1.
Introduction of pyrolysis and cracking
• Pyrolysis is a thermochemical conversion at high temperatures in the absence of oxygen
• Purpose is to crack larger molecules into smaller ones
• Non-catalytic pyrolysis and catalytic cracking are possible in petroleum industry
• In non-catalytic pyrolysis, higher molecular weight compounds are also produced
simultaneously
• Purpose of utilizing catalysts in pyrolysis is:
• 'To lower temperatures and pressures of process
• 'To obtain higher selectivity of cracking with less side reactions
• Commercial thermal pyrolysis started in 1913 in united states
• Fixed bed cracking was applied in 1936
• Moving and fluid bed catalytic cracking in 1945
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2. Reactions: Pyrolysis and Cracking
Various reaction mechanisms were proposed for endothermic thermal pyrolysis and catalytic cracking
A) Thermal pyrolysis reaction mechanism: thermal cracking, polymerization and coking
(i) Thermal cracking - free radical theory
• Free radicals are electrically neutral, highly reactive particles
• Formed by rupture of C-C or C-H bonds with each particle retaining one of the pair of shared
electrons that make up the bond
(a) C4H10 C4H9• + H•
(b C4H9• C3H6 + CH3•
(c) CH3• + RH CH4 + R•
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• If R• is a large alkyl group, it breaks down into an olefin and a small free radical
• This small free radical further reacts as in reaction (c) to produce a chain reaction: (c) CH3• +RH
CH4+R•
• It is terminated only when free radical species react with each other or with solids such as coke or surface
of reactor
(ii) Thermal polymerization
• Larger molecules than present in feedstock formed by polymerization of olefins formed above
(for e.g, C4H9• C3H6 + CH3•, + condensation of any aromatics
(iii) Coke formation
Free carbon always occurs to a degree when hydrocarbons undergo complete degradation:
(d) RH xC + ỵH
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B) Catalytic cracking mechanisms
• Catalytic cracking produces no C1 and C2 fractions and
isomerizes to secondary and tertiary HCs
• These HCs are desirable components of current petrol
• In general, relatively little free carbon (coke) is formed
• Aromatic rings are stable, but any long alkyl side chains
attached to the rings are subject to cracking
3. Reaction conditions: Pyrolysis and Cracking
• Important conditions
• Optimum time
• Temperature
• Pressure and
• Catalyst-to-feed ratio
• These are process specifications which depend on feed Catalytic cracking mechanism
reactivity, desired product and coking tendency. Some
examples shown in the table: 4
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Some observations from variations in reaction conditions:
• Though have more coking tendency, higher molecular weight feeds crack more readily
• High pressure increases rates of polymerization but high pressure also increases the throughput
• Advantage of catalytic cracking is that it lowers pressure and temperature requirements
• In the plant, where low contact time-high temperature conditions exist, quenching to avoid back
or side reaction is required
4. Catalytic cracking process design and operation
Following points important from understanding viewpoint
(a) Selection of catalyst
(b) Process variables
(c) Process characteristics
(d) Equipment design
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(a) Introduction: Catalyst Deactivation, Regeneration, Type of Reactors, etc.
• Catalyst deactivation:
• Cracking on acidic catalysts is endothermic operation in which tarry materials (coke) deposit gradually and
deactