FCC PROPYLENE PRODUCTION AND TECHNOLOGY ALTERNATIVES

TO OPTIMIZE PROPYLENE YIELDS

Keith A. Couch
Senior Manager
UOP LLC
Jim P. Glavin
Product Line Manager
UOP LLC
Dave Wegerer
Senior Associate
UOP LLC
Jibreel Qafisheh
Process Specialist
UOP LLC

Abstract: According to Purvin & Gertz(4), global FCC capacity is projected to grow by
approximately 19% between 2006 and 2015. Across that same time, polymer grade
propylene production from FCC units is projected to grow by nearly 32%(3). Although the
current average propylene yield from the installed FCC base is 4 to 5 wt%, (weight percent
of fresh feed to the FCC unit) many of the new FCC units that come on line over the next
ten years will produce even higher propylene yields, some projected to be as high as ~20
wt%.
Pushing higher propylene production from the FCC unit requires the refiner to make
some significant economic decisions. The optimum cash cost of production for propylene is
an intricate balance between CAPEX, OPEX, and throughput, versus operating severity to
produce the highest value product slate. To effectively optimize overall economics, it is
important to understand the dynamic impact of varying feed pretreatment severity on FCC
product yields. In this paper UOP will discuss the expected world demand for propylene,
present a study on the synergies associated with proper integration of Hydroprocessing and
FCC technologies on overall product yields, and evaluate the factors that influence the
selection of a propylene yield design point for the FCC unit. UOP will also present other
routes to on purpose propylene, such as our MTO, Olefin Cracking and Oleflex
technologies.

609
2

Propylene Market and the FCC Unit

The demand for petrochemical feedstocks, particularly the light olefins for the
production of polypropylene is expected to increase in the future. According to Purvin &
Gertz(4), the global FCC capacity will grow by approximately 19% between 2006 and 2015.
Over this same time frame, according to CMAI(3) the polymer grade propylene demand
filled by FCC units will grow by nearly 32%.
The FCC process has proven to be a very flexible process and is in a unique position
to help satisfy the expected increase in propylene demand. Although its principal
application has been to produce gasoline, the FCC unit is frequently operated to maximize
other products, such as distillates or LPG. The LPG mode can be considered a step towards
a petrochemical mode of operation since it provides enhanced yields of petrochemical
feedstocks.
With the strong market demand for propylene and the capability of a FCC unit to
achieve elevated propylene yields, there is a natural desire to maximize the propylene yield
from new FCC units. However, there are competing economic forces that suggest that the
optimal yield of propylene from a FCC unit is on the order of 10 11 wt%, which is
substantially lower than what current technology can produce. One of the primary
questions being asked of UOP today is how to properly balance design and operation of the
FCC unit between Maximum Gasoline and Maximum Propylene production. The optimum is
typically somewhere between these two extremes.
At the same time as the crude diet is changing, the demand for light, clean, highquality fuels has risen to an all-time high due to increasingly stringent fuel specifications.
Shifts toward gasoline and diesel fuels combined with regulations requiring ppm levels of
sulfur and demand for improved combustion properties to help reduce emissions of polyaromatics and NOx are driving this increase. The challenge for todays refiner is to identify
and implement technology which produces lighter, higher-quality products containing
virtually no sulfur from crudes containing large concentrations of sulfur, low native yields of
naphtha and distillate or both.
As is the case today, propylene production is projected to come from a number of
sources, both refinery and petrochemical-complex based. On the refining side, increased
propylene production from FCC units is expected to be a major contributor to the onpurpose requirement. On the petrochemical side, there are more alternative routes to
propylene available than ever before. These alternatives include propane dehydrogenation,
methanol-to-olefins, and olefin conversion including metathesis and olefin cracking
processes. Each of these alternatives can offer competitive economics in certain situations.

610
3

Refinery Configuration Analysis

The optimum configuration for a refinery is very specific to geography, local markets
and individual core business objectives. While the optimum complex configuration will vary
from client to client, understanding some of the integration synergies will help establish the
fundamental heart of the complex.
Refiners that operate with an objective of maximum propylene are most often
integrated with a petrochemicals complex, both for the production of polypropylene and the
production of benzene, toluene, and xylene (BTX). With this objective, the core of the
complex becomes a Coker, hydroprocessing unit, a FCC unit, and a Platforming unit; see
Figure 1.

Coker

Dry Gas
Propylene
LPG

Hydroprocessing
Complex
VGO Hdt
(Option 1)
Raw
VGO

C5 & C6

FCC

C7 C9 Platforming BTX
Unit
C10 C11

MHC
(Option 2)

LCO

HCK
(Option 3)

MCB

Figure 1: Refinery Conversion Configuration

The optimum design and operation of this conversion complex is an economic
balance between the severity of hydroprocessing applied to the VGO feeding the FCC unit,
the severity of FCC operation to make petrochemical feedstocks, and the severity of the
Platforming unit to optimize BTX production. The proper design envelope for each of these
units is heavily impacted by answering two questions; 1) how much hydrogen should be
put in the FCC feedstock, and 2) how severely should the FCC Unit be operated.

