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Propylene Production

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Propylene Production
a
Abdullah M. Aitani
a
Center for Refining and Petrochemicals , King Fahd University of Petroleum and Minerals ,
Dhahran , Eastern , Saudi Arabia

Published online: 12 Dec 2007

To cite this entry: Abdullah M. Aitani . Propylene Production. In Encyclopedia of Chemical Processing. Taylor and Francis: New
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 Propylene Production
Abdullah M. Aitani
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
INTRODUCTION
Propylene is one of the main building blocks for petro-
chemicals and for clean fuel alkylate blends. It is used
in the production of a wide variety of petrochemical pro-
ducts such as polypropylene, acrylonitrile, cumene,
oxo-alcohols, propylene oxide, acrylic acid, isopropyl
alcohol, and polygas chemicals. Polypropylene accounts
for about half of the world propylene consumption,
which consequently drives the demand. Other uses of
propylene within a refinery include alkylation, catalytic
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polymerization, and dimerization for the production of
high-octane gasoline blends. In general, propylene is
supplied in three separate quality grades: refinery
( 70%), chemical ( 92 to 96%), and polymer (99.6%).
The two major commercial sources of propylene are
ethylene steam cracker plants and refinery fluid cataly-
tic cracking (FCC). Other routes include olefin metath-
esis and propane dehydrogenation. About 68% of
world propylene is produced as coproduct to ethylene
by the steam cracking of hydrocarbons and about 29%
is produced as coproduct to gasoline in the FCC of
gas oils. The remaining 3% is produced via propane
dehydrogenation and olefin metathesis.[1,2]. Other
emerging technologies include catalytic cracking of
higher hydrocarbons, olefin interconversion, and
methanol conversion. Table 1 presents a summary of
world propylene sources and production data.
Current global production of propylene stands at
about 54 million metric tons per year (tpy) and is
valued roughly at $17 billion.[2] The bulk of propylene
production and consumption is concentrated in North
America, Western Europe, and Japan. These areas
represent about 68% of world capacity and 70% of
demand. Propylene demand is expected to grow fast
C, 1–1.2 atm, and
and to nearly double in the next 10 yr, reaching more
than 91 million tons by 2010 at a growth rate of 4.7%=yr.[2]
Because world consumption is forecast to grow faster
than production capacity, propylene has been termed as
C, 1 atm,
‘‘olefin of the future.’’[1] This increase is driven by the
demand for derivatives, especially polypropylene.
STEAM CRACKING OF HYDROCARBONS
The main route for producing light olefins, especially
ethylene and propylene, is the steam cracking of
Encyclopedia of Chemical Processing DOI: 10.1081/E-ECHP-120037901
Copyright # 2006 by Taylor & Francis. All rights reserved.
hydrocarbons, which was commercialized in the
1950s. Currently, world capacity of ethylene steam
crackers stands at about 112 million tpy and the
amount of propylene coproduced in these steam crack-
ers is about 36 million tpy. The capacity and the
throughput of steam crackers are continuously grow-
ing due to the ever-increasing world demand for poly-
mers (polyethylene and polypropylene in particular)
and other olefin-based derivatives. Ethane, LPG, and
naphtha are the dominant steam cracker feedstocks.
Natural gas condensate is abundant in North America
and the Middle East, while naphtha is commonly used
in Asia and Europe.
Steam cracking reactions are principally bond
breaking and a substantial amount of energy is needed
to drive the reaction toward olefin production. The
reaction is highly endothermic; so it is favored at
higher temperatures and lower pressures. Superheated
steam is used to reduce the partial pressure of the
reacting hydrocarbons. It also reduces carbon deposits
that are formed by the pyrolysis of hydrocarbons at
high temperatures. Long chain hydrocarbons crack
more easily than shorter chain compounds and require
lower cracking temperatures.
A typical steam cracker consists of several identical
pyrolysis furnaces in which the feed is cracked in the
presence of steam as a diluent.[3] The cracked gases
are quenched and then sent to the demethanizer to
remove hydrogen and methane. The effluent is then
treated to remove acetylene, and ethylene is separated
in the ethylene fractionator. The bottom fraction is
separated in the de-ethanizer into ethane and C3þ,
which is sent for further treatment to recover propyl-
ene and other olefins. Typical operating conditions of
ethane steam cracker are 750–800
steam=ethane ratio of 0.5. Liquid feeds are usually
cracked at lower residence time and higher steam
dilution ratios compared to gaseous feeds. Typical
conditions for naphtha cracking are 800
steam=hydrocarbon ratio of 0.6–0.8, and a residence
time of 0.35 sec. Liquid feedstocks produce a wide
spectrum of coproducts including BTX aromatics that
can be used in the production of variety of chemical
derivatives.
In the cracking furnaces, the achievable propylene
to ethylene ratio (P=E) is limited to a value of about
0.65, because at higher ratios the total olefin yield
2461
 2462 Propylene Production

Table 1 Sources of propylene and world production data

World production in Annual growth for
Propylene source 2002 (million tpy) Share (%) 2002–2015 (%)
Steam crackers 35.9 68.0 4.3
Refinery FCC units 15.3 29.0 5.0
Metathesis=dehydrogenation 1.6 3.0 6.5
Total 52.8 100.0 4.7
[1,2]
(From Refs. .)

