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Fluid Catalytic Cracking

• • • • • General process and history Hardware installations and operation Catalytic reactions Catalysts New developments

What is cracking?
• Cracking is the cleaving of large hydrocarbons into smaller hydrocarbons without addition of hydrogen • Thermal cracking • Radicals as intermediates • Catalytic cracking • Carbenium ions as intermediates

• Long chain (high boiling point) hydrocarbons are converted to gasoline range products. • Cracking changes the H/C ratio via removal of carbon.

Cracking 1

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Cracking - feed and products

FAU

• Worldwide production capacity – 500 million ton/year • Between 20 and 50 % of the gasoline pool consists of cracked products.

History of cracking processes
1936 Eugene Houdry, Socony Vacuum Oil and Sun Oil introduce the first commercial units, • Fixed bed reactor that are replaced by continuous processes. – transport by means of mechanical devices – transport by gases Fluid bed catalytic cracking (FCC) introduced; catalyst is suspended by means of gaseous hydrocarbons Introduction of zeolite catalysts Riser FCC with extremely short contact times Controlled combustion zeolite cracking catalyst Octane optimization catalyst

1941

1960 1971 1975 1980

Cracking 1

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• Each reactor had to be taken offstream for catalyst regeneration. Cracking 1 3 . • Several reactors in parallel.History of the petroleum cracking process • Houdry catalytic cracking unit reactor consists of tubular reactors in molten salt medium. History of the petroleum cracking process • Continuous reaction and regeneration process • Moving bed reactor with catalyst transport by buckets or gas lift.

Typical operating conditions • Riser dimensions (44 m height.Modern FCC unit 25-200°C The oxidative regeneration is highly exothermic and delivers largest part of the energy necessary for cracking. 12 t/hour circulate. 1. 80 ton/hour oil converted FCC units Cracking 1 4 . favored by high temperatures. The process is endothermic. 200-340°C 340-425°C >425°C Cracking reactions involve the rupture of the C-C bond.4m inner diameter) • Oil/cat ratio of 7 • 510°C reaction temperature (80% conversion) • 5-7 seconds residence time • 100 tons catalyst.

Separator and regenerator Riser-Reactor • Plug flow to realize short contact times • Separation of catalyst and products via cyclones • Catalyst passed via a stripper (removal of products). catalyst particles 20-60µm. Regimes in fluidized beds Increasing gas velocity Cracking 1 5 . Catalyst 3-5% wt% of the zeolite (crystal diameter 1µm) in oxide matrix. • The heat in the regenerator provides the energy for the process. • Flue gas is treated in a CO boiler (CO→CO2) and filtered electrostatically. Regeneration • Oxidation of coke to CO + CO2 and water • Dense fluidized bed reactor Particles below 5µm will be removed by cyclones.

Naphtenes (cycloalkanes) H2 H2C C C CH2 H2 Olefins H C Ring opening does not occur with C6 units H3C C H CH3 6. Alkylaromatics H2 C C H2 H2 C Side chain cracking CH3 H2 C H C CH3 + + H2C CH2 H3C CH3 CH2 Secondary cracking reactions 5.Primary cracking reactions 1. Hydrogen transfer reactions Naphtenes + alkenes aromatics + alkanes Aromatic coke precursor + alkene coke + alkane CH3 CH3 CH3 + H3C C H + CH3 C H3C H C H2 Cracking 1 6 . Alkylaromatics H2 C CH3 Dealkylation + H2C CH2 4. Alkanes H3C H2 C Alkenes and smaller alkanes C H2 H2 C C H2 H2 C CH3 H3C H2 C C H2 CH3 +HC 3 H C CH2 2. Alkenes H3C H2 C C H Smaller alkenes H C C H2 H2 C CH3 H3C H C C H CH3 +HC 3 H C CH2 3.

Alkyl group transfer H3C CH3 + CH3 + CH3 9.Secondary cracking reactions 7. Condensation reactions (Dehydrocyclization) H C CH2 H2 C H C H2 C CH3 + H3C C H C H2 C H2 H2 + C C CH3 C CH2 H2 H2 H3C HH Equilibria of hydrocarbon reactions under cracking conditions Cracking 1 7 . Isomerization (Alkene H2 C H C Iso-alkene) CH3 H3C C H CH3 H3C C H CH3 8.