611
4

Impact of VGO Hydroprocessing on FCC Performance

To address the question of how much hydrogen should be put in the FCC feedstock,
we considered three different hydroprocessing options: (1) hydrotreating, (2) mild
hydrocracking, and (3) hydrocracking. The higher the hydrogen content of the FCC
feedstock, the higher the propylene selectivity on feed; however, the higher conversion
operation of the hydroprocessing unit reduces the remaining feedstock to the FCC unit. To
demonstrate this relationship, UOP conducted a set of sequential pilot plant studies that
quantified the results very effectively.
In this pilot plant study, a single source raw Light Arabian VGO was used for all of
the testing. The raw VGO was processed at different levels of severity: 15 lv-% conversion
to emulate hydrotreating, 45 and 55 lv-% conversion to emulate mild hydrocracking, and
70 lv-% conversion to emulate hydrocracking. All of these runs were completed using
commercially available hydrotreating and hydrocracking catalyst systems available through
UOP. The full-range of products from each of the hydroprocessing runs were collected,
then fractionated in an Oldershaw lab to collect the 343qC+ material as feedstock to an
FCC pilot plant. The product properties of this material are shown in Table 1.
Table 1 Hydroprocessing Conversion and 343qC+ Properties
HP Conversion, lv%
qAPI Gravity
UOP K

15

45

55

70

30.25
12.29

37.88
12.92

39.06
12.91

40.37
13.01

The FCC pilot plant was inventoried with a commercially produced maximum LPG
equilibrium catalyst that was high in ZSM-5 content. Additional lab deactivated ZSM-5
additive (25% ZSM-5 content), was used to blend the total level of ZSM-5 in the equilibrium
catalyst system to 20%.
The FCC pilot plant was run in RxCat mode of operation, with a riser outlet
temperature of 566qC (1050qF) utilizing a regenerated catalyst-to-oil ratio of 10, and a
carbonized catalyst-to-oil ratio of 10. The results are shown in Table 2.
Table 2 FCC Product Selectivities with Hydroprocessing Severity
HP Conversion, lv-%

15

45

55

70

Methane, wt%

2.8

2.8

3.1

2.9

Ethylene, wt%

4.7

5.9

6.2

6.3

Ethane, wt%

2.1

2.4

2.7

2.6

Propylene, wt%

16.6

22.4

23.1

23.7

Propane, wt%

2.0

2.3

2.4

2.4

Total C4s, wt%

19.1

25.3

25.8

27.0

612
5

Although progressively higher severity hydroprocessing resulted in greater propylene

selectivity, when considered on a constant crude basis, the total tonnes of propylene
produced were dramatically reduced; see Table 3 and Figure 2.

Table 3 FCC Product Selectivities with Hydroprocessing Severity

HP Conversion, lv-%

15

45

55

70

Low
Severity

High
Severity

Hdt VGO Feed to FCC, BPSD

130,000

110,500

71,500

58,500

39,000

Propylene Produced, k-MTA

N/A

895

743

623

423

30.0

1000

28.0

900

26.0

800

24.0

700

22.0

600

20.0

500

18.0

400

16.0

300

14.0

200
Propylene

12.0
10.0
0

10

20

30

40

50

60

K-MTA
70

K-MTA

Propylene Yield wt%

(PetroFCC Propylene Yields)

100
80

Volume Percent Hydrocracking Severity

Figure 2: FCC Propylene Yields with Hydroprocessing Severity

This data was subsequently used to support a commercial project, with 130,000
BPSD of raw vacuum gas oil feeding a hydroprocessing complex. In this case the refiner
determined that increased hydrogen content of the VGO and contaminant removal
improved the conversion capability in the FCC unit and decreased downstream product
treating requirements. Further optimization of the complex identified that optimized product

613
6

values were obtained by loading the VGO hydrotreater with a catalyst system that
maximized hydrogen uptake for hydrodenitrification and improved aromatics saturation
with minimal barrels converted.
To further validate this analysis, the data was used to help populate the overall
complex LP model. This LP model included every process unit in the overall refinery and the
petrochemicals complex. Each of the configurations was ranked on a basis of NPV divided
by CAPEX, and the clear winner was the VGO Hydrotreater; see Table 4.
Table 4 FCC Propylene Yields with Hydroprocessing Severity
Primary Configuration
Coking + VGO Hydrotreating

NPV/
CAPEX
0.70

+ FCC
Coking + Mild Hydrocracking

0.60

Coking + Hydrocracking

0.40

+ FCC

It is clear from the data herein that for refiners targeting high propylene production,
the VGO should only be hydrotreated to the extent required to achieve contaminant
removal targets. Over-conversion of the VGO results in a barrel loss to the FCC unit that
dramatically outpaces the increase in propylene selectivity. Catalyst systems that maximize
hydrogen uptake with minimal converted barrels should also be considered.
FCC Design Conditions and Yields as a Function of Operating Severity
The second portion of this analysis focused on optimizing the design and operating
severity of the FCC unit. Increased propylene production from FCC units has been a widely
discussed topic over the past three to five years, not only with new unit construction, but
also with existing units. One of the primary questions being asked of UOP today is how to
properly balance design and operation of the FCC unit between Maximum Gasoline and
Maximum Propylene production. The optimum is typically somewhere between these two
extremes.
The average propylene yield from the installed FCC base is around 5 wt% (on fresh
FCC unit feed, exclusive of recycle) on a global basis. Many of the new FCC units that come
on line over the next ten years will produce even higher propylene yields, some with design
points as high as ~20 wt%.
With the strong market demand for propylene and the capability of a FCC unit to
achieve elevated propylene yields, there is a natural desire to maximize the propylene yield
from new FCC units. However, there are competing economic forces that suggest that the

614
7

optimal yield of propylene from a FCC unit is on the order of 10 11 wt%, which is
substantially lower than what current technology can produce.

60
20

30

10
5

f (Rx T, PP, C/O, PT)

Maximum
Gasoline

Gasoline
+ LPG

Gasoline Yield, wt-%FF

Propylene Yield, wt-%FF

The yield pattern for the FCC unit is a continuum of operating severity and process
design that can be optimized for refinery specific economics and objectives. The optimum
process design provides the refiner with the flexibility to move up or down the most
economic range of the propylene yield curve; see Figure 3.

