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Propylene Production

P
Abdullah M. Aitani
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

INTRODUCTION Propylene is one of the main building blocks for petrochemicals and for clean fuel alkylate blends. It is used in the production of a wide variety of petrochemical products 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 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 catalytic cracking (FCC). Other routes include olefin metathesis 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 N orth America, W estern E urope, and J apan. These areas represent about 68% of world capacity and 70% of demand. Propylene demand is expected to grow fast 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] B ecause world consumption is forecast to grow faster than production capacity, propylene has been termed as ‘ ‘ olefin of the future.’ ’ [1] This increase is driven by the demand for derivatives, especially polypropylene.

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The main route for producing light olefins, especially ethylene and propylene, is the steam cracking of
Encyclopedia of Chemical Processing D OI: 10.1081/ E -E CHP-120037901 Copyright # 2006 by Taylor & Francis. All rights reserved.
© 2006 by Taylor & Francis Group, LLC

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 crackers is about 36 million tpy. The capacity and the throughput of steam crackers are continuously growing due to the ever-increasing world demand for polymers (polyethylene and polypropylene in particular) and other olefin-based derivatives. E thane, L PG , and naphtha are the dominant steam cracker feedstocks. N atural gas condensate is abundant in N orth America and the M iddle E ast, while naphtha is commonly used in Asia and E urope. S team 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. S uperheated 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. L ong 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 propylene and other olefins. Typical operating conditions of ethane steam cracker are 750– 800 C, 1– 1.2 atm, and steam=ethane ratio of 0.5. L iquid feeds are usually cracked at lower residence time and higher steam dilution ratios compared to gaseous feeds. Typical conditions for naphtha cracking are 800 C, 1 atm, steam=hydrocarbon ratio of 0.6– 0.8, and a residence time of 0.35 sec. L iquid feedstocks produce a wide spectrum of coproducts including B TX 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
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R iser reactor outlet temperature (severity).4 12.2 million bbl=d or 715 million tpy..0 A n n u a l g ro w th fo r 20 0 2– 20 15 ( %) 4. Type of feedstock. it is not economical to build an FCC for on-purpose propylene production because of low T a b l e 2 Product yields from steam cracking of various hydrocarbons G a se o u s fe e d s P r o d u c t y ie ld (w t%o n u n it) H2 and methane E thylene Propylene B utadiene M ixed butenes C5 þ L iq u id fe e d s B u ta n e s 24 37 16.11 1. A fluidized catalyst system is used to facilitate catalyst and heat transfer between the reactor and the regenerator.4 98.3 5.3 G a s o il 23 25 14. about 50% of this capacity is in N orth America alone.0 3. and Fluid catalytic cracking catalyst type and additives. The propylene yield from FCC unit is a function of the following parameters:     Processing capacity of the FCC unit.8 S h a r e ( %) 68. fractionator.3 1.7 P ro p a n e 28 45 14. 1.2462 P r o p y le n e P r o d u c tio n T a b l e 1 S ources of propylene and world production data P r o p y le n e s o u r c e S team crackers R efinery FCC units M etathesis=dehydrogenation Total (From R efs. Fluid catalytic cracking converts heavy oil feedstocks such as vacuum gas oil. a fraction of the propylene and all light gases are normally diverted into sweet fuel gas. D elayed cokers and visbreakers produce the remaining 3%.) © 2006 by Taylor & Francis Group. the sum of ethylene and propylene) drops to an uneconomically low level.[5] A schematic flow diagram of a conventional FCC unit is shown in Fig. There are several commercial FCC processes currently employed with major differences in the method of catalyst handling.5 0. stripper.1 4. Cracking reactions are endothermic. the hydrogen content of the feedstock must be increased and the sulfur content reduced.9 15.7 (i.0 6.e.0 N a p h th a 26 30 14.7 E th a n e 13 80 1.[1.6 0.4 5 6 32 0.[3]. residues. the highest possible P=E in steam crackers is very desirable. particularly propylene. Currently.03 86.5 8 18.0 2 1 9 0. In general. In some refineries.3 Propylene=ethylene (wt=wt) Propylene (wt% of C3) (From R ef.6 0.4 2 6. deasphalted oil into lighter products that are largely olefinic for light fractions and strongly aromatic for heavy fractions. Fluid catalytic cracking is the largest refining process for the production of gasoline with a global capacity of more than 14.0 29.5 99.6 1.[4] F L UID CA TA L Y TIC CRA CK ING Fluid catalytic cracking units account for about 97% of propylene produced at the refineries as a coproduct to gasoline. the heat balance is obtained by the combustion of catalyst-deposited coke in the regenerator. and how the C5þ liquid byproducts increase dramatically with heavier feeds. all cracking reactions are characterized by the production of appreciable amounts of corresponding olefins. LLC . The main FCC sections comprise feed injection system.4 1.6 52.2]. This can be achieved by the utilization of low sulfur crude oils or using a higher performance feed hydrotreater upstream of the FCC unit. reactor (riser). To achieve higher outputs of light olefins. D ue to the higher annual growth rates of propylene compared to ethylene.3 58. and regenerator.6 96. About 60% of FCC propylene is used in chemical production and the remaining is used in the production of high-octane gasoline blends.5 4.0 100.) W o r ld p r o d u c tio n in 20 0 2 ( m i l l i o n t p y ) 35. Table 2 shows typical propylene yields from steam cracking of different hydrocarbon feedstocks.