10. p. LCO (light cut oil) has a maximum. Process Des. Ind. Eng.Simplified operation scheme for FCC k1 Gas oil Gasoline + diesel k2 Gases + coke k3 Three-component model of Weekman and Nace (Nace et al. Chem.. Dev. while HCO (heavy cut oil) decreases continuously To maximize gasoline yield it is necessary to work at intermediate conversions Cracking 1 8 . 1971) Prediction of gasoline yield vs. Coke and Gases increase continuously. the gasoline yield has a maximum.. conversion At moderate conversions. 530.

Basic variations of conversion along riser Reaction temperature influences products 482°C 537°C 583°C Cracking 1 9 .

• Shift of the electron with the radical is not possible or very slow no isomerization • Larger hydrocarbon radicals may terminate via hydrogen abstraction. but do so at a lower rate compared to the methyl radical. Cracking 1 10 . Observations in thermal cracking • Empirical β-rule: The cleavage of the C-C bound occurs at the β carbon atom in respect to the unpaired electron. • This results in large amounts of ethene and small amounts of methane and α-olefins. R1 H2 C C H2 H2 C C H2 H2 C C H2 R2 R1 H2 C C H2 H2 C CH2 + H2C H2 C R2 R1 H2 C C H2 H2 C CH2 R1 H2 C CH2 + H2C CH2 • Reaction continues until CH3 radical is formed.Thermal cracking • Industrially widely applied prior to catalytic cracking. • At the moment used to convert naphtha into olefins and for visbreaking of heavy feeds. R1 H2 C C H2 H2 C CH3 + CH3 R1 H2 C C H2 H2 C CH2 + CH4 Free radicals is generally observed. • Stability of the radicals: primary > secondary > tertiary > methyl. • Larger molecules that contain a tertiary carbon atom may "coil back" to undergo internal hydrogen transfer.

which decomposes into hydrogen/alkane and a carbenium ion. the lower the stability Relative gas phase stabilities of carbenium ions Generation of carbenium ions • Protonation of olefins by – Brønsted acidic hydroxyl groups – carbonium ions (proton transfer) • Hydride abstraction from alkanes – with metal cations – with carbenium ions (hydride transfer) • Carbonium ion decomposition Very strong acid sites protonate a paraffin forming a pentacoordinated carbocation (carbonium ion). Cracking 1 11 .Catalytic cracking • Catalyzed by acidic sites on the surface • Transition states along the reaction pathway are – carbonium ions – carbenium ions • The higher the energy necessary to form the carbocation.

H3C O Si O H2 H C + CH3 C O O Si Al Hydride abstraction and dehydrogenation H3C C H2 H2 C CH3 H3C H C C H CH3 Al HAl H O Si O O Si O H O Si H+ O O Si O • Lewis acid sites abstract hydride.Proton addition to olefins H CH 3 C C H H 3C O Si O Si H O Al O O Si H2 H C CH3 C H3C O O Si Al O • Carbenium ions of small olefins exist only as transition states. Cracking 1 12 . which leads to dehydrogenation and formation of an olefin. • In the ground state they form alkoxy groups. • The olefin is protonated at a nearby Brønsted acid site. • Carbenium ions of sterically hindered olefins are stable.

• Carbenium ions of sterically hindered olefins are stable H3C O Si O H2 H C CH3 C O Al O Si Cracking 1 13 . Decomposition of carbonium ions H3C H2 C C H2 CH3 H3C O O Si O Si O Si O Si H O Al H2 C C + CH3 HH O OAl .Activation via hydride abstraction H CH 3 C C H H 3C O Si O Si H O Al H3C O O Si O H2 H C CH3 C O Al CH3 C H3C H CH3 O Si H3C H2 C C H2 CH3 CH3 H3 C O Si O Si C O Al CH3 O • Hydride abstraction helps activating alkanes in the presence of alkenes.H2 • Carbonium ions are transition states that decompose readily into alkoxy groups.

concentration of reactants .Carbonium ions (monomolecular pathway) cleavage of the C-C bond next to the positive charge . the monomolecular pathway is important at the entrance of the riser reactor.Carbonium ions .Carbenium ions • The way alkanes are converted depends upon the reaction conditions.Mono.concentration of acid sites .Carbenium ions (bimolecular chain reaction) cleavage of the C-C bond in -position to the positive charge Overall mechanism of protolytic cracking H3C H2 C C H2 H2 C CH3 H3C H2 C C H2 H2 C CH3 [SiOHAl] [SiOHAl] H3C CH2 H3C CH H2 H2 C H C C + CH3 H H CH2 H3C CH2 + [SiO-Al] H3C CH3 • Under industrial conditions. .and bimolecular cracking • Cleavage of alkanes can be achieved involving carbocations as intermediates .conversion • Cracking of the alkane fraction may proceed via a mono or a bimolecular (chain) reaction pathway. . • Bimolecular mechanism dominate at all other stages Cracking 1 14 .