Maximum
Propylene

Figure 3: FCC Unit Design and Operating Modes

While propylene generation from a FCC unit certainly varies with feedstock quality,
catalyst formulation and the use of LPG additives such as ZSM-5, from a mechanical design
perspective it is primarily a function of reactor temperature, hydrocarbon partial pressure,
catalyst-to-oil ratio and total pressure. With a full range hydrotreated VGO the technology
exists to operate over a range from about 5 wt% to around 20 wt% propylene on feed. It
is important to note that higher propylene production comes at the expense of gasoline. As
we work with refiners to meet their processing objectives, we see that three design modes
emerge: 1) Maximum Gasoline which is traditional of most U.S. refiners, 2) Gasoline +
LPG for refiners that want the most market flexibility, and 3) Maximum Propylene for
true petrochemical applications. The inflection point typically defines the optimum, because
any increase above this point requires a greater change in the operating severity for the
same change in propylene yield. It is important to note that the inflection point occurs in
the Gasoline + LPG mode of operation, not maximum Propylene.

615
8

Table 5 below provides the yields for 3 different modes of operation for a FCC unit
processing a typical 24 API full range hydrotreated Vacuum Gas Oil (VGO) feedstock.

Table 5 FCC Product Yield Comparisons across Operating Modes

Ethylene
Ethane
Propylene
Propane
Butylenes
i-Butane
n-Butane
Debutanized
Gasoline
LCO
Clarified Oil
Naphtha
Composition
Aromatics
Benzene in
Gasoline

Gasoline
0.83
0.90
4.76
1.84
6.62
3.92
1.21

wt% Yield on Fresh Feed

Gasoline + LPG
1.42
0.94
10.50
3.52
9.62
4.87
1.51

Propylene
7.10
1.21
18.10
2.18
9.83
2.98
0.82

54.36
11.57
7.93

43.94
10.10
6.89

35.21
8.32
5.59

34.70

44.00

54.70

0.46

0.59

1.29

Yield Comparison

As the operation of the FCC unit is shifted towards the higher propylene production
there is a coincident increase in ethylene and butylene. Along with this shift towards light
products, there is also a decrease in gasoline yield and a change in the gasoline
composition. While most refiners expect that higher propylene generation comes at the
expense of gasoline yield, what is often not understood is that the quality of the gasoline is
progressively reduced the more severe the operation of the FCC unit. This is due to both
existing aromatics being concentrated in less gasoline, as well as the production of
additional aromatics. In this case, total aromatics increased by 58%, and benzene
increased by 280%. With gasoline benzene limits already in force, the high benzene
content of the propylene mode is often not suitable for gasoline blending without either
extraction or saturation. For most refiners, maximum propylene operation reduces gasoline
quality and devalues the product.
Refiners that practice propylene mode operation typically process the FCC naphtha
through a naphtha hydrotreater and a Platforming unit as feed preparation upstream of a
Petrochemical Complex for the production of benzene, toluene, and xylene (BTX). However,
high severity FCC operation actually reduces the overall aromatics production by reducing

616
9

precursors that would be more selectively converted to BTX in the Platforming unit; see
Table 6 and Figure 4.
Table 6 FCC + Platforming Unit Aromatics Production across Operating Modes
Modes of Operation
Gasoline
+ LPG
12,840

Gasoline
18,230

Feed to Platforming Unit, BPSD

Aromatics Production
C8 Aromatics, t/hr
C9 Aromatics, t/hr
C10+ Aromatics, t/hr
Total Aromatics, t/hr
FCC Aromatics, % of Production
FCC Propylene, t/hr
FCC Dry Gas, t/hr
Total Aromatics + C3= - Dry
Gas, t/hr

Propylene
10,015

21.77
17.78
18.83
79.01
46.15
14.31
8.43

16.18
14.32
15.70
61.81
62.71
31.62
11.11

13.31
12.10
12.07
51.06
77.63
54.49
31.44

84.90

82.32

74.06

Total Product, tonnes/hr

90

90

80

80

70

70

60
60

50

50

40
Total Aromatics

30

40

Propylene
Aromatics + C3= - Dry Gas

20

30

FCC Aromatics, % of Total

10
4

Maximum
Gasoline

8
10
12
14
Wt% Propylene Yield from FCC

Gasoline
+ LPG

16

18

20
20

FCC Aromatics, % of Total Aromatics

*Basis: 50,000 BPSD feedstock to the FCC Unit

Maximum
Propylene

Figure 4: FCC + Platforming Unit Aromatics Production across Operating Modes

As the operating severity of the FCC unit is increased through the Gasoline + LPG
mode of operation, the percentage of aromatics produced in the FCC with respect to the
total production (FCC + Platforming unit) steadily increases. However, the higher operating

617
10

severity of the FCC unit reduces the naphtha feedstock to the Platforming unit faster than
the increased rate of aromatics from the FCC unit, resulting in a net lower aromatics
production from the complex. This relationship is shown by the pink and blue lines in Figure
4.
Polymer-grade propylene has higher product value than that of mixed BTX. Although
the aromatics production does go down with higher FCC severity the propylene production
goes up, thereby offsetting the reduced value from the production loss on aromatics. This
remains true as the FCC severity is increased through the gasoline + LPG production mode.
However, as severity is increased towards maximum propylene generation, the dry gas (C2-)
production increases by a factor of 3.7 times base. Although a large percentage of the dry
gas production is ethylene, recovery of the ethylene is expensive and most refiners
consider the ethylene market to be outside of their core business objectives, and as such,
devalue ethylene to fuel gas. Worse yet, refiners can push themselves into situations where
the higher severity operation of the FCC unit results in a fuel gas long situation requiring
them to either cut back on severity or capacity.
For most petrochemicals producers, the gasoline + LPG mode appears to be a
reasonable balance between propylene and BTX production with negligible product
devaluation to fuel gas. Similarly, for the fuels focused refiner, the gasoline + LPG mode
appears to be a reasonable balance between the world demand for higher propylene
production and the need to maintain acceptable gasoline blend stock quality. In the
Gasoline + LPG mode we are able to obtain a 180% increase in propylene production with
only a 28% increase in the benzene content of the gasoline. Although the benzene content
increases, more than 80% of this increase is due to the concentration of existing benzene
production in the gasoline as a result of selectively cracking olefinic naphtha to LPG with
the use of ZSM-5 additives.
It is also important to note in Table 5 that butylene production hits a plateau around
medium severity; so if the FCC unit is being operated to produce alkylation feedstock,
medium severity operation is sufficient.
Whether operating for fuels for petrochemicals, with the intricate balance of
hydrotreating, FCC, and Platforming unit technology integrations, optimizing the overall
complex LP is critical to defining the proper design and operating envelope for the refinery.
In the analyses completed by UOP, although the technology currently exists to operate the
FCC for maximum propylene production, this does not appear to be an economic optimum
for most. To cross-check this result, the next section of this paper will discuss what UOP
has observed in the market place with respect to several recent commercial FCC projects.

