BITS Pilani

K K Birla Goa Campus

Catalytic cracking
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11/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 FCC unit

11/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalytic cracking - Introduction

• Most widely used process to convert heavy oil into

gasoline of high octane no
• The following effects of thermal cracking can be avoided
in catalytic cracking
• Unsaturation of products
• High coke formation
• Low yields of gasoline
• Reaction mechanism
• Carbonium ion mechanism
• leads to formation of more stable saturated compounds (with isomeric
reactions
• Guided by nature of molecule undergoing cracking 4

11/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Carbonium ion chemistry

• Carbonium ion: a positively charged ion acting in

chemical reaction
• Protonation  formation of charged ions
• Formation of branched chain compounds
• Steps
• Proton elimination, Hydride shift, Methyl shift, Addition, Cracking, Hydride
transfer, Termination of carbonium ions
• Acid sites of catalyst provides such charges
• Heats of formation of carbonium ions (pg. 361)
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 Feedstock
• Gas oils or blends of thermally cracked oils
• Feedstock with sulfur, oxygen compounds, basic nitrogen and metals
should be avoided as these compounds harm the catalyst
• Straight run / vacuum gas oil  preferred without pretreatment
• Residuum  preferred to be pretreated to remove impurities
• Pretreatment
• Increases the life of the catalyst
• Avoid purification process for different fractions obtained
• Pretreatment techniques
• Sulfuric acid treatment  removal of sulfur and nitrogen compounds
• Phenol or furfural treatment  specially for aromatic rich stocks
• Deasphalting  Residuum
• Adding additives like antimony  To passivate the metal contaminants
• CCR < 4% to limit carbon formation 6

13/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalytic cracking
conditions/variables
• Operating/important parameters
– Temperature  450 – 510 C (relatively lower than TC)
– Pressure (mostly < 2 atm)
» Reactor pressure: set by unit capacity
» Regenerator pressure: coupled to reactor system
– Catalyst to oil ratio
– Catalyst activity
– Space velocity
• Conversion is affected due to drop in surface area and increase in
bulk density (it happens generally with increase in cracking time)
• Catalyst to oil contact time
– < 4 seconds (60 % conversion results)
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13/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalyst
• Amorphous silica – alumina and silica – magnesia
• Zeolites with rare earth exchanged ions were added to amorphous
matrix  to improve catalyst activity and selectivity
• Nobel metals (small amounts)  added to assist in improving the
performance of the catalyst
• Nitrogen and sulfur  May cause issues (sulfur can be converted to
H2S (cracking) and separated. N2 is relatively difficult to remove
• Heavy metal complexes in feedstock  leads to coke formation /
blocking metal sites; Demetallization of feed or addition of metal
passivators are the possible solutions.
• Cracking of hydrocarbons take place on acid sites (Synthetic silicates
possess higher activity and give better product distribution
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13/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalyst

• Zeolites [Crystalline aluminium silicates] (against

amorphous catalyst)
• Have more active sites and adsorption capacity  faster cracking
rates
• High surface area
• Have more selectivity for intermediates (gasoline)
• Hydrogen transfer is also very high  saturation
• More resistant to heat and steam
• Less deposition of coke (with 70% conversion, 6% of coke
deposits)
• Amorphous: ambiguous structural assemblies creates problems
for having wide range of active sites
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13/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 • Zeolites (aluminium silicates) – commercially used
catalysts
• X – zeolite and Y – zeolite
• Typical characteristics:
– Surface area: 100 – 400 m2/gm
– Pore volume: 0.2 – 0.5 ml/g
– Average pore dia: 50 – 80 0A
– Si/Al ratio : 4.5
• Thermal stability of these catalysts is still a challenge (Used
catalyst shows less activity due to coke deposits)

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13/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalytic Crackers (Processes)

• Fixed bed (Houdry)  Obsolete (No new units)

• Moving bed (Air lift)  20% of the catalytic crackers
– Thermofor
– Houdry flow
• Fluidized bed  80 % of the catalytic crackers

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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Fixed bed catalytic process (Houdry
fixed bed process)
• Three reactors in parallel (for continuous operation)
• Four valves at the bottom of each reactor (only one in operation)
• Operation  process (reaction), steam purge, regeneration,
air/steam purge
• Molten salt circulation is used from reactor (under regeneration) to
reactor (under process) to maintain heat balance by providing
necessary heat of reaction
• Cyclic operation times
– Process (on stream) – 10 min
– Downward purging (steam) to remove HCs – 5 min
– Regeneration by blowing hot air through bottom – 10 min
– Air and steam purge – 5 min
• Operating conditions
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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Fixed bed catalytic process
(Houndry fixed bed process)

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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Moving bed – Air-lift Thermofor
catalytic cracking unit
• Catalyst  Spherical or beads
• Catalyst and oil (feed) move
concurrently move downward
• Reactor is stacked over the regenerator
• Steam purging between reactor and
regenerator
• Spent catalyst regenerated using hot air
blowing
• Catalyst disengager
• Disadvantage: Low catalyst to oil ratio
which leads to coke deposits
• Operating conditions
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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Moving bed – Houdry flow catalytic
cracking unit
• Advantages over TCC
– Ease of operation
– Low cost of maintenance
– High catalyst activity
– Flexibility in handling charge stocks
• Reactor is placed above the regenerator
• System works on self heat balance
• Operating conditions (pg 372)