4 37. Table 3 presents a comparison of the yield structure of conventional FCC and selected high-olefin technologies.0 4.) 500 1. LLC .5 © 2006 by Taylor & Francis Group.3 P e t r o FC C 590 6.5 H S . S elective Component Cracking (L ummus). and IndM ax (Indian Oil).0 15. licensed by S tone & W ebster=S haw S haw and R IPP=S inopec.0 28.3 14. Processes in various stages of development include PetroFCC (U OP).[5] R ecent catalyst developments have helped increase the propylene yield of conventional FCC from 4. S audi Aramco).5 5.3 15. High S everity-FCC (K FU PM .5 21.[5– 7].5 R eaction temperature ( C) Product yield (wt%) E thylene Propylene M ixed butanes G asoline Heavy and light oils Coke (From R efs. D eep catalytic cracking.8 9. M axofin (K B R .6 4.[5– 7] T a b le 3 P a ra m e te r Product yields of conventional and emerging FCC processes FC C  D C C 530 5.P r o p y l e n e P r o d u c t io n 2 4 6 3 P Fig. J CCP.9 51.0 14. In particular. the use of Z S M -5 catalyst additive is increasing to boost propylene production.4 14. 1 S chematic flow diagram of a conventional FCC process.8 6. E xxonM obil).7 39.FC C 600 2. it is economical to recover propylene from an FCC unit for chemical uses.0 22. however.9 17.5 4.0 14.9 6. is the only high-olefin FCC process that reached the commercialization stage.5% to 10% or greater. propylene yield.

