length to diameter Ratio = L/D = 3
𝜋𝐿𝐷2 3𝜋𝐷3
V = =
4 4
84.63 = 3𝜋D3/4
D3 = 84.63 × 4 / 3 × 3.14
D = 3.29 m = 10.80 ft
L = 3×D
L = 3×3.29
L = 9.87 m = 32.37 ft
79
Table 8: Specification sheet for reactors
Description Unit Duty

Reactor inlet Temperature K 422
Reactor outlet Temperature K 477
Pressure in the Reactor Psig 480
Liquid Hourly Space Velocity(LSHV) Hr-1 1.43
Volume of Reactor m3 84.6

3
Flowrate Kg/h , m / hr 44160 , 66.5
Fractional Void age Ɛ 0.4
%ag additional space provided M 30
Length of Reactor m , ft. 9.87 , 32.37
Diameter of Reactor m , ft. 3.29 , 10.80
Volume occupied by Catalyst m3 38.13
Material of Construction Carbon Steel
5.4 Mechanical Design of vessel

Material of construction is carbon steel
Internal diameter =DI = 3.29 m
Operating pressure = 480 psig
Design pressure allowance = 10 % of operating pressure
Total design pressure =PI = = 528 psig = 36.39 bar
= 36.39 × 105 N/m2
From Table 9 = 3.639 N/mm2
Design stress at 450 K (177 C) and 3.369N/mm2
F = 105 N/mm2
Welding joint efficiency = j = 1
The joint is double welded with 100% radiography
80
Table 9: Typical design stress for plate
5.4.1 Cylindrical section

Thickness of wall is given by
e = (PI×DI)/2f-PI
e = (3.29×3.639×1000)/(210-3.639)
e = 58 mm
Adding corrosion allowance which is 2 mm
E = 58 + 2 = 60 mm
5.4.2 Doomed Section

Ellipsoidal head
e = PI × DI / 2 × j × f - .2PI
e = (3.29×3.639×1000)/(210×1-3.639×0.2)
e = 57.30 mm

e = 57.30 + 2
= 59.30 mm
81
Tori spherical head
Where
Cs = Stress concentration factor for tori spherical head
Where
Rc = Crown radius = Internal diameter
Rk = Knuckle radius
The ratio of the knuckle to crown radii should not be less than 0.06, to avoid buckling;
and the crown radius should not be greater than the diameter of the cylindrical section.
3.639×3.29×1000×1.77
e =
2×105×3.639(1.77−2)
e = 98.26 mm
e = 98.26 + 2 = 100.2 mm
The wall thickness of reactor is 60 mm also the thickness of ellipsoidal head is 60 mm while the
thickness of tori spherical head is 100 mm so both head and vessel will be casted from same metal.
5.5 Distillation Column Design

5.5.1 Number of Plates
Minimum number of plates
x is the mole fraction, lk and hk corresponds to light key and heavy key respectively. b and d
corresponds to bottoms and distillate respectively. lk is the relative volatility of light key
(butane) with respect to heavy key(Iso-pentane).
So
82
log [(0.343941/0.001182) ×
Nmin +1 = (0.097786/0.000403)] / log (1.83)
= log (70631.75) / log (1.83)
Nmin +1 = 18.45
Nmin = 17.45 say 18
5.5.2 Minimum reflux ratio

Underwood’s Equation:
Value of θ is calculated from the following equation
ℎ𝑒𝑎𝑡 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑒𝑑 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑓𝑒𝑒𝑑

𝑞=
𝑚𝑜𝑙𝑎𝑟 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑
Temperature of feed is 120 0C and the average boiling point of feed at 480 psig
is 200.28 0C. Average molar latent heat of the feed
= 23873.675 J/mol
Average specific heat of feed = 135.1 J/mol-0C

So,
[135.1× (200.28-120)+23873.675]/
q = 23873.675
q = 1.45
Value of θ is obtained by hit & trial
method.
θ = 1.14
so
Rmin = 0.78
Erbar-Maddox correlation Rm/(Rm+1) , R/(R+1) using these ratios, Nm/N [6]
Rm/(Rm+1) = 0.44
83
Table 10: Possible number of plates according to reflux ratio
R R/(R+1) Nm/N N
1 0.5 0.49 35.61
1.5 0.6 0.72 24.23
2 0.67 0.82 21.28
2.5 0.71 0.84 20.77
3 0.75 0.86 20.39
3.5 0.78 0.89 19.60
This shows that the number of plates falls off rapidly at first, though more slowly later, and
a value of R≈2 is probably the most economic.
5.5.3 Plate efficiency

Using O’Connell relation => Eo = 51 – 32.5 log (µaαa)
µa = Molar average liquid viscosity mNs/m2

= 0.366
αa = average relative volatility of the light key with respect to heavy key
= 1.698
Overall column’s efficiency = Eo = 66.80% or 0.6680

5.5.4 Actual number of plates
𝑁𝑂. 𝑜𝑓 𝑖𝑑𝑒𝑎𝑙 𝑝𝑙𝑎𝑡𝑒𝑠
𝐸𝑒𝑓𝑓𝑒𝑐𝑖𝑒𝑛𝑐𝑦 =
𝑁𝑜. 𝑜𝑓 𝑟𝑒𝑎𝑙 𝑝𝑙𝑎𝑡𝑒𝑠
NO. of real stages including reboiler

𝑁𝑜. 𝑜𝑓 𝑖𝑑𝑒𝑎𝑙 𝑠𝑡𝑎𝑔𝑒𝑠
𝑒𝑓𝑓𝑒𝑐𝑖𝑒𝑛𝑐𝑦
= 21.28/.6680
N = 31.85 say 32
5.5.5 Feed point location
Empirical equation given by Kirkbride (1944) is;
Where
Number of stages above the feed, including any
Nr = partial
condenser,
Number of stages below the feed, including the
Ns = reboiler,
84
Molar flow bottom
B = product,
D = Molar flow top product,
xf,hK = Concentration of the heavy key in the feed,
xf,lK = Concentration of the light key in the feed,
xd,hK = Concentration of the heavy key in the top product,