618
11

FCC Commercial Production Targets

With the strong market demand for propylene and the capability of a FCC unit to
achieve elevated propylene yields, there is a natural desire to maximize the propylene yield
in terms of wt% from the design of new FCC units. There has been a significant increase in
FCC capacity licensed over the past few years, and a clear trend in refiners requests for
greater propylene production from those units. With these projects, many refiners have
started with the objective to push propylene yields towards the upper limits of what the
equipment, catalyst, and feedstock can produce. However, there are competing economic
forces at hand and real market data that suggests an optimal yield of propylene from a FCC
unit is on the order of 10 12 wt%, which is substantially lower than the theoretical limits
associated with most feeds and operating systems. Table 7 shows the initial propylene
targets as originally cited in the request for quotation (RFQ) and the final design basis for
seven new FCC projects over the past two years. While propylene production from a FCC
unit is desired, the information in Table 7 strongly suggests that there are economic forces
that push the refiner from maximum propylene back towards the Gasoline + LPG mode.

Table 7 Initial RFQ Propylene Requests versus Final Design Point

Unit A
Unit E
Unit J
Unit P
Unit R
Unit S
Unit T

wt% Propylene Yield on Fresh Feed

Initial RFQ
Final Design
--10.5
20.0
8.0
20.0
10.5
18.0
15.1
21.0
11.3
15.0
11.1
16.0
10.0

The optimum cash cost of production for propylene from a FCC unit is an intricate
balance of capital, throughput, operating severity and overall product values. Refiners often
optimize their FCC unit by maximizing converted barrels (throughput), minimizing their
operating and capital costs and producing a flexible product slate. The main problem with
pushing the limits of propylene production from a FCC unit is that in doing so, all of the
above optimization factors are negatively impacted. The operating conditions needed to
maximize propylene yield as a weight percent of fresh feed require significantly larger
equipment per barrel processed, resulting in a higher capital cost. To move the operation
from Gasoline to Propylene mode derates the operating capacity by approximately 50%; i.e.
if a unit is designed for a Gasoline mode throughput of 50,000 BPSD, to maximize severity
to Propylene mode operation in the same equipment, the feed rate would need to be
reduced to approximately 25,000 BPSD.
The operating costs associated with maximum propylene production are higher than
for Gasoline mode operation. This further penalizes the economics of maximum propylene
production. Lower hydrocarbon partial pressure to maximize propylene selectivity requires
additional steam use, and maximizing C3= over C4= requires lower absolute operating
pressure, both contributing to larger vessel requirements per barrel throughput. The

619
12

catalyst systems for maximum propylene production command a premium; and although all
patents and royalty requirements for ZSM-5 expired globally as of January 01, 2007, the
costs for ZSM-5 additives remain high. Lastly, the increased production of LPG and net
lower molecular weight of the reaction products increases the overall compression costs for
product recovery.
As a net result of detailed CAPEX, OPEX, and product value evaluations, we are not
surprised to see the market selecting an optimal propylene production that is far less than
theoretical limits. While there will always be exceptions, the ideal balance point across a
variety of feedstocks and market regions appears to be around 11 wt% propylene yield.
When determining the optimum design and operating point for a unit, it is important
to understand the relationship between propylene selectivity as a function of percentage of
feed processed, and yield as a function of tons produced. Within a fixed unit size, the
economic influence of feed rate is much greater than that of operating severity. In almost
all cases, it is better to maximize throughput over severity. To help demonstrate this
relationship, consider a FCC unit that is constrained based on maximum cyclone velocity. At
this point, there is a trade-off to be realized between operating severity and throughput. If
throughput is increased, the operating severity must be reduced; likewise, if severity is
increased, throughput has to be reduced. By carefully evaluating this relationship, UOP can
work with the refiner to determine the most economic unit design. This relationship is
demonstrated in Figure 5.

100
90
80
70
60
50
40
30
20
10
0

1300
1250
1200
1150
1100
1050
1000
950
900
850
800
30

40

50

60

70

C3= Production, Tonnes/day

Percent, or
Pressure (psig), or
Temperature (T-1000oF)

Existing Reactor Constrained at 65 ft/sec Cyclone Inlet

80

Hydrotreated Feed, kBSD

C3= wt-% FF
Reactor Temp (T1000F)
C3= Production Tonnes/day

Reactor Pressure
Conversion vol-%

Figure 5: Unit Size versus Throughput and Severity

Figure 5 shows a set of operating variables for a unit that is constrained on cyclone
velocity. In this example we start with a unit designed to operate at 35,000 barrels per day,
at a maximum severity to achieve 20 wt% propylene on feed. The combination of operating
variables results in a maximum recommended cyclone inlet velocity. As the feed rate is

620
13

increased, one of the other operating variables (reactor temperature, steam rate, or total
pressure) has to be changed, to maintain the same flowing volume of products to the
cyclones. Increased reactor pressure has the least detrimental effect on propylene
selectivity; as such, it is the first variable to be moved. The propylene yield from feed rate
outpaces the selectivity loss with increased reactor pressure. Although the weight percent
propylene on feed goes down, the actual tonnes per day of production go up. This
relationship can be maintained until the reactor nears a design pressure limit. At this point,
any additional throughput requires the reactor temperature to be reduced and propylene
production starts falling rapidly. In this example, we have been able to double the feed rate
to the unit and end up with nearly the same tonnes per day of propylene production.
The peak propylene production (tonnes/day) occurs at a propylene yield of
approximately 15 wt%, which is well under the maximum theoretical propylene yield of the
feedstock. Since the other key products such as gasoline have good market value, refiners
have the incentive to push capacity higher and accept lower propylene yields.