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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Fluid Catalytic Cracking (FCC)

• Mostly used catalytic cracker

• Gasoline from FCC – contributes > 40% of overall production
• Feedstock: Naphtha to deasphalted oil
• FCC complex:
– Reactor – riser
– Regenerator – flue gas separation
– Distillation and recycling
• Fluidized catalyst : Reactor ↔ Regenerator
• Heat transfer from regenerated catalyst to feed oil and reactor

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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Fluid Catalytic Cracking (FCC)

• Types and designs

– Side by side : Reactor and regenerator are separate vessels
adjacent to each other
» Exxon Mobil
» CB&I Lummus
» Shell
» Axens / Stone and Webster Technology (currently Technip)
» UOP (Universal Oil Products) (currently part of Honeywell)
– Stacked (orthoflow): Reactor is mounted on the top of
regenerator
» KBR (Kellog Brown and Root)

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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Fluid Catalytic Cracking (FCC)

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 Riser

• Contact between feed oil and catalyst occurs in the riser

– Cracking reaction takes place mostly in the riser
– Contact time between oil and catalyst is very short (< 5
seconds)
– Feed oil temperature to the riser: 315 – 430 C
– Feed to riser also contains recycled slurry oil
• With increased cracking
– Coke deposition increases
– Catalyst activity degrades
– Vapor velocity increases sharply
» Slip velocity (relative velocity between catalyst and oil) decreases 
improper cracking
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18/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Riser

• Control of reactions
– Accelerating
regenerated catalyst to
velocity desired in
riser/reactor
– Injecting feed using
spray nozzles (efficient
feed injection)
• Profiles of different
parameters in a riser
cracker with distance
(Fig. 5.7)
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 Reactor

• Cracking to a very less extent

• Operating parameters
– Temp: 500 – 535 C; Pressure: 1.75 bar(g)
• Cyclone separators
– To separate cracked oil vapors (products) and spent catalyst
• Fluidization in reactor
– Dense phase : at the bottom of the reactor
– Dilute phase: in the upper part of the reactor
• Steam stripping at the bottom of the reactor
– To remove trapped cracked products (Hydrocarbons)
• Products are sent to distillation (fractionation) column
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20/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Regenerator

• Burning off the coke deposited on the catalyst

• Combustion air is used for regeneration
• Temperature: 620 – 845 C ; Pressure : 2.0 – 2.5 bar (g)
• Cyclone separators
– To separate flue gas from the catalyst
• Regenerated catalyst
– 0.1 – 0.4 wt% coke
– Sent back to the riser-reactor through a catalyst withdrawal well
• Regenerator flue gas
– Sent to catalyst fines separator (before sending it to atmosphere)
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20/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 FCC – Other important details
• FCC catalysts
– crack 2% outside the pores and remaining inside the pores  pore structures
are very important
– Catalyst conversion, product selectivity and regeneration efficiency
– Bigger pore size  decrease surface area (but increases regen efficiency)
• Factors affecting FCC operations
– Attrition, entrainment in cyclone separators and regeneration systems
• Ideal recovery and addition systems
– Minimizes additions of fresh catalyst
– Maintains an optimum size distribution of circulating catalyst
• Efficient feed injection in risers
– Avoids larger pressure drop and erosion of riser pipes
• Efficient steam stripping
– Augments quick separation of products from catalyst and prevent over cracking
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20/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process variables - Operation

• Conversion, yield (efficiency)

– Cracking temperature (oC)
– Catalyst/oil ratio (kg of catalyst/kg oil)
– Space velocity
» LHSV (vol of feed/(vol of cat) (hr))
» WHSV (kg of feed/(kg of cat)(hr))
• WHSV = 1/(t x (C/O)) (where t is catalyst residence time)
– Catalyst type and activity
• Yield of gasoline
• Heat recovery
• Waste heat boilers (production of steam)
• Power recovery turbines (Power generation)
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 Process variables - Operation

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 Flexi crackers

• Developed by Exxon Mobil

• Model IV
– Riser cracker model (with no dense phase
in the bed)
– Space velocities as high as 50
– Do not require catalyst control valves
– Adv: Maximum liquid products and least
problems in handling different feedstocks
– Cyclones: designed to provide plug flow
without backmixing
– U bend design increased recovery of
catalysts

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23/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Flexi crackers

• Transfer line configuration

– All the cracking takes place in
transfer line and is terminated by
disengaging oil from catalyst in a
cyclone separator

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23/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Ortho-flow reactors

• Developed by KBR
• Highly selective in
converting heavy petroleum
fractions to valuable light
olefins and furnace oils
• Less investment and
operating cost
• Operating conditions
(pg 380)

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23/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 FCC - Technologies

• UOP, Axens, Exxon mobil, Lummus, etc.

• Kellog (Ortho flow)
• ESSO – Flexi cracking
• Standard oil – Ultra cracking

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23/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 RFCC (Residue FCC)

• Provided by UOP and Axens

• Feed is residue (fraction with bp > 565 C; CCR upto 6 wt%,
impurities)
• Generally two stage regeneration sections (to minimize premature
catalyst deactivation)
– First stage  partial burning of coke
– Second stage  remaining burning of coke
– Catalyst cooling in between

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23/09/2024 Amol Deshpande BITS Pilani, K K Birla Goa Campus