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 renery include alkylation, catalytic polymerization, and dimerization for the production of high-octane gasoline blends. In general, propylene is supplied in three separate quality grades: renery (70%), chemical (92 to 96%), and polymer (99.6%). The two major commercial sources of propylene are ethylene steam cracker plants and renery uid catalytic cracking (FCC). Other routes include olen 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 olen metathesis.[1,2]. Other emerging technologies include catalytic cracking of higher hydrocarbons, olen 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 olen of the future. [1] This increase is driven by the demand for derivatives, especially polypropylene.

S TE A M

CRA CK ING

OF H Y DROCA RB ONS

The main route for producing light olens, 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 olen-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 olen 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 efuent 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 C3, which is sent for further treatment to recover propylene and other olens. 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 olen yield
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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 enery FCC units M etathesis=dehydrogenation Total
(From R efs.[1,2].)

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 ) 35.9 15.3 1.6 52.8

S h a r e ( %) 68.0 29.0 3.0 100.0

A n n u a l g ro w th fo r 20 0 2 20 15 ( %) 4.3 5.0 6.5 4.7

(i.e., the sum of ethylene and propylene) drops to an uneconomically low level. D ue to the higher annual growth rates of propylene compared to ethylene, the highest possible P=E in steam crackers is very desirable. Table 2 shows typical propylene yields from steam cracking of different hydrocarbon feedstocks, and how the C5 liquid byproducts increase dramatically with heavier feeds.[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 reneries as a coproduct to gasoline. D elayed cokers and visbreakers produce the remaining 3%. In some reneries, a fraction of the propylene 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 rening 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 N orth America alone. Fluid catalytic cracking converts heavy oil feedstocks such as vacuum gas oil, residues, deasphalted oil into lighter products that are largely olenic for light fractions and strongly aromatic for heavy fractions.[5]

A schematic ow 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 uidized 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 characterized by the production of appreciable amounts of corresponding olens. The propylene yield from FCC unit is a function of the following parameters:     Processing capacity of the FCC unit; Type of feedstock; R iser reactor outlet temperature (severity); and Fluid catalytic cracking catalyst type and additives.

To achieve higher outputs of light olens, particularly 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 commercial 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

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

L iq u id fe e d s B u ta n e s 24 37 16.4 2 6.4 12.6 0.5 99.0 N a p h th a 26 30 14.1 4.5 8 18.5 0.4 98.3 G a s o il 23 25 14.4 5 6 32 0.6 96.7

E th a n e 13 80 1.11 1.4 1.6 1.6 0.03 86.7

P ro p a n e 28 45 14.0 2 1 9 0.3 58.3

Propylene=ethylene (wt=wt) Propylene (wt% of C3)

(From R ef.[3].)

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P r o p y l e n e P r o d u c t io n

2 4 6 3

Fig. 1 S chematic ow diagram of a conventional FCC process.

propylene yield; however, it is economical to recover propylene from an FCC unit for chemical uses. D eep catalytic cracking, licensed by S tone & W ebster=S haw S haw and R IPP=S inopec, is the only high-olen FCC process that reached the commercialization stage.[5] R ecent catalyst developments have helped increase the propylene yield of conventional FCC from 4.5% to 10% or greater. In particular, the use of Z S M -5

catalyst additive is increasing to boost propylene production. Processes in various stages of development include PetroFCC (U OP), High S everity-FCC (K FU PM , J CCP, S audi Aramco), M axon (K B R , E xxonM obil), S elective Component Cracking (L ummus), and IndM ax (Indian Oil). Table 3 presents a comparison of the yield structure of conventional FCC and selected high-olen technologies.[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 5.4 14.3 14.7 39.0 15.6 4.3

P e t r o FC C 590 6.0 22.0 14.0 28.0 14.5 5.5

H S - FC C 600 2.3 15.9 17.4 37.8 9.9 6.5

R eaction temperature ( C) Product yield (wt%) E thylene Propylene M ixed butanes G asoline Heavy and light oils Coke
(From R efs.[5 7].)

500 1.5 4.8 6.9 51.5 21.0 4.5

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T a b l e 4 Typical properties of commercial propane dehydrogenation processes P ro c e ss Caton FB D -3 Oleex PD H S TAR

(From R ef. .)
[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, > 0.5 atm 540 590 C, 1 atm 550 650 C, > 1 atm 590 C, > 1 atm 500 C, 3.5 atm

P ROP A NE

DE H Y DROG E NA TION

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 olen in the reactor efuent is dependent on the reactor outlet conditions. Thermal cracking reactions limit the maximum practical temperature, and pressure, therefore, becomes the dominant variable. C3 H8 ) C3 H6 H2 DHr;298 K 129:4 kJ =mol

Fig. 2 presents a typical schematic ow diagram for propane dehydrogenation. In a process with xed-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 uidized bed is that the catalyst can be continuously removed from the reactor and be regenerated. The disadvantage is that a separate regeneration unit is needed.