•• Scission of bond ß to carbon with positive charge Scission of bond ß to carbon with positive charge yielding an α-olefin and aaprimary carbenium ion yielding an α-olefin and primary carbenium ion •• Primary carbenium ion undergoes rapid hydride shift Primary carbenium ion undergoes rapid hydride shift to form more stable secondary ion to form more stable secondary ion H2 C C H CH3 Hydride transfer propagation in ß-cracking O H2 C H CH3 C H3C O O Al Si Si H2 C CH 3 R1 C H3C H C H2 O O Si O CH3 R1 C C H3C O O H2 Si Al H3 C H2 C C H2 CH 3 H3 C C H H C CH3 + [SiOHAl] H3 C H2 C H + C H2 C [SiOAl]CH3 H3 C + C H2 H + C CH3 H3 C [SiOAl]H3C CH3 C H2 H2 C C H2 H + C CH3 CH2 CH3 H2 C H2 C Hydride transfer H3C C H2 CH3 H3C H C CH2 Cracking 1 15 . Secondary carbenium ions form at random.Carbenium ion cracking H3 C H C C H H2 C C H2 CH3 H3 C H C CH2 + H3 C H C CH2 H3 C H C C H H2 C C H2 CH3 H3 C H C [SiOHAl] [SiO-Al] CH2 H3C CH2 + C H H2 C C H2 CH3 Si-O-Al CH2 H 3C CH2 [SiOHAl] H3 C H + C [SiO-Al] CH2 H3C CH C H2 H2 C C H2 CH3 CH2 H3C CH2 + [SiO-Al] •• Secondary carbenium ions form at random.

scission not possible H2 C H2 C + CH3 energetically not favored Major features of thermal and catalytic cracking Cracking 1 16 . H3 C H + C C H2 H2 C Catalytic cracking Radical cracking C H2 CH3 β .scission H 3C H C CH2 H2C CH2 H3 C H + C CH3 ß .Ethene hardly formed in catalytic cracking Methane and ethane are less observed in catalytic cracking in contrast to thermal and protolytic cracking.

Reaction network for catalytic cracking Cracking 1 17 .

donor concentration Increase in carbenium ion lifetime Cracking performance can be predicted Cracking 1 18 .Hydride transfer influences catalyst selectivity no measurable reaction cracking isomerization no reaction Increase in H.

Once a carbocation is formed.Concentration of hydrocarbons at the surface • Relative activity of hydrocarbons with tertiary C secondary C 1 0. • The formation of the carbonium ion seems to determine the rate. then the energetically most difficult step is the hydride transfer.Cracking of single components • The rate depends upon . • Olefins enhance the reaction rate Comparison of hydrocarbon classes in reactions Al2O3/SiO2/ZrO2 catalyst. average activities over 1 hour Cracking 1 19 .h.1 primary C 0.05 • Branched hydrocarbons crack faster • Larger hydrocarbons adsorb stronger. The higher surface concentration leads to higher rates.13.Structure of the hydrocarbon .7 mol HC feed/l catalyst. T= 773 K.

Weisz shows that the rate of cracking of alkanes is enhanced by olefins.Olefins increase the cracking rate Dehydrogenation Cracking 1% Impurity Classic experiment of P. Cracking of gas oil – gasoline selectivity Cracking 1 20 .B.

Effect of reaction temperature on the OPE for gasoline Cracking of gas oil – C5+ and butene selectivity Cracking 1 21 .

Cracking of gas oil – n-butane selectivity Cracking of gas oil – iso-butane selectivity Cracking 1 22 .

Cracking of gas oil – propane and ethene selectivity Reaction network for cracking of paraffins Cracking 1 23 .

Coke formation • Negative consequences: catalyst deactivates • Positive consequences: Heat for endothermic reactions generated Carbon removed. source of hydrogen • Coking is high with olefinic and aromatic feeds • The aromatic character of the coke increases with the aromatic character of the feed • Coking increases with – Increasing acid strength – Increasing concentration of acid sites – Presence of Lewis acids Cracking of gas oil – coke selectivity Cracking 1 24 .

Reaction pathway to coke Initiation Propagation Termination Cracking 1 25 .