(i.e., the sum of ethylene and propylene) drops to an
uneconomically low level. Due to the higher annual
growth rates of propylene compared to ethylene, the
highest possible P=E in steam crackers is very desir-
able. Table 2 shows typical propylene yields from
steam cracking of different hydrocarbon feedstocks,
and how the C5þ liquid byproducts increase dramati-
cally with heavier feeds.[4]
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A schematic flow diagram of a conventional
FCC unit is shown in Fig. 1. The main FCC sections
comprise feed injection system, reactor (riser), stripper,
fractionator, and regenerator. A fluidized catalyst
system is used to facilitate catalyst and heat transfer
between the reactor and the regenerator. Cracking
reactions are endothermic; the heat balance is obtained
by the combustion of catalyst-deposited coke in the

regenerator. In general, all cracking reactions are char-

FLUID CATALYTIC CRACKING
Fluid catalytic cracking units account for about 97% of
propylene produced at the refineries as a coproduct to
gasoline. Delayed cokers and visbreakers produce the
remaining 3%. In some refineries, a fraction of the pro-
pylene and all light gases are normally diverted into
sweet fuel gas. About 60% of FCC propylene is used
in chemical production and the remaining is used in
the production of high-octane gasoline blends. Fluid
catalytic cracking is the largest refining process for
the production of gasoline with a global capacity of
more than 14.2 million bbl=d or 715 million tpy; about
50% of this capacity is in North America alone. Fluid
catalytic cracking converts heavy oil feedstocks such as
vacuum gas oil, residues, deasphalted oil into lighter
products that are largely olefinic for light fractions
and strongly aromatic for heavy fractions.[5]
acterized by the production of appreciable amounts of
corresponding olefins. The propylene yield from FCC
unit is a function of the following parameters:
 Processing capacity of the FCC unit;
 Type of feedstock;
 Riser reactor outlet temperature (severity); and
 Fluid catalytic cracking catalyst type and additives.
To achieve higher outputs of light olefins, particu-
larly propylene, the hydrogen content of the feedstock
must be increased and the sulfur content reduced. This
can be achieved by the utilization of low sulfur crude
oils or using a higher performance feed hydrotreater
upstream of the FCC unit. There are several commer-
cial FCC processes currently employed with major
differences in the method of catalyst handling.
Currently, it is not economical to build an FCC for
on-purpose propylene production because of low

Table 2 Product yields from steam cracking of various hydrocarbons

Gaseous feeds Liquid feeds

Product yield (wt% on unit) Ethane Propane Butanes Naphtha Gas oil
H2 and methane 13 28 24 26 23
Ethylene 80 45 37 30 25
Propylene 1.11 14.0 16.4 14.1 14.4
Butadiene 1.4 2 2 4.5 5
Mixed butenes 1.6 1 6.4 8 6
þ
C5 1.6 9 12.6 18.5 32
Propylene=ethylene (wt=wt) 0.03 0.3 0.5 0.4 0.6
Propylene (wt% of C3) 86.7 58.3 99.0 98.3 96.7
(From Ref.[3].)
 Propylene Production 2463
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Fig. 1 Schematic flow diagram of

a conventional FCC process.

propylene yield; however, it is economical to recover
propylene from an FCC unit for chemical uses. Deep
catalytic cracking, licensed by Stone & Webster=Shaw
Shaw and RIPP=Sinopec, is the only high-olefin FCC
process that reached the commercialization stage.[5]
Recent catalyst developments have helped increase
the propylene yield of conventional FCC from 4.5%
to 10% or greater. In particular, the use of ZSM-5
catalyst additive is increasing to boost propylene
production. Processes in various stages of development
include PetroFCC (UOP), High Severity-FCC
(KFUPM, JCCP, Saudi Aramco), Maxofin (KBR,
ExxonMobil), Selective Component Cracking (Lum-
mus), and IndMax (Indian Oil). Table 3 presents a
comparison of the yield structure of conventional
FCC and selected high-olefin technologies.[5–7]