) [8] L ic e n s o r L ummus-Houdry S namprogetti-Y arsintez U OP L inde-B AS F-S tatoil K rupp U hde R e a c to r ty p e Fixed bed Fluidized bed M oving bed Fixed bed Fixed bed C a ta ly s t Cr2O3=Al2O3 Cr2O3=Al2O3 Pt=Al2O3 Cr2O3=Al2O3 Pt=S n=Z n=Al2O3 R e a c tio n c o n d itio n s 560– 620 C. N ew carbon– carbon double bonds are formed at or near room temperature even in aqueous media from starting materials. B ecause olefin metathesis is a reversible reaction. In a process with fixed-bed reactors. © 2006 by Taylor & Francis Group. C3 H8 ) C3 H6 þ H2 DHr. M etathesis can be added to steam crackers to enhance the production of propylene by the transformation of ethylene and the cracking of mixed butenes. The disadvantage is that a separate regeneration unit is needed. 2 presents a typical schematic flow diagram for propane dehydrogenation. a functional group that is unreactive toward many reagents that react with many other functional groups. Thermal cracking reactions limit the maximum practical temperature. The amount of olefin in the reactor effluent is dependent on the reactor outlet conditions. different concepts have been used to enable regeneration of the catalyst. . S everal commercial processes have been developed for the catalytic dehydrogenation of propane to propylene as presented in Table 4.2464 P r o p y le n e P r o d u c tio n T a b l e 4 Typical properties of commercial propane dehydrogenation processes P ro c e ss Catofin FB D -3 Oleflex PD H S TAR (From R ef. propylene can be produced from ethylene and butene-2. > 1 atm 590 C. 3 shows a schematic flow diagram of a typical metathesis process. E xamples of metathesis S ide 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. and pressure. > 1 atm 500 C.298 K ¼ 129:4 kJ =mol Fig. > 0. High temperatures and relatively low pressures are used to get a reasonable conversion of propane. 2 Flow diagram of catalytic dehydrogenation of propane to propylene. six use U OP’ s Oleflex continuous moving-bed process.5 atm P ROP A NE DE H Y DROG E NA TION Propane dehydrogenation is a highly endothermic process. Other processes include K rupp U hde’ s S TAR process. B ecause of the fast deactivation by coke formation. M E TA TH E S IS Olefin metathesis is a useful reaction for the production of propylene from ethylene and butenes using certain transition-metal compound catalysts.[9] F i g . The advantage with a moving bed or a fluidized bed is that the catalyst can be continuously removed from the reactor and be regenerated.[8] Of the seven commercial propane dehydrogenation plants in operation. M etathesis transforms the carbon– carbon double bond. Two different catalyst systems based on chromium and platinum are used within a temperature range of 500– 650 C. 3. The two main equilibrium reactions that take place simultaneously are metathesis and isomerization. The reaction is equilibrium limited. The other uses AB B L ummus’ Catofin cyclic multiple-reactor system. as well as technologies from L inde and S namprogetti. becomes the dominant variable. therefore.5 atm 540– 590 C. 1 atm 550– 650 C. LLC . at least two reactors must be used so that the catalyst in one reactor can be regenerated without stopping the process. Fig.

LLC . none of these processes have been used in commercial olefin production.[1]. P r o p y le n e fr o m M e th a n o l B ecause the market for olefins currently greatly exceeds that for methanol production. L urgi 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 presence of steam. there are two processes for the production of propylene from methanol: the first process is methanol to olefin (M TO) process. D espite numerous patents and demonstration plant trials. Ol e fi n In t e r c o n v e r s i o n S everal on-purpose propylene production technologies are based on the catalytic interconversion of C4– C8 olefins in a fixed. olefin production could become an important new outlet for the potentially vast quantities of low-cost methanol. T a b le 5 S election criteria for on-purpose propylene production processes R e fi n e ry D C C G as oils N o M oderate S everal D e h y d r o ge n a t io n Propane N o High S everal M e t a t h e s is C2– C4 Olefins Y es M oderate One O l e fi n c r a c k in g C4– C8 Olefins Y es M oderate N one M T O /M T P M ethanol N o V ery high N one S e l e c t io n c r it e r ia Feedstock S team cracker integration Investment Commercial units (From R ef. All developed processes use shape-selective medium-pore zeolitic catalysts that crack olefin-rich streams to predominately ethylene and propylene. M ethanol conversion produces a mixture of ethylene and propylene of various ratios or primarily propylene depending on the process. However. The process key element is a potassium– vanadium catalyst doped with boron oxide and supported on a robust mullite– corundum carrier. Other technologies include Atofina= U OP’ s olefin cracking process (OCP). The process can be added to conventional steam cracking plants or FCC units. L yondell= K ellogg’ s fluidized-bed S uperflex process. Currently. it is unlikely that these processes will replace steam cracking for ethylene production in the foreseeable future.P r o p y l e n e P r o d u c t io n 2 4 6 5 P Fig. processes include the low temperature M eta-4 by Axens and the Olefins Conversion Technology (OCT) by AB B L ummus (acquired from Phillips). R eaction thermodynamics determine the product slate and the selectivity independent of feedstock sources. developed by U OP and Hydro.) © 2006 by Taylor & Francis Group. L inde’ s fixedbed catalytic cracking (FB CC). The main objective is to achieve higher yields of light olefins and to lower capital and operating costs. The fluidized-bed technologies are based on a reactor=regenerator design similar to conventional FCC. and E xxonM obil’ s olefin interconversion (M OI) and fluidized-bed propylene catalytic cracking (PCC). E M E RG ING TE CH NOL OG IE S Ca t a l y t i c Cr a c k i n g o f H i g h e r H y d r o c a r b o n s A number of nonconventional technologies such as the catalytic cracking of naphtha are being explored as an alternative conventional steam cracking of hydrocarbons. 3 Typical flow diagram of olefin metathesis process. V niios has developed a conceptually new technology for the catalytic cracking (pyrolysis) of petroleum fractions using heterogeneous catalysts.or fluidized-bed reactor configuration.