Concentration of the light key if in the bottom
xb,lK = product.
Log(Nr/Ns) = 0.206 log[(524.508/52.1548) ×

(0.3128/0.0098)×(0.0001182/(0.000403)2]
= 0.206 log [0.27289]
Log (Nr/Ns) = -0.116
Nr/Ns = antilog (-0.116)

Nr/Ns = 0.765
Nr = 0.765N
No. of stages excluding reboiler = 32 – 1 = 31
Nr + Ns = 31
0.765Ns + Ns = 31
Ns = 31/1.765 = 17.56 say 17

So
Nr = 31-17 = 14
So feed enters at plate number 17.
Reflux ratio, R = 2
R = Lr/D
Where, Lr is liquid flow rate in
rectifying section.
Lr = R×D
= 2 × 52.1548
Lr = 104.3096 kgmol/h
85
Vr = Lr + D
= 104.3096 + 52.1548
Vr = 156.4644 kgmol/h
Where, Vr is vapor flow rate in rectifying section.
Ls = Lr + F
Where, Ls is liquid flow rate in stripping section.
Ls = 104.3096 + 576.678
Ls = 680.9814 kgmol/h
Vs = Ls - B
Where, Vs is vapour flow rate in stripping section.
Vs = 680.98 - 524.508
Vs = 156.47 kgmol/h
5.5.6 Column diameter

From ChemCad simulator
Est. T top 0C = 36.6667
Est. T bottom 0C = 200.3698
Density of liquid, ρL = 612.7 kg/m3

Density of Gas, at top ρv= 14.6
kg/m3
Density of liquid ,at bottom ρL = 545.57 kg/m3

Density of Gas, at bottom ρv = PM/RT
Where,
P = Operating pressure of the column
M = Average molecular mass of product

Temperature of the bottom product
T = in K
R = 8314 J/kgmol.K
P = 494.17psia or 3.406*106pascal
Mavg = 43.99 kg/kmol
86
T at bottom = 200.28 0C or 473.33 K
So
Density of Gas, ρg = 14.6 kg/m3
The liquid-vapour flow factor FLV is given by:
Where
L = Liquid mass flow rate, kg/s
V = Vapor mass flow rate, kg/s
104.3096 14.6
𝐹𝐿𝑉 = √
156.4644 612.7
FLV top = 0.103
680.98 12.395
𝐹𝐿𝑉 𝑏𝑜𝑡𝑡𝑜𝑚 = √
156.47 545.6
FLV bottom = 0.65
Take plate spacing as 0.5m
From figure 11.27 [6]
87
Top K1 = 0.09
Bottom K1 = 0.066
Surface Tension at Top =
= [151.260(612.7-14.6)/43.99]^4 *10-12
= 17.88 *10-3 N/m
Surface tension at bottom = [264.46(545.6-12.395)/79.77]^4*10-12
= 9.73*103 N/m
Surface tension correction factor top = 0.007*(17.88/20)0.2

= 0.088
Surface tension correction factor at bottom
= 0.0086*(9.73/20)0.2
= 0.0744
Flooding Velocity =
= 0.088[(612.7-14.6)/14.4]1/2
= 0.088*6.4
= 0.5632 m/s
At bottom
= 0.0744[(545.6-12.395)/12.395]1/2
= 0.4879 m/s
In design normally we take 85% flooding velocities
So
At top = 0.5632×0.85
= 0.4782
At bottom = 0.4879×0.85
= 0.414
88
Volumetric flow rate
Rectifying section
= (567.1134*43.99)/(14.6*3600)
= 0.4746 m3/s
Stripping section
= (565.612*79.77)/(12.395*3600)
= 1.013 m3/s
Area at top
= 0.4746/0.4782
= 2.41 m2
Area of base = 1.013/0.4141
= 1.146 m2
Diameter of column
𝑑2
= 𝜋
4
Diameter at bottom = 1.76m

Diameter at top = 1.36m
5.5.7 Column height

The tower height can be related to the number of trays in the column. The following formula
assumes that a spacing of two feet between trays will be sufficient including additional five to
ten feet at both ends of the tower. This includes a fifteen percent excess allowance of space
(Douglas, 1988).
Htower = 2.3 Nactual
= 2.3 31
= 71.3 ft = 71./3.28
= 21.74 m
5.6 Provisional plate design

Diameter of column= Dc = 1.76 m
Column area Ac = 2.43m2
89
Down comer Area = Ad = 15% of Ac
= 0.15×2.43 = 0.364 m2
Net Area = An = Ac- Ad = 2.43 – 0.364
= 2.047 m2
Active area Aa = Ac - 2Ad = 2.43 – 2(0.364)
= 1.70 m2
Hole area Ah take 12 % of Aa as first trial
= 0.12× 1.70 = 0.204 m2
From the graph 11.31 Coulson volume 6
[Lw/Dc] vs[ Ad/Ac]×100
[Lw/Dc] = 0.8
Lw = 0.8 × 1.76 = 1.408 m
Take weir length = 50 mm
Hole diameter = 5 mm
Plate thickness = 5 mm
Plate spacing = 500 mm = 0.5 m
5.6.1 Check weeping
Maximum flow rate = 1090.13*43.9/3600

= 13.32
Maximum Liquid rate at 70% turn down = 13.32×0.7 = 9.32 kg/s
Maximum how = 750[Lm (ρL×Lw)]2/3