Table 3 Product yields of conventional and emerging FCC processes

Parameter FCC DCC PetroFCC HS-FCC

Reaction temperature ( C) 500 530 590 600

Product yield (wt%)
Ethylene 1.5 5.4 6.0 2.3
Propylene 4.8 14.3 22.0 15.9
Mixed butanes 6.9 14.7 14.0 17.4
Gasoline 51.5 39.0 28.0 37.8
Heavy and light oils 21.0 15.6 14.5 9.9
Coke 4.5 4.3 5.5 6.5
(From Refs.[5–7].)
 2464 Propylene Production

Table 4 Typical properties of commercial propane dehydrogenation processes

Process Licensor Reactor type Catalyst Reaction conditions
Catofin Lummus-Houdry Fixed bed Cr2O3=Al2O3 560–620
C, > 0.5 atm
FBD-3 Snamprogetti-Yarsintez Fluidized bed Cr2O3=Al2O3 540–590
C, 1 atm
Oleflex UOP Moving bed Pt=Al2O3 550–650
C, > 1 atm
PDH Linde-BASF-Statoil Fixed bed Cr2O3=Al2O3 590
C, > 1 atm
STAR Krupp Uhde Fixed bed Pt=Sn=Zn=Al2O3 500
C, 3.5 atm
(From Ref.[8].)

PROPANE DEHYDROGENATION Fig. 2 presents a typical schematic flow diagram for

Propane dehydrogenation is a highly endothermic
process. High temperatures and relatively low pressures
are used to get a reasonable conversion of propane. The
reaction is equilibrium limited. The amount of olefin
in the reactor effluent is dependent on the reactor
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propane dehydrogenation. In a process with fixed-bed
reactors, at least two reactors must be used so that the
catalyst in one reactor can be regenerated without
stopping the process. The advantage with a moving
bed or a fluidized bed is that the catalyst can be conti-
nuously removed from the reactor and be regenerated.

outlet conditions. Thermal cracking reactions limit The disadvantage is that a separate regeneration unit is
the maximum practical temperature, and pressure, needed.
therefore, becomes the dominant variable.

C3 H8 ) C3 H6 þ H2 DHr;298 K ¼ 129:4 kJ=mol

METATHESIS

Side reactions that occur simultaneously with the
main reaction cause the formation of some light and
heavy hydrocarbons that result in the deposition of a
small amount of coke on the catalyst. Two different
catalyst systems based on chromium and platinum
are used within a temperature range of 500–650
C. transforms the carbon–carbon double bond, a func-
Because of the fast deactivation by coke formation,
different concepts have been used to enable regenera-
tion of the catalyst.
Several commercial processes have been developed for
the catalytic dehydrogenation of propane to propylene as
presented in Table 4.[8] Of the seven commercial propane
dehydrogenation plants in operation, six use UOP’s
Oleflex continuous moving-bed process. The other uses
ABB Lummus’ Catofin cyclic multiple-reactor system.
Other processes include Krupp Uhde’s STAR process,
as well as technologies from Linde and Snamprogetti.[9]
Olefin metathesis is a useful reaction for the produc-
tion of propylene from ethylene and butenes using
certain transition-metal compound catalysts. The two
main equilibrium reactions that take place simulta-
neously are metathesis and isomerization. Metathesis
tional group that is unreactive toward many reagents
that react with many other functional groups. New
carbon–carbon double bonds are formed at or near
room temperature even in aqueous media from starting
materials. Because olefin metathesis is a reversible reac-
tion, propylene can be produced from ethylene and
butene-2. Metathesis can be added to steam crackers
to enhance the production of propylene by the trans-
formation of ethylene and the cracking of mixed
butenes. Fig. 3 shows a schematic flow diagram of a
typical metathesis process. Examples of metathesis

Fig. 2 Flow diagram of catalytic dehydrogenation of propane to propylene.