FCC Propylene Production

There have been many published market projections over the past few years
indicating a shortage of propylene supply to the market. Purvin and Gertz project the
world-wide FCC capacity to grow at an average annual rate of 2.7%, while the 2005 CMAI
data indicates that propylene production from FCC units will increase at an average annual
rate of 4.3 % from 2005 to 2015. This is consistent with the data presented in Table 7
showing that the weight percent of propylene produced from the average new FCC unit is
expected to increase over historical norms. However, it is also important to note that not all
of the future growth has to come from new FCC units. There is definitely a place for
leveraging existing assets to help close the market gap on propylene.
The average propylene production from FCC units in Europe is about 4.7 wt%. This
is significantly lower than the 10 11 wt% optimum discussed herein. There are two ways
to increase propylene production from existing FCC units: 1) improve the recovery
capability of the existing gas concentration unit, and 2) increase the quantity of propylene
produced in the FCC reactor.
CMAI estimates that on average the recovery of polymer grade propylene from FCC
units across the world is approximately 67%. Irrespective of where the propylene product
is sent, the economic incentives to improve recovery have increased dramatically over the
past few years. The incentive for the refiner to invest in gas con recovery projects is the
value differential between propylene and natural gas. Prior to 2003, the value gap was only
about $215 per tonne, which made it difficult to justify recovery projects. However, since
that time, the value gap has dramatically increased to around $900 per tonne, making C3
slippage to fuel gas much more costly to the refiner; see Figure 6.

621
14

1400

$/Tonne

1200
1000

Polymer Grade Contract Value

Refinery Grade Contract Value
Natural Gas

800
600

$900

400

$215

200
0
Dec
98

Dec
99

Dec
00

Dec
01

Dec
02

Dec
03

Dec
04

Dec
05

Dec
06

Figure 6: Propylene and Natural Gas Values

An optimized FCC unit should operate between 3 to 5 mol-% C3+ in the fuel gas.
When operating below 3 mol-% C3+ there is a risk of over-absorption of H2S in the gas
concentration unit which can result in a pH imbalance that can lead to elemental sulfur
precipitation in the gasoline and/or accelerated corrosion in the system. Operating the Gas
Con above 5 mol-% C3+ in the fuel gas results in a downgrade of valuable product. If we
consider the operation of a 50,000 BPSD FCC unit, at a value gap of $900 per tonne,
slipping from 3 to 7 mol% C3+ in the fuel gas results in a product value loss of about $4.6
MM per year; see Table 8.
Table 8 Propylene Product Down-Grade(1)
C3+ mol-%
in Dry Gas(2)
3 mol-%
5 mol-%
7 mol-%

C3= Slippage
to Dry Gas
(tonne/day)
10.2
17.4
24.8

C3= Downgrade
to Natural Gas(4)
($/day)
$0
$6,480
$13,460

'=$4.6 MM/year

Notes:
(1) Economics based on a 50,000 BPSD FCC unit.
(2) Additional slippage of C3+ was considered at 61.2% C3= and 38.8% C3.
(3) C3= was valued at Refinery Grade as a feedstock to an alkylation unit valued at $680
per metric tonne per CMAI for October 2006.
(4) C3= was valued as natural gas at $195 per metric tonne per CMAI for October 2006.

With respect to increased operating severity, the incentive to move higher on the
propylene production curve is the value gap between propylene to alkylate feed and regular
gasoline; see Figure 7. There have been substantial periods of time over the past 3 years
when this differential has been quite significant, extending to around $450 per metric ton.
The market does appear to be taking advantage of this opportunity. UOP has recently

622
15

completed over 500 k-BPSD of revamp designs for existing FCC capacity with the objective
of increasing propylene yields in the range of 7 to 10 wt%.

1400
1200

C3= to Alkylate
Regular Gasoline

$450

$/Tonne

1000
800
600
400
200
0
Dec
98

Dec
99

Dec
00

Dec
01

Dec
02

Dec
03

Dec
04

Dec
05

Dec
06

Figure 7: CMAI U.S. Short-Term Propylene Prices

Revamp Unit Designs

The feasibility to employ the absorption based gas con with high LPG and low
naphtha yields has occasionally been challenged, based on a perception that there simply is
not enough naphtha absorbent available to maintain system efficiency. While in fact, there
is more than enough. The primary absorber is designed to circulate both stabilized and wild
naphtha absorbent; see Figure 8. In gasoline mode operation, 80% of the absorbent is wild
naphtha from the main column overhead receiver and 20% is stabilized naphtha from the
debutanizer. As the unit is moved to maximum propylene generation, the absorbent ratio
changes towards 80% stabilized naphtha and 20% wild naphtha, but the net liquid leaving
the bottom of the absorber stays essentially the same. This is a very important point, as
the same equipment capacity is applicable over a large range of operating severity.