= 750[13.32/(612.7×1.408)]
= 47.81 mm say 48 mm
Minimum liquid flow rate = 750[9.32/ (612.7×1.408)]
= 37.77 say 38 mm
90
At minimum liquid rate (hw+how) = 50 + 38 = 88 mm
From figure 11.30 [6]
K2 = 30.9
Uh (min) = [K2-0.90(25.4-Dh)] /(ρv) 0.5
= [30.9-0.90(25.4-5)]/ (14.6)0.5
= 3.28 m/s
Actual minimum liquid velocity = Minimum vapor rate /Ah
= 0.7×1.13/ 0.204 =3.47m/s
So minimum operating velocity is well above the weeping velocity
5.6.2 Plate pressure drop

Maximum vapor velocity through the hole
= 4.96 m/s
Plate thickness/ hole area =1 and
[Ah/Ap] = [Ah/Aa] = 0.1
Co from graph = 0.84
hd + = 51 × [uh/Co]2 [ρv ρL]
= 51× [4.96/0.84]2 [14.6/614.5]

= 53 mm
Residual head = 12.5× 103 ρL = 12500/614.5

= 20.34 mm
Total pressure drop = ht = hd + (hw+how) + hr
= 53 + 87 + 20.34 = 160 mm
Assumed plate pressure drop is 100 mm
Down comer liquid backup
hap = hw-10
= 40 mm = 0.04 m
Area under Apron = hap × weir length
91
= 0.04 × 1.408 = 0.0563 m2
hdc = 166× [Lwd ρL × Am ]2
= 166× [13.32/ 614.5 × 0.0563]2

= 24.58 mm say 25 mm
hb = ( hw+how) + ht + hdc
hb = 87 + 160 + 25 = 272 mm
= 0.272 m of liquid
½(plate spacing + weir height) = ½(500 + 50) = .275m

hb should not greater than ½(plate spacing + weir height) so, it is acceptable
5.6.3 Residence time
Tr = (Ad*Hb*density of liquid)/Lwd
= (0.365*0.275*614.6)/13.32= 4.62 sec
Is satisfactory
5.6.4 Check Entrainment
Uv = maximum flow rate/ net area

= 1.013/2.045 = 0.49%
% Flooding = (0.49/0.5632)*100 = 87%
92
Chapter 6
Process Flow Diagrams
93
6.1 Introduction
The chemical process industry is involved in the production of a wide variety of products that
improve the quality of our lives and generate income for companies and their stock holders.
In general, chemical processes are complex, and chemical engineers in industry encounter a
variety of chemical process flow diagrams. These processes of then involve substances of
high chemical reactivity, high toxicity, and high corrosivity operating at high pressures and
temperatures. These characteristics can lead to a variety of potentially serious consequences,
including explosions, environmental damage, and threats to people’s health. It is essential
that errors or omissions resulting from missed communication between persons and/or groups
involved in the design and operation do not occur when dealing with chemical processes.
Visual information is the clearest way to present material and is least likely to be
misinterpreted. For these reasons, it is essential that chemical engineers be able to formulate
appropriate process diagrams and be skilled in analyzing and interpreting diagrams prepared
by others. The most effective way of communicating information about a process is through
the use of flow diagrams. Here we will discuss flow diagram of UOP penex process. [11]
6.2 Block flow diagram

This diagram consisted of a series of blocks representing different equipments or unit
operations that are connected by input and output streams. Important information such as
operating temperatures, pressure conversions and yields are included on diagrams along with
flow rates and chemical compositions. However the diagram does not include any details of
equipment within any of the blocks.
The block flow diagrams can take any of the two forms. First a block flow diagram may be
drawn for single process. Alternatively, a block flow diagram may be drawn for a complete
chemical process involving many different chemical processes. We distinguished between
these two by first block flow diagram and second block flow diagram.
6.3 Conventions and format

1. Operations are shown by blocks
2. Major flow lines shown arrows giving directions of flow
3. Flow goes from left to right whenever possible
4. Critical information unique to the process is supplied
5. Light streams gases are towards top and heavy streams (liquids) are towards bottom
6. If lines cross then horizontal line is continuous and vertical line is broken.
7. Simplified material balance is provided
The major advantage of block flow diagram is to give an over view that how the plant
operates and how the equipment’s interact with one another. On the other in other to the
block uncluttered, only limited information is available about each process. The BFD orients
the viewer the products and major areas of operation, in addition they are used to sketch out
and screen potential process alternatives.
94
6.4 Process flow diagram
The process flow diagram represents quantum setup from the BFD in terms of amount of
information that it contains. The PFD contains the bilk of chemical engineering data
necessary for the design of chemical process. If there are PFD’s from different sources for the
same process then most of them will be delivering the same set of major information needed
to take an overview of the process. Most PFD’s deliver following information in particular: .
1. All major pieces of equipment’s are shown with unique description of the equipment
and a numbers.
2. All process flow streams and utility streams are shown and identified by a number. A
description of process condition and chemical composition of each stream is included
either directly on PFD or in table accompanying flow summery table
3. Basic control loops illustrating the control strategy used to operate the process during
normal conditions.
Often PFD’s are drawn on large sheets of paper (for example size D: 24” × 36”) and several
connected sheets may be required to complete the process. The basic information provided by
PFD is categorized into following
1. Process topology
2. Stream information
3. Equipment information
6.4.1 Process topology

Conventions used for identifying process are given in the table below
Table 11: Conventions for Process Equipment
Process equipment General format