G ulf Professional Publishing: B oston. Et hylene: K eyst one t o t he Pet rochemical I ndu st ry. A. 4. and methanol conversion.. Ino. S ept. Farrauto. RE F E RE NCE S 1. 6. 91 pp. 66. 2nd E d. However. The selection criteria for on-purpose propylene production processes are summarized in Table 5. CONCL US IONS 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 dehydrogenation and olefin metathesis. 6 (1).. 184 pp. The role of the FCC in the refinery of the future.. Akzo N obel Paris.. 1 0 1 (4).. 1980. 2003. R efinery sources will fill the future ‘ ‘ propylene gap. T. Propylene on demand. 8. M arcel D ekker: N ew Y ork. B oth processes start from converting natural gas into methanol. 3. Plotkin. 141. M . K . R .. B lackie Academic and Professional: L ondon. 9. D own-flowing FCC reactor increases propylene and gasoline make. K niel. Hatch.. 2 0 0 0 .. research is ongoing to develop new on-purpose technologies such as catalytic cracking of hydrocarbons. Chemical and E ngineering N ews 2 0 0 3. L . 2 0 0 3. S tork. 15.. D eveloping a process for the new century. U pson. Presented at Akzo N obel Technical S eminar on How to M eet E nvironmental Targets. J . M atar. B artholomew. Aitani. 9 8 (33). 2002.. 8 1 (50). Okuhara. W . S . M . Pittman. Propylene: olefin of the future? Presented at the 21st Annual Petrochemical W orld Trade Conference. Abul-Hamayel. LLC . which is then converted to light olefins. M a’ adhah. 2001. Oil G as J . developed by L urgi.’ ’ Oil G as J . The processes are attractive as part of a complex for the utilization of stranded natural gas reserves. Chemical W eek and Chemosystems: Houston. C. © 2006 by Taylor & Francis Group. W alther. L . 65. Houdek. R . To meet strong demand for propylene derivatives. A.. T. A. M uch of the increase in propylene demand is expected to come from steam crackers. 411 pp. 1997. Chemist ry of Pet rochemical Processes.. olefin interconversion. followed by refineries and dehydrogenation plants. W inter.2 4 6 6 P r o p y l e n e P r o d u c t io n and the second process is methanol to propylene (M TP) process. L etzsch. C. L . These processes uncouple propylene production from steam crackers and refineries allowing higher production flexibility. Tullo. Hemler. J . they will remain more expensive than the coproduct routes and will continue to provide only marginal production volumes in niche circumstances. F u ndament als of I ndu st rial Cat alyt ic Processes. 2. 5. Petroleum Technology Q uarterly 2 0 0 1 . N ov. O. 7.