623
16

Operating
Mode
Gasoline:
C3= + Aromatics:

Wild
Naphtha

Stabilized
Naphtha

0.8 X
0.2 X

0.2 X
0.8 X

Absorber/
Stripper

C1 / C2
Main
Column

C3 / C4 / C5

Figure 8: Absorption Based Gas Con Flexibility

This flexibility in the absorption based FCC gas con design has enabled many
refiners in recent years to shift their operations toward higher propylene yields in the range
of 7 to 12 wt% within existing main equipment constraints while maintaining high levels of
light olefin recovery. Balancing the target propylene generation, percent recovery and the
cost of modifications to achieve the refiners objectives are an important part of every
revamp study. When trying to maximize the value of existing assets, the additional capital
required to achieve a propylene recovery of 97% may not be economic when compared to
that of a 96% recovery case. A single percentage change in design recovery can require
substantial equipment modifications or replacement. A process study normally reveals unit
limitations and provides the refiner with answers that lead to the most economic case for
revamp implementation.
UOP has been involved in many unit revamps with high propylene recovery targets.
In one of the more aggressive cases, UOP worked with the client to achieve a 58%
increase in throughput while simultaneously achieving a 30% increase in propylene yield
over the original nameplate design. To achieve this goal, the unit was progressively debottlenecked in stages so as to identify the true limits of equipment components enabling
the best use of capital investment to achieve the refiners objectives.
While no two units are ever designed or operated exactly the same, there are some
typical capacity constraints that require revamp to enable higher severity or higher
throughput operation of the gas concentration unit. These include:

Wet Gas Compressor Capacity: The increase in light ends and LPG make will
increase the load in the wet gas compressor. However, for most revamps the reactor
pressure is normally increased to accommodate the reactor cyclone design within

624
17

existing reactor shell constraints. Increasing the reactor pressure results in an

increase of the compressor suction pressure, which often offsets the decrease in
molecular weight to the compressor. Due to the high cost of wet gas compressor
replacement, in many cases the operating conditions for the revamp are set within
the maximum capacity of the existing compressor casing. It is important to note that
rotating equipment vendors have also improved their technical offerings over time,
and can often re-rate existing equipment beyond previously considered limitations.

Fractionators/Absorbers Capacity: In most revamps, the capacity constraints of

trayed columns can be overcome with the use of high capacity trays, such as MD
trays, or packing. The typical limiting areas are the HCO section of the main
fractionator, top section of the debutanizer, the stripper, and the absorber.

Cooling Temperature and Absorber Lean Oil Circulation: For propylene yields
less than 12 wt%, a traditional cooling water heat removal system is generally
sufficent to meet the desired propylene recovery. A chilled water system can be
applied if the unit has other constraints that can not be overcome; however, they
are not typically required. Absorber lean oil circulation is normally the primary
variable that can be adjusted for a revamped unit to achieve a higher propylene
recovery.

Heat Integration with the FCC Main Fractionator: Proper design of the main
fractionator heat integration with the gas concentration unit is typically the most
complex part of most revamps. Different scenarios of heat exchange with the main
fractionator are normally identified to stay within the main fractionator limitations
and reduce equipment modifications.

Alternative Absorber Configuration: The conventional UOP scheme can be

modified to increase propylene recovery to the stripper bottoms and C2 minus
rejection to the primary absorber lean gas. The traditional recycle of stripper
overhead vapor back to the inlet of the high pressure condenser is eliminated. This
off-loads the condenser and the high pressure receiver, allowing for more economic
new unit design, and greater potential to retain existing equipment in revamp
situations. This also provides a means to revamp units for higher throughput or
severity of operation that are constrained by plot space to increase high pressure
condenser duty. The stripper feed preheater can also be eliminated to improve feed
conditioning to the stripper to improve propylene recovery. These changes can result
in greater than 99% propylene recovery and C2 minus rejection sufficient to make
polymer grade propylene specification while eliminating the need for a downstream
deethanizer column.

625
18

Alternative Routes to Propylene

The many alternatives available for propylene production offer a wide variety of
opportunities but determining the right route to propylene can be confusing. There are
certain factors that apply to each alternative that can narrow the choices and help
determine which one is best for a particular project.

Propane Dehydrogenation (PDH)

Since 1990, propane dehydrogenation has been providing a growing source of

propylene for petrochemical applications. There are currently eight plants in operation
producing approximately 2.5% of the worldwide propylene supplied for petrochemicals. Six
of these plants use the Oleflex process licensed by UOP. Five additional Oleflex process
units are currently in design or construction phases which will add another 2 million metric
tons of propylene capacity when these units come on-stream over the next few years.
The Oleflex process uses a proprietary platinum on alumina catalyst. Four adiabatic
reactors are operated in series as shown in Figure 9. The dehydrogenation reaction is
endothermic so interheaters are included between each reactor to maintain the desired
reactor temperatures. The Oleflex process uses a CCR regenerator to continuously
regenerate the catalyst and maintain high conversion and selectivity.