Compressor or turbine C
Heat Exchanger E
Fired heater H
Pump P
Reactor R
Tower T
Vessel V
Storage tank TK
A/B Parallel or back up equip.
This table provides necessary information for the identification of a process equipment icon
shown in PFD. For example P-101 shows
1) P-101 identifies equipment as pump

2) P-101 indicates that the pump is located in the area 100 of the plant
3) P-101 Indicates that the specific pump is numbered as 01 in the area 100
95
6.4.2 Stream information
Each process stream is identified by a number in the diamond box located over the stream.
The direction of the stream is identified by one or more arrow heads. Utility streams are
shown in the similar way. Utilities are needed services that are needed at the plant.[11]
Table 12: Indication of utility streams
Names Description
lps Low pressure steam 3-5 bar
mps Medium pressure steam 10-15 bar
hps High pressure steam 40-50 bar
cw Cooling water from cooling tower at 30 C
wr River water In at 25 C and returned at 35 C
rw Refrigerated water In at 5 C and out at 15 C
rb Refrigerated brine In at -45 C and returned at < 0 C
cs Chemical waste water with high BOD
ss Sanitary waste water with high BOD
el Electrical heat supply (220V, 240V, 660V service)
ng Natural Gas
fg Fuel Gas
fo Fuel Oil
fw Fire water
Table 13: Stream Information Table
Stream no. 1 2 3 4 5 6 7 8 9 10 11 12 13
Temperature C
Pressure bar
Mass flow
Molar flow
Component Flow
hydrogen 0 0 131.2 131.2 131.2 131.2 131.2 41.72 41.72 31.10 31.10
0 31.1
Methane 0 0 0 0 0 0 0 0.721 0.721 0.721 0.721
0 0.721
Ethane 0 0 0 0 0 0 0 0.366 0.366 0.416 0.416
0 0.416
Propane 0 0 0 0 0 0 0 8.494 8.494 8.494 8.494
0 8.494
Iso-butane 0.644 0.644 0 0 0.641 0.641 0.641 5.054 5.054 6.10 6.10
0 6.1
n-butane 11.35 11.35 0 0 11.29 11.29 11.29 6.324 6.324 5.72 5.72
0 0.07
Iso-pentane 97.85 97.85 0 0 97.84 97.84 97.84 148.7 148.7 180.4 180.4
0 31.1
n-pentane 137.6 137.6 0 0 137.6 137.6 137.6 86.72 86.72 55.06 55.06
5.72 0
Cyclopentane 12.25 12.25 0 0 5.192 5.192 5.192 180.4 0
2,2-Dimethybutane 5.129 5.129 0 0 10.10 10.10 10.10 66.13 66.13 98.38 98.38 55.06 0
2,3- 0 0 108.7 108.7 108.7 21.21 21.21 26.81 26.81 0
98.38
dimethyl 10.10 10.10
2-Methylpentane
butane 63.63 63.63 0 0 105.3 105.3 105.3 0
3-methypentane 45.27 45.27 0 0 19.52 19.52 19.52 107.4 107.4 105.5 105.5 105.4
n-hexane 105.3 105.3 0 0 17.24 17.24 17.24 50.56 50.56 25.07 25.07 25.07 0
methylcyclopentan 19.52 19.52 0 0 20.85 20.85 20.85 18.62 18.62 17.75 17.75 17.75 0
e
Cyclohexane 17.25 17.25 0 0 8.59 8.59 8.59 17.60 17.60 7.83 7.83 7.83 0
Benzene 20.86 20.86 0 0 0 0 0 0 0 0 0 0 0
n-heptane 8.627 8.627 0 0 0.050 0.050 0.050 7.41 7.41 7.12 7.12 7.12 0
HCl 0 0 0.202 0.202 0.202 0.202 0 0
96
Figure 19: PFD of UOP Penex Once through process in Hysys
97
Chapter 7
HAZOP
98
7.1 What is HAZOP?
A HAZOP study, as the name implies, identifies hazards and operability problems. The
concept involves investigating how the plant might deviate from the design intent. If, in the
process of identifying problems during a HAZOP study, a solution becomes apparent, it is
recorded as part of the HAZOP result. The prime objective for the HAZOP is problem
identification. Although the HAZOP study was developed to supplement experience-based
practices when a new design or technology is developed, its use has expanded to almost all
phases of a plant's life. HAZOP is based on the principle that several experts with different
backgrounds can interact and identify more problems when working together than when
working separately and combining their results.
7.1.1 Objectives of HAZOP

The objectives of HAZOP study are following:
 To identify (area of the design that may possess a significant hazard potential.
 To identify and study features of the design that influence of a hazardous incident
occurring.
 To familiarize the study team with the design information available
 To ensure that a systematic study is made of the areas of significant hazard potential.
 To identify the pertinent design information not currently available to the team.
 To provide a mechanism for feedback to the client of the study team`s detailed
comments.
7.1.2 How and Why HAZOP is used.
 HAZOP identifies potential hazards, failures and operability problems.
 Its use is recommended as a principal method by professional institutions and