 Propylene Production
Fig. 3 Typical flow diagram of olefin metathesis process.
processes include the low temperature Meta-4 by
Axens and the Olefins Conversion Technology (OCT)
by ABB Lummus (acquired from Phillips).
EMERGING TECHNOLOGIES
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Catalytic Cracking of Higher Hydrocarbons
A number of nonconventional technologies such as the
catalytic cracking of naphtha are being explored as an
alternative conventional steam cracking of hydro-
carbons. The main objective is to achieve higher yields
of light olefins and to lower capital and operating costs.
Vniios has developed a conceptually new technology for
the catalytic cracking (pyrolysis) of petroleum fractions
using heterogeneous catalysts. The process key element
is a potassium–vanadium catalyst doped with boron
oxide and supported on a robust mullite–corundum
carrier. Despite numerous patents and demonstration
plant trials, none of these processes have been used in
commercial olefin production. However, it is unlikely
that these processes will replace steam cracking for
ethylene production in the foreseeable future.
Olefin Interconversion
Several on-purpose propylene production technolo-
gies are based on the catalytic interconversion of
C4–C8 olefins in a fixed- or fluidized-bed reactor
Table 5 Selection criteria for on-purpose propylene production processes
Selection criteria Refinery DCC Dehydrogenation
Feedstock Gas oils Propane
Steam cracker integration No No
Investment Moderate High
Commercial units Several Several
(From Ref.[1].)
2465
configuration. The process can be added to con-
ventional steam cracking plants or FCC units. All
developed processes use shape-selective medium-pore
zeolitic catalysts that crack olefin-rich streams to pre-
dominately ethylene and propylene. The fluidized-bed
technologies are based on a reactor=regenerator design
similar to conventional FCC. Reaction thermo-
dynamics determine the product slate and the selectivity
independent of feedstock sources. Lurgi developed a
low-pressure catalytic process known as Propylur that
uses adiabatic fixed-bed technology for converting
higher olefins to propylene and ethylene in the pre-
sence of steam. Other technologies include Atofina=
UOP’s olefin cracking process (OCP), Lyondell=
Kellogg’s fluidized-bed Superflex process, Linde’s fixed-
bed catalytic cracking (FBCC), and ExxonMobil’s
olefin interconversion (MOI) and fluidized-bed propyl-
ene catalytic cracking (PCC).
Propylene from Methanol
Because the market for olefins currently greatly exceeds
that for methanol production, olefin production could
become an important new outlet for the potentially vast
quantities of low-cost methanol. Methanol conversion
produces a mixture of ethylene and propylene of various
ratios or primarily propylene depending on the process.
Currently, there are two processes for the production of
propylene from methanol: the first process is methanol
to olefin (MTO) process, developed by UOP and Hydro,
Metathesis Olefin cracking MTO/MTP
C2–C4 Olefins C4–C8 Olefins Methanol
Yes Yes No
Moderate Moderate Very high
One None None
 2466
and the second process is methanol to propylene (MTP)
process, developed by Lurgi. Both processes start from
converting natural gas into methanol, which is then
converted to light olefins. The processes are attractive
as part of a complex for the utilization of stranded
natural gas reserves.
CONCLUSIONS
Propylene is conventionally produced as a coproduct
in steam cracking of naphtha or FCC of gas oil in
refineries and to a lesser extent via propane dehydro-
genation and olefin metathesis. To meet strong
demand for propylene derivatives, research is ongoing
to develop new on-purpose technologies such as cata-
lytic cracking of hydrocarbons, olefin interconversion,
and methanol conversion. The selection criteria for
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on-purpose propylene production processes are sum-
marized in Table 5. These processes uncouple propy-
lene production from steam crackers and refineries
allowing higher production flexibility. However, they
will remain more expensive than the coproduct routes
and will continue to provide only marginal produc-
tion volumes in niche circumstances. Much of the
increase in propylene demand is expected to come
from steam crackers, followed by refineries and dehy-
drogenation plants.
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Propylene Production
REFERENCES
1. Plotkin, J. Propylene: olefin of the future?
Presented at the 21st Annual Petrochemical World
Trade Conference, Chemical Week and Chemosys-
tems: Houston, Sept, 2003.
2. Walther, M. Refinery sources will fill the future
‘‘propylene gap.’’ Oil Gas J. 2003, 101 (4), 65.
3. Matar, S.; Hatch, L. Chemistry of Petrochemical
Processes, 2nd Ed.; Gulf Professional Publishing:
Boston, 2001; 91 pp.
4. Kniel, L.; Winter, O.; Stork, K. Ethylene: Keystone
to the Petrochemical Industry; Marcel Dekker:
New York, 1980; 184 pp.
5. Letzsch, W. The role of the FCC in the refinery of
the future. Presented at Akzo Nobel Technical
Seminar on How to Meet Environmental Targets,
Akzo Nobel Paris, Nov, 2002.
6. Houdek, J.; Hemler, C.; Pittman, R.; Upson, L.
Developing a process for the new century. Petro-
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7. Ma’adhah, A.; Abul-Hamayel, M.; Aitani, A.; Ino,
T.; Okuhara, T. Down-flowing FCC reactor
increases propylene and gasoline make. Oil Gas J.
2000, 98 (33), 66.
8. Farrauto, R.; Bartholomew, C. Fundamentals of
Industrial Catalytic Processes; Blackie Academic
and Professional: London, 1997; 411 pp.
9. Tullo, A. Propylene on demand. Chemical and
Engineering News 2003, 81 (50), 15.