C
C
R

Rx

Rx

Rx

Rx

Heaters

Propane

Propylene
Recovery
H2

Figure 9: C3 Oleflex Process

626
19

The yield of propylene from propane feedstock is over 85 wt% with the Oleflex
process. The amount of ethylene produced is very small, such that it is usually not
recovered. The ethylene together with the other reactor byproducts is typically used to
supplement the fuel consumption for a propane dehydrogenation unit. This means that
propylene is the only product produced from a propane dehydrogenation unit unless there
is a local demand for the hydrogen produced by the dehydrogenation reaction.
PDH offers opportunities for simple back-integration for propylene derivative
producers looking for a secure, economical source of propylene. PDH produces a single
product (propylene) so there is no need to market any co-products unless there is a local
need for hydrogen, which can easily be recovered from an Oleflex unit.
The key for any PDH project is the propylene-propane price differential. About
$200/MT is the minimum long-term average price differential required between propylene
and propane in order to achieve good economics with an Oleflex complex. The price
differential has been ranging between $300/MT to more than $500/MT over the past few
years, which has driven the growth in PDH capacity. It is not true that PDH is only feasible
when tied to discounted propane. In fact, most of the PDH plants that have been installed
are located where propylene is needed as opposed to where cheap propane is located.
PDH offers three specific advantages to propylene derivative producers. First, a PDH
plant makes a single product, propylene. A company specifically interested in producing
propylene derivatives may not want to produce ethylene or C4+ co-products that are made
from naphtha crackers, or gasoline and fuels from refineries. PDH focuses an investment
specifically on propylene capacity. Second, production costs for a PDH plant are tied to the
cost of propane. Propane prices are not tied directly to naphtha prices or the propylene
market; therefore, PDH allows large propylene derivative producers to diversify the overall
cost structure of their feedstock. Finally, some of the best locations for propylene derivative
plants do not have good access to byproduct propylene. Given the high cost of shipping
and storing propylene, PDH is generally more cost-effective than buying propylene for
these locations, if propane is available.
PDH requires a relatively low capital investment compared to other grass-roots
alternatives for producing similar amounts of propylene. Good economies of scale are
achieved with unit capacities of 250,000 MTA or larger. UOPs Oleflex process offers
experience and reliability with six commercial units in operation. Over 1.25 million MTA of
propylene capacity has come on-stream using the Oleflex process since 1990 and the onstream Oleflex process capacity will exceed 3 million MTA of propylene within the next few
years.

627
20

MTO

The UOP/HYDRO MTO process (Figure 10) was jointly developed by UOP and Norsk
Hydro for the selective production of ethylene and propylene from methanol derived from
natural gas or coal. MTO combines well proven FCC and naphtha cracker technologies with
a proprietary new catalyst from UOP. The catalyst used in the process is based on a
silicoaluminophosphate, SAPO-34. The technology has been extensively demonstrated in a
demo plant by Norsk Hydro and more than fifteen years of development have been
completed. The MTO process converts methanol to ethylene and propylene at close to 80%
carbon selectivity in a fluidized bed reactor. The carbon selectivity approaches 90% if MTO
is combined with olefin cracking technology as discussed later in this paper.

Reactor Regenerator

Caustic
Wash

Quench
Tower

De-C2

De-C1

C2
Splitter

C3
De-C3 Splitter

De-C4
Tail Gas
Ethylene

Regen Gas

Propylene
Dryer

Mixed C4

DME
Recovery
C2H2
Reactor
C5+

Air

Propane

Water

Ethane
Methanol
Water

Figure 10: UOP/HYDRO MTO Process

The MTO reaction is exothermic. Carbon or coke accumulates on the catalyst and
must be removed to maintain catalyst activity. The coke is removed by combustion with air
in a catalyst regenerator system. Other co-products include very small amounts of C1-C4
paraffins, hydrogen, CO and CO2, as well as ppm levels of heavier oxygenates that are
removed to ensure that the product olefins meet polymer-grade specifications.
The UOP/HYDRO MTO process offers the greatest flexibility of any propylene
producing technology. The ratio of propylene/ethylene product can range from less than
0.8 to more than 1.3. When combined with the TOTAL PETROCHEMICALS/UOP Olefin
Cracking process (to be discussed later) to convert the heavier olefins, the
propylene/ethylene product ratios can range from less than 1.0 to more than 2.0.

628
21

MTO is part of a two-step process, which converts natural gas to methanol followed
by the conversion of methanol to light olefins. MTO projects are driven by the desire to
minimize costs of production by utilizing cost-advantaged natural gas or coal and the
market demands for ethylene and propylene and their derivatives. In many locations,
natural gas prices are not directly tied to crude oil and naphtha market prices so MTO
provides another means for olefin derivative producers to diversify the cost structure for
their feedstocks. MTO can provide much lower costs of production and higher returns on
investment than naphtha crackers when crude oil market prices are above $20 per barrel.
MTO
amount of
production
methanol).
low enough

projects are tied to mega-scale methanol projects for two reasons. First, the
methanol required for an MTO project is consistent with the methanol
from todays latest world-scale methanol projects (5,000 to 10,000 t/d
Second, the costs of methanol production from a mega-scale methanol unit are
to support alternative uses for methanol such as fuel applications or MTO.

MTO plants can be located near or integrated with the methanol plant or they can be
located separately with the methanol plant located near the gas source or coal fields and
the MTO plant located near the olefin markets or olefin derivative plants.

Olefin Conversion

Olefin cracking technology offers an alternative to upgrade C4 to C8 olefins to

propylene and ethylene at high propylene to ethylene ratios. In mid-2003, the TOTAL
PETROCHEMICALS/UOP Olefin Cracking process was introduced after TOTAL
PETROCHEMICALS and UOP completed extensive development and demonstration activities.
Following initial work by TOTAL PETROCHEMICALS in the mid 1990s, UOP and
TOTAL PETROCHEMICALS formed a joint-development alliance in late 2000.
The
development activities included successful operation of a demonstration unit, catalyst
performance testing in pilot plants, feed-yield determination, catalyst manufacturing scaleup and process design development. The demo unit, started in 1998 at an industrial facility
associated with TOTAL PETROCHEMICALS in Antwerp, Belgium, processes commercial
feedstocks from operating plants. The demo unit includes feed pretreatment, a reactor
section, catalyst regeneration facilities, and internal recycle capabilities.
The TOTAL PETROCHEMICALS/UOP Olefin Cracking process (Figure 11) features
fixed-bed reactors operating at temperatures between 500 and 600C and pressures
between 1 to 5 bars gauge. The process utilizes a proprietary zeolitic catalyst from UOP
and provides high yields of propylene at propylene/ethylene product ratios of about 4.0.
The catalyst minimizes the reactor size and operating costs by operating at high space
velocities and high conversions and selectivities without requiring an inert diluent stream.

629
22

A swing reactor system is used for catalyst regeneration. The layout of the product
separation facilities is dependent on how the olefin cracking unit is integrated with other
processing plants such as a naphtha cracker, an FCC or an MTO unit (Figure 12).