legislators on the basis of proven capabilities for over 40 years.
 It is most effective as a team effort consists of plant and prices designers, operating
personnel, control and instrumentation engineer etc.
 It encourages creativity in design concept evaluation.
 Its use results in fewer commissioning and operational problems and better informed
personnel, thus confirming overall cost effectiveness improvement.
99
7.1.3 Advantages of HAZOP
 Systematic and comprehensive technique.
 Team work, everyone is available in discussion.
 Everyone is responsible for his or her work, so no one can blame can blame the
others.
 Ownership is divided among the participants,
7.1.4 Limitations of HAZOP
 Qualitative technique
 Very time consuming and laborious for complex systems
 Required detailed drawings design.
 Guide word would need to be developed.
7.2 Technical Approach to HAZOP
7.2.1 Guidewords, Selection of parameters and Deviation
The HAZOP process creates deviations from the process design intent by combining guide
words (No, more, less, etc.) with process parameters resulting in a possible deviation from
design intent, for example, when the guide word “No” is combined with the parameter “flow”
the deviation “no flow” results. The team should then list all credible causes that will in a no
flow condition for the node. A sample list of guide words is given below. It should be pointed
out that not all guideword/parameters combination will be meaningful.
Guidewords:
No or not-no part of the intent is achieved and nothing else occurs (e.g., no flow)
More-quantitative increase (e.g., higher temperature)
Less-quantitative decrease (e.g., lower pressure),
Part of-qualitative decrease (e.g., only one of two components in mixture)
Reverse-opposite (e.g., backflow)
Other than-no part of the intent is achieved and something completely different occurs (e.g.,
flow of wrong material).
As well as-qualitative increase (e.g., an impurity) The application of parameters will depend
on the type of process being considered, the equipment in the process and the process intent,
100
the HAZOP-PC software include two pop-up menus that lists both specific parameters and
general parameters, The most common specific parameters that should be considered are
flow, temperature, pressure, and where appropriate, level. In almost all instances, these
parameters should be evaluated for every node. The scribe shall document, without
exception, the team’s comments concerning these parameters.
7.3 The System for HAZOP Method.

 Those system, engineered designs and written procedures that are designed to prevent
catastrophic release of hazardous or flammable material.
 Those systems that are designed to detect and give early warning following the
initiating cause of a release of hazardous or flammable material
 Those system or written procedures that mitigate the consequences of a release of

hazardous or flammable material.
The team should use care when listing safeguard, Hazard analysis require an evaluation of the
consequences of failure of engineering and administrative controls, so a careful determination
of whether or not these items can actually be considered safeguard must be made. In addition,
the team should consider realistic multiple failures simultaneous events when considering
whether or not any of the above safeguards will actually function as such in the event of an
occurrence.
7.4 HAZOP Study Procedure

 Procedure in HAZOP study consists of examining the process and instrumentation
(P&I) line diagram, process line by process line.
 A list of guide words is used to generate deviations from normal operation

corresponding to all conceivable possibilities.
 Guide words covering every parameter relevant to the system under review i.e. flow
rate and quality, pressure, temperature, viscosity, components etc.
 Flowchart for application of HAZOP is shown in figure.
7.5 Hazards Identification Related To Naphtha

7.5.1 Emergency Overview
This product is a clear to amber liquid with a strong hydrocarbon odor, it may also have a
sulfurous or rotten egg odor. Hydrogen sulfide, an extremely flammable and very toxic gas is
expected to be present. This product is a volatile and extremely flammable liquid that may
cause flash fires. Keep away from heat, sparks and flames and other sources of ignition. This
product contains benzene, which may cause cancer or be toxic to blood forming organs.
101
Figure 20: Hazop study flow chart
7.5.2 Potential Acute Health Effects.
Inhalation: Breathing high concentrations may be harmful. Mist or vapor can

irritate the throat and lungs. Breathing this material may cause central
nervous system depression with symptoms including nausea, headache,
dizziness, fatigue, drowsiness or unconsciousness.
Eye Contact: This product can cause eye irritation from short-term contact with
liquid, mists or vapors. Symptoms include stinging, watering, redness
and swelling.
102
Skin Contact: This product is a skin irritant. Contact may cause redness, itching,
burning and skin damage.
Ingestion: Ingestion may result in nausea, vomiting, diarrhea and restlessness.

Aspiration (inadvertent suction) of liquid into the lungs must be
avoided as even small quantities in the lungs can produce chemical
pneumonitis, pulmonary edema or hemorrhage and even death.
7.5.3 Potential Chronic Health Effects

Signs: Chronic effects of overexposure are similar to acute effects including
central.
Symptoms: Nervous system (CNS) effects and CNS depression.
Carcinogenic This material may contain benzene, ethyl benzene and naphthalene at
concentrations above 0.1%. Benzene is considered to be a known
human carcinogens by OSHA, IARC and NTP. IARC has identified
ethyl benzene and naphthalene as possibly carcinogenic to humans
(Group 2B) based on laboratory animal studies.
7.5.4 Fire-fighting measures

Flammability: Flammable Liquid,
Classification: OSHA Classification (29 CFR 1910.1200): NFPA Class-1B
Flash Point 38o C, < 100o F (ASTM D-56)
Flammable Lower Limit: 0.7% Upper Limit: 7.0%

Limits:
Auto ignition 2610C, 5020 F

Temperature
Combustion Highly dependent on combustion conditions. Fume, smoke,carbon monoxide,

Products carbon dioxide, sulfur and nitrogen oxides, aldehydes and unburned
Hydrocarbons.
Fire and This material is extremely flammable and can be ignited by heat, sparks,
Explosion flames or other sources of ignition.
Hazards
Extinguishing Dry chemical, carbon dioxide or foam is recommended. Water spray is