M E TA TH E S IS Olen metathesis is a useful reaction for the production of propylene from ethylene and butenes using certain transition-metal compound catalysts. The two main equilibrium reactions that take place simultaneously are metathesis and isomerization. M etathesis transforms the carbon carbon double bond, a functional group that is unreactive toward many reagents that react with many other functional groups. N ew carbon carbon double bonds are formed at or near room temperature even in aqueous media from starting materials. B ecause olen metathesis is a reversible reaction, propylene can be produced from ethylene and butene-2. 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. Fig. 3 shows a schematic ow 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. Two different catalyst systems based on chromium and platinum are used within a temperature range of 500 650 C. B ecause of the fast deactivation by coke formation, 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.[8] Of the seven commercial propane dehydrogenation plants in operation, six use U OP s Oleex continuous moving-bed process. The other uses AB B L ummus Caton cyclic multiple-reactor system. Other processes include K rupp U hde s S TAR process, as well as technologies from L inde and S namprogetti.[9]

F i g . 2 Flow diagram of catalytic dehydrogenation of propane to propylene.

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P r o p y l e n e P r o d u c t io n

2 4 6 5

Fig. 3 Typical ow diagram of olen metathesis process.

processes include the low temperature M eta-4 by Axens and the Olens Conversion Technology (OCT) by AB B L ummus (acquired from Phillips).

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. The main objective is to achieve higher yields of light olens and to lower capital and operating costs. V niios 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. D espite numerous patents and demonstration plant trials, none of these processes have been used in commercial olen production. However, it is unlikely that these processes will replace steam cracking for ethylene production in the foreseeable future. Ol e 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 olens in a xed- or uidized-bed reactor

conguration. The process can be added to conventional steam cracking plants or FCC units. All developed processes use shape-selective medium-pore zeolitic catalysts that crack olen-rich streams to predominately ethylene and propylene. The uidized-bed technologies are based on a reactor=regenerator design similar to conventional FCC. R eaction thermodynamics determine the product slate and the selectivity independent of feedstock sources. L urgi developed a low-pressure catalytic process known as Propylur that uses adiabatic xed-bed technology for converting higher olens to propylene and ethylene in the presence of steam. Other technologies include Atona= U OP s olen cracking process (OCP), L yondell= K ellogg s uidized-bed S uperex process, L inde s xedbed catalytic cracking (FB CC), and E xxonM obil s olen interconversion (M OI) and uidized-bed propylene catalytic cracking (PCC).

P r o p y le n e fr o m

M e th a n o l

B ecause the market for olens currently greatly exceeds that for methanol production, olen production could become an important new outlet for the potentially vast quantities of low-cost methanol. M ethanol 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 rst process is methanol to olen (M TO) process, developed by U OP and Hydro,

T a b le 5

S election criteria for on-purpose propylene production processes R e 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 Olens Y es M oderate One O l e n c r a c k in g C4 C8 Olens 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.[1].)

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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, developed by L urgi. B oth processes start from converting natural gas into methanol, which is then converted to light olens. The processes are attractive as part of a complex for the utilization of stranded natural gas reserves.

RE F E RE NCE S 1. Plotkin, J . Propylene: olen of the future? Presented at the 21st Annual Petrochemical W orld Trade Conference, Chemical W eek and Chemosystems: Houston, S ept, 2003. 2. W alther, M . R enery sources will ll the future propylene gap. Oil G as J . 2 0 0 3, 1 0 1 (4), 65. 3. M atar, S .; Hatch, L . Chemist ry of Pet rochemical Processes, 2nd E d.; G ulf Professional Publishing: B oston, 2001; 91 pp. 4. K niel, L .; W inter, O.; S tork, K . Et hylene: K eyst one t o t he Pet rochemical I ndu st ry; M arcel D ekker: N ew Y ork, 1980; 184 pp. 5. L etzsch, W . The role of the FCC in the renery of the future. Presented at Akzo N obel Technical S eminar on How to M eet E nvironmental Targets, Akzo N obel Paris, N ov, 2002. 6. Houdek, J .; Hemler, C.; Pittman, R .; U pson, L . D eveloping a process for the new century. Petroleum Technology Q uarterly 2 0 0 1 , 6 (1), 141. 7. M a adhah, A.; Abul-Hamayel, M .; Aitani, A.; Ino, T.; Okuhara, T. D own-owing FCC reactor increases propylene and gasoline make. Oil G as J . 2 0 0 0 , 9 8 (33), 66. 8. Farrauto, R .; B artholomew, C. F u ndament als of I ndu st rial Cat alyt ic Processes; B lackie Academic and Professional: L ondon, 1997; 411 pp. 9. Tullo, A. Propylene on demand. Chemical and E ngineering N ews 2 0 0 3, 8 1 (50), 15.

CONCL US IONS Propylene is conventionally produced as a coproduct in steam cracking of naphtha or FCC of gas oil in reneries and to a lesser extent via propane dehydrogenation and olen metathesis. To meet strong demand for propylene derivatives, research is ongoing to develop new on-purpose technologies such as catalytic cracking of hydrocarbons, olen interconversion, and methanol conversion. The selection criteria for on-purpose propylene production processes are summarized in Table 5. These processes uncouple propylene production from steam crackers and reneries allowing higher production exibility. However, they will remain more expensive than the coproduct routes and will continue to provide only marginal production volumes in niche circumstances. M uch of the increase in propylene demand is expected to come from steam crackers, followed by reneries and dehydrogenation plants.

2006 by Taylor & Francis Group, LLC