Light
Olefin
Product

Olefinic
C4 - C8
Feed

Depropanizer
Column

SHP
OC
Reactor

C4 & C5
Purge

Recycle

Rerun
Column

C6+
Purge

Figure 11: TOTAL PETROCHEMICALS/UOP Olefin Cracking Process

Naphtha
Product
Recovery
Product&
Purification
Recovery &

Furnace
Furnace

C4/C5
C5/C6
Paraffin-Rich

Light
Olefins

Refineries

Gas
Oils

C4-C5
Olefins

FCC
Olefin
Cracking

Naphtha Crackers

C2=
C3=

Olefin
Cracking

C3=
Light
Olefins

Gasoline
Cycle Oils

FCC

C4-C8

C2=

MTO

MeOH

C2=
C3=
Fuel Gas
Pygas

Olefin
Cracking

MTO Plants

Olefin
Olefin
Recovery
LPG
Light
Olefins

Figure 12: Olefin Cracking Applications

630
23

C4+

Olefin conversion technologies offer opportunities for upgrading low-value heavier

olefins to light olefins via either metathesis or olefin cracking. These technologies favor
high yields of propylene so they are especially well suited for projects looking to maximize
propylene production. Olefin conversion units integrate with other olefin production and
recovery facilities such as ethylene plants (steam crackers), refinery FCC units, or MTO
units.
The TOTAL PETROCHEMICALS/UOP Olefin Cracking process was developed to utilize
low value byproduct streams containing C4 to C8 olefins from steam crackers, fluid catalytic
cracking (FCC) refineries, and/or methanol-to-olefins (MTO) plants.5 When combined with
steam crackers, the process allows the steam cracker to expand capacity and achieve
higher propylene/ethylene production ratios. For FCC refineries, the technology utilizes FCC
byproduct streams to increase propylene and ethylene production while reducing the olefin
content of gasoline blending streams with little or no loss of octane. For MTO complexes,
the technology increases the yield of light olefins for a given amount of methanol feedstock
and reduces or eliminates the C4+ byproduct streams. (Refer to Figure 12 for an overview
how Olefin Cracking can integrate with these other processes)
The TOTAL PETROCHEMICALS/UOP Olefin Cracking process is generally economical
when propylene to ethylene price ratio is between 0.8 and 1.2. Approximately 0.25 tons of
ethylene are produced per ton of propylene produced. Olefin cracking feedstocks can
include Raffinate-1, Raffinate-2 and/or C5, C6, C7, or C8 olefins from naphtha crackers,
FCC, cokers, or MTO. The feedstocks can be pooled together from various sources to
achieve good economies of scale while reducing the amounts of C5 olefins that are blended
into gasoline. The C4-C8 purge streams from olefin cracking can be recycled to cracker
furnaces to further supplement olefin production.
Summary
Global propylene demand trends remain strong, and with the change towards lighter
feedstocks in new steam crackers there will be a growing reliance on FCC units to balance
the supply side of the propylene equation. The technology exists today to help make this
happen. UOP believes that the FCC process is flexible enough to meet the challenge
associated with closing the global market gap for propylene. We believe that this will
happen through a combination of new units designed for elevated propylene yields and
revamps of existing facilities to increase propylene yield and recovery within logical
equipment constraints.
Refiners that operate with the objective of maximum propylene are most often
integrated with a petrochemicals complex for the production of polypropylene, benzene,
toluene, and xylene (BTX). With this objective, the core of the complex becomes a Coker,
hydroprocessing unit, a FCC unit, and a Platforming unit. It is clear from the data herein
that the VGO should only be hydrotreated to the extent required to achieve contaminant
removal targets. Over-conversion of the VGO results in a barrel loss to the FCC unit that

631
24

dramatically outpaces the increase in propylene selectivity. Catalyst systems that maximize
hydrogen uptake, hydrodenitrification, and aromatics saturation with minimal converted
barrels should be used.
There are competing economic forces and real market data that suggests that the
optimal yield of propylene from a FCC unit is on the order of 10 12 wt%, which is
substantially lower than the theoretical limits associated with most feeds and operating
systems. The premium that propylene and butylene command over other products, such as
gasoline, is sufficient to provide many refiners the incentive to invest in their existing assets.
UOPs expertise in overall refinery complex design enables us to work with the refiner to
optimize new units and revamp designs for the best overall economic return on investment.

References

1. Thakkar, Ackelson, Rossi, Dziabala, and McGehee, Innovative Hydrocracking

Applications for Conversion of Heavy Feedstocks, 2007 NPRA Annual Meeting,
Publication AM-07-47
2. Chemical Market Associates Inc. (CMAI), 2004 World Light Olefins Analysis,
www.cmaiglobal.com
3. Chemical Market Associates Inc. (CMAI), 2006 World Light Olefins Analysis,
www.cmaiglobal.com
4. Purvin & Gertz, 2006 Global Petroleum Market Outlook, www.purvingertz.com
5. U.S. Energy Information Administration (EIA), Annual Energy Outlook,
www.eia.doe.gov
6. Couch, Glavin, Wegerer and Qafisheh, FCC Propylene Production Closing the Market
Gap by Leveraging Existing Assets, 2007 NPRA Annual Meeting, Publication AM-07-63
7. Houde, Mark, Rebalance Gasoline Surplus by Maximizing FCC Propylene, ERTC 2005,
www.uop.com/objects/RebalanceGasolineSurplus.pdf
8. Leliveld, RG, STARS Ketjenfine 860 Exceptional New Catalyst for Hydrocracking
Pretreat, Albemarle Catalyst Courier, Spring 2007, Issue 67
9. Houdek, and Anderson, On-Purpose Propylene Technology Developments, ARTC 8th
Annual Meeting

632
25