Media recommended to cool or protect exposed materials or structures. Carbon
dioxide can displace oxygen.
103
7.6 Benzene Toxicological Overview
7.6.1 Kinetics and metabolism
Benzene is well absorbed by inhalation. Systemic absorption of benzene from the lungs is
greatest over the first few minutes of exposure (70 – 80% of inhaled dose) and decreases
thereafter to approximately 50% of the inhaled dose after one hour.
Dermal absorption of benzene is generally considered to be poor. When applied as a discrete
droplet, 99.9% of an applied dose may vaporize from the skin surface before being absorbed.
However, excessive dermal contamination may make a substantial contribution to the daily
intake and so skin contact with benzene should be avoided. Systemic absorption of benzene
after ingestion is likely to be high, especially when dissolved in water and case reports of
poisoning indicate that benzene is extensively absorbed by the oral route.
7.6.2 Sources and route of human exposure
Benzene is a global air pollutant which can vary in concentration in area where it is exposed
to, therefore the person working near Isomerization reactors should take necessary safety
measures so that they will not exposed in case there might be leakage in the line carrying the
light naphtha to the reactors.
7.6.3 Health Effects of Acute / Single Exposure
Benzene is not generally regarded as an acutely toxic material and there are correspondingly
few reports pertaining to the (human) health effects of a single exposure. In general, acute
exposure to concentrations of benzene in excess of 500 ppm may illicit signs and symptoms
consistent with solvent intoxication. Recovery from an acute exposure is dose-dependent,
with breathlessness, nervous irritability and unsteadiness in gait persisting in severe cases for
two to three weeks.
Table 14: Summary of acute benzene vapor toxicity
Concentration(ppm) Duration of exposure(min) Effects

25 480 No observable effect
50-150 300 Headache, lassitude, weakness
500 60 Symptoms of illness
1500 60 Serious symptoms
3000 30 Endurable
7500 30 Dangerous to life
19000-20000 5-10 Fatal
7.6.5 Health Effects of Chronic / Repeated Exposure

The adverse health effects of chronic benzene exposure have been extensively documented
and primarily relate to impairment of the haemopoietic system with bone marrow depression
leading to aplastic anaemia being the most common clinical manifestation (occurring in
approximately 1% of individuals exposed to > 100 ppm benzene).
Exposures to 1 ppm benzene for 40 working years has been considered not to be associated
with any increase in leukaemia or any other haematological abnormality. However, since
104
benzene is a genotoxic carcinogen the assumption is made that there is no threshold for its
effect. I.e. any exposure is associated with some increase in risk, although this may be very
small.
7.7 Recommendations for the Storage of Naphtha

Many of the problems which may arise during the storage of LSR Naphtha can easily be
prevented by good housekeeping which should include:
 Regular draining of tanks to remove water, so helping to prevent the possibility of

microbiological contamination.
 Periodic inspection of tanks for evidence of corrosion.
 Periodic internal cleaning of tanks to remove any accumulated sludge.
 Avoidance of translucent plastic tanks for storage purposes.
105
Chapter 8
Cost Estimation
106
8.1 Why Estimation?
Before the plant to be operated, specified money must be supplied to purchase and install
the equipment. The capital needed to supply the necessary plant facilities is called fixed
capital investment while that for the operation of the plant is called the working principal
and sum of two capitals is called total capital investment.
An acceptable plant design must present a process that is capable of operating under
conditions which will yield a profit. Since, Net profit total income-all expenses. It is
essential that chemical engineer be aware of the many different types of cost involved in
manufacturing processes. Capital must be allocated for direct plant expenses; such as those
for raw materials, labor, and equipment. Besides direct expenses, many other indirect
expenses are incurred, and these must be included if a complete analysis of the total cost is
to be obtained. Some examples of these indirect expenses are administrative salaries,
product distribution costs and cost for interplant communication.
8.2 Cost estimation of equipment

8.2.1 Cost of Pump
Material of construction = Carbon steel
Ce = a + bSn
Ce = Purchased equipment cost on a
US
gulf cost basis Jan 2007
a,b = Cost constants
S = Size parameter
n = Exponent for that type of equipment
a,b = 6900,206
n = 0.9
S = 66.5 m3/hr or 18.47 lit/sec

Putting values in formula
Ce = 6900 + (206 × (18.47)0.9)
107
Purchased cost in 2007 = $ 9742.42
Average inflation rate from 2007 to 2015 = 3%
Purchased cost in 2015 = $ 9742.42 * (1.03)8
= $ 12341.41
8.2.2 Cost of Reactor 1

Material of Construction = Stainless Steel
Ce = a + bSn
a,b = 53000,28000
n = 0.8
S = 84.6 m3
Putting the values
= 53000 + (28000 * (84.6)0.8)
= $ 1028111.6
Purchased cost in 2015 = 1028111.6 × (1.03)8
= $ 1302381
8.2.3 Cost of Reactor 2

The size of reactor 2 is same as of reactor 1.
So cost of reactor 2 = $ 1302381
Cost of both reactors = 1302381 + 1302381
= $ 2604762
8.2.4 Cost of Heat exchanger 1

Ce = a + bSn
a,b = 24000,46
N = 1.2
S = 133 m2
108
Putting values
= 24000 + (46 * (133)0.8)
= $ 40269.71
Purchased cost in 2015 = $ 40269.71* (1.03)8
= $ 51012.5
8.2.5 Cost of heat exchanger 2

Ce = a + bSn
a,b = 24000,46
N = 1.2
S = 129 m2
Putting values
= 24000 + (46 *
(129)0.8)
= $ 39684.31

= $ 50270.89
8.2.6 Cost of Distillation Column

Material of construction = Carbon steel
Ce = a + bSn
a,b = 10000,29
N = 0.85
S = mass of shell in kg
Length of column, L = 21.74 m
109
Inner diameter of column, = 1.76 m
Di
Thickness of column = 60 mm or 0.06 m
Outer diameter of column, = 1.76 + (2*0.06)

Do
Do = 1.88 m
Volume of column = π 4*(Do2 – Di2)*L

Volume of column = π 4*(1.882 – 1.762)*21.74
= 7.46 m3
Density of carbon steel = 7800 kg/m3
Mass of carbon steel, S = 7800 * 7.46
S = 58188 kg
Putting values
= 10000 + (29 * (581880.85)
= $ 335466.6
Average inflation rate from 2007 to 2015
= 3%
= $ 424959
Cost of Sieve trays

Ce = a + bSn
a,b = 110,380
n = 1.8
S = 1.76m
110
Putting values
= 110 + 380 (1.76)1.8
Average inflation rate from 2007 to 2015
= 3%
Purchased cost in 2015 = 1161.25 * (1.03)8
= $ 1471
Number of plates = 32
Total cost of trays = 32 * 1471
= $ 47073.18
Total cost of distillation = 47073.18 + 424959
= $ 472032.18
Table 15: Total Purchased cost
Total Purchased Cost
Equipment Cost
Pump $ 12341.41
Heat Exchanger-1 $ 51012.50
Heat Exchanger-2 $ 50270.89
Reactor-1 $ 1302381
Reactor-2 $ 1302381
Distillation Column $ 472032.18
Total $ 3190419
111
8.3 Fixed Capital Investment
Direct Cost
Table 16: Fixed capital Investment (Direct Cost)
Component % Fix Capital Investment Cost million $
Purchased equipment, E' 3.200
Delivery, fraction of E' 10 0.320
Subtotal: delivered equipment 3.520
Purchased equipment installation 10 0.352
Instrumentation & Controls(installed) 11 0.387
Piping (installed) 09 0.317
Electrical systems (installed) 06 0.211
Buildings (including services) 10 0.352
Yard improvements 03 0.106
Service facilities (installed) 20 0.704
Total direct costs 5.949
Indirect Cost
Table 17: Fixed Capital Investment ( Indirect Cost)
Component % Fix Capital Investment Cost million $
Engineering and supervision 10 0.352
Construction expenses 09 0.317
Legal expenses 02 0.070
Contractor's fee 04 0.141
Contingency 07 0.246
Total indirect costs 1.126
112
Fix capital investment = Direct cost + Indirect cost
F.C.I = D.C + I.C

= 5.949*106 + 1.126*106
F.C.I = $ 7.075 *106
Working capital
Allowing 5% of fix capital investment to cover the cost of initial charge
Working capital = 0.05 * $ 7.075 *106

Working capital = $ 0.354*106
Total capital investment
Total capital investment = fixed capital investment + working

capital
= $ 7.075 *106 + $ 0.354*106
Total capital investment = $ 7.429*106
Production cost per year

Variable cost
Plant attainment = 95%
Total stream days = 0.95 x 365
= 347 days/year
Raw material
Hydro treated naphtha purchase cost

= $ 606/metric
ton
Density of naphtha = 662.62 kg/ m3
Hydro treated naphtha purchase cost
=$ 606/metric ton * 662.62 kg/m3 * 1metric ton/1000 kg
= $ 401.55/m3 * 1m3/6.29 bbl
113
= $ 63.84 /bbl * 10000 bbl/ day *
347 days/year Hydro treated naphtha purchase cost per year
= $ 221524800/ year
Table 18: Variable Cost
Basis cost, Cost,

Item Factor Basis
million $/y million $/y
Raw materials 221.525
Operating labor $37.5/h 0.313
Operating supervision 0.15 of operating labor 0.313 0.047
Utilities 0.05 Naphtha cost 221.525 11.08
Maintenance and repairs 0.05 of FCI 7.075 0.425
0.15 of maintenance & 0.425

0.064
Operating supplies repair
Laboratory charges 0.15 of operating labor 0.313 0.047
Royalties (if not on lump-sum basis) 0.01 of co 260.378 2.604
Variable cost = 236.105
Fixed Cost
Table 19: Fixed Cost
Basis cost, million Cost, million

Item Factor Basis
$/y $/y
Taxes (property) 0.02 of FCI 7.075 0.1415
Financing (interest) 0 of FCI 7.075 0.000
Insurance 0.01 of FCI 7.075 0.0708
Rent 0 of FCI 7.075 0.000
Fixed Charges = 0.2123
114
Plant Overhead
Table 20: Plant Overhead
Basis cost, million Cost, million

Item Factor Basis
$/y $/y
Plant overhead, of labor, supervision and

general 0.6 maintenance 0.784 0.471
Plant Overhead = 0.471
General Expenses
Table 21: General Expenses
Basis cost, Cost, million

Item Factor Basis
million $/y $/y
of labor, supervision and

Administration 0.2 maintenance 0.784 0.157
Distribution & selling 0.05 of co 260.378 13.019
Research &
Development 0.04 of co 260.378 10.415
General Expense = 23.591
Total product cost = $260.378*106/year
Manufacturing cost = T.P.C – general

expenses
Manufacturing cost = $236.787*106/year
115
References
1. James G. Speight, Handbook of petroleum product analysis. New York: Wiley-
intersciences , 2002.
2. Robert A. Meyers, Hand book of Petrolium refining process.: McGraw-Hill
Handbooks.
3. D.J. David, Peter, and R. Pujado, Handbook of Petroleum Processing. Netherlands ,
Springer 2006.
4. James, H. ,Handwork, Glenn E. Garry, Petroleum refining Technology and practice.
New York: Marcel Dekker, 2001.
5. http://en.wikipedia.org/wiki/Naphtha.
6. R K SINNOT and Coulson and Richardson, Chemical Engineering Design ,
Fourth edition.
7. Schmidt Lanny D., The Engineering of Chemical Reactions. New York : Oxford
University press , 1998.
8. Robert W. Serth, Process Heat Transfer Principles and Applications. New York:
Elsevier Science & Technology Books , 2007.
9. (2013) Tioga. [Online]. www.tiogapipe.com
10. Igor J. Karassik, Joseph P messina, Paul Coper, and Chales C Heald, Pump
Handbook , Third edition ed.: McGRAW HILL, 1976.
11. Richard Turton/ Ricard C., Bailic Wallace B., Whiting/ joseph, and A shaeiwitz,
Analysis, Synthesis and Design of Chemical Process Control, Third edition ed.
Mexicao City : Prantice Hall PTR , 1998.
12. Fundamentals of instrumentation and process control. New York : Control

station Inc., 2005.
13. William Dunn, Fundamentals of industrail instrumentation and process cantrol.

San Fransisco : McGRAW HILL, 1994.
14. (2008) Instrumentation and control, Process Control Fundamentals. [Online].

www.PAcontrol.com
15. M.S.& Timmerhaus K.D. Peter, Plant Design and Economics for Chemical
Engineers , Fourth Edition ed. Mexico City: McGRAW HILL Inc., 1991.
16. Crowl Daniel A. & Louver Joseph F., Chemical Process Safety ; Fundamentals
with Applications. New Jersy, USA: Prantice Hall , 1990.
17. (2014) Govermernt of UK ; Benzene Toxicological Overview. [Online].
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/337
516/hpa_benzene_to xicological_overview_v2.pdf
116
18. (2014) J.P. MORGAN. [Online]. https://www.jpmorgan.com/pages/jpmorgan
19. Mayers Robert A, Handbook of Petroleum Refinnig Process, Third Edition ed.:
Elsevier , 2001.
20. Byco Petroleum limited. Operating Manuals of Isomerization Plant.
21. Travis F. Glover, Understanding NPSH for Pumps.: Technical Publishing Co.,
1975.
22. Walter Driedger, Controlling Centrifugal Pumps.: Hydrocarbin Processing ,
1995.
23. Centrifugal Pump Design and Applications, Val S. Lobanoff ; Robert R.Ross.:
Gulf Publishing company Houston, TX., 1992.
24. Alfa Laval pump Handbook, First edition ed., 2001.
25. Engineering toolbox. [Online]. http://www.engineeringtoolbox.com/
26. Heinz P. Bloch and Allan R. Budris, Pump User’s Handbook.
27. (2012) Pump School. www.pumpschool.com
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A Plant Design Project On

Production of 10,000 BPSD High Octane Gasoline

B.Sc. Chemical Engineering

1.1 Naphtha ............................................................................................................................................. 11

1.2 Gasoline ............................................................................................................................................. 12

1.3 Environmental Regulations to Improve Octane Number ................................................................. 14

1.4 Isomerization ..................................................................................................................................... 15

Process description .................................................................................................................................. 19

2.1 Introduction ....................................................................................................................................... 20

2.2 Feed Stock Requirements .................................................................................................................. 20

2.3 Process Flow ...................................................................................................................................... 22

2.4 Process chemistry .............................................................................................................................. 22

2.5 Process Variables ............................................................................................................................... 24

2.6 Catalysts for Light Naphtha Isomerization ....................................................................................... 26

2.7 Selection of Catalyst........................................................................................................................... 27

Material Balance ..................................................................................................................................... 28

3.1 Introduction ....................................................................................................................................... 29

3.2 Feed Streams...................................................................................................................................... 29

3.3 Material balance around first reactor ............................................................................................... 32

3.4 Material Balance around Reactor 2 .................................................................................................. 38

3.5 Material balance around Stabilizer column ...................................................................................... 43

Energy Balance ........................................................................................................................................ 45

4.1 Introduction ....................................................................................................................................... 46

4.2 Energy balance around heat exchanger 1 ......................................................................................... 46

4.3 Energy Balance around heat exchanger 2 ......................................................................................... 47

4.4 Energy balance around isomerization reactor 1 ............................................................................... 48

4.5 Energy balance around Isomerization reactor 2 ............................................................................... 52

4.6 Energy balance around Stabilizer column ........................................................................................ 56

Design of Process Equipment .................................................................................................................. 58

5.1 Heat exchanger design ....................................................................................................................... 59

5.2 Pump Design ...................................................................................................................................... 75

5.3 Reactor Design ................................................................................................................................... 78

5.4 Mechanical Design of vessel ............................................................................................................... 80

5.5 Distillation Column Design ................................................................................................................ 82

Process Flow Diagrams ........................................................................................................................... 93

6.1 Introduction ....................................................................................................................................... 94

6.2 Block flow diagram ............................................................................................................................ 94

6.3 Conventions and format .................................................................................................................... 94

7.1 What is HAZOP? ............................................................................................................................... 99

7.2 Technical Approach to HAZOP ...................................................................................................... 100

7.3 The System for HAZOP Method. .................................................................................................... 101

7.4 HAZOP Study Procedure ............................................................................................................... 101

7.5 Hazards Identification Related To Naphtha ................................................................................... 101

7.6 Benzene Toxicological Overview ..................................................................................................... 104

7.7 Recommendations for the Storage of Naphtha ............................................................................... 105

Cost Estimation ..................................................................................................................................... 106

8.1 Why Estimation? ............................................................................................................................. 107

8.2 Cost estimation of equipment .......................................................................................................... 107

1.1.2 Light Naphtha

By definition, an octane number is that percentage of isooctane in a blend of isooctane and

1.3 Environmental Regulations to Improve Octane Number

1.4.1 Hydroisomerization History of LSR Naphtha.

1.4.2 Hydroisomerization Processes.

1.4.2.1 UOP BenSat Process

1.4.2.2 UOP Butamer Process

1.4.2.3 UOP Penex Process

1.4.3 Reason for Selection of Isomerization

Polymer gasoline is manufactured by polymerizing olefinic hydrocarbons to produce

2.2 Feed Stock Requirements

2.2.2 Undesirable Hydrocarbons

2.2.2.2 Cyclic Compounds

Table 2: Typical Limits on Stream Impurities

Total sulfur 0.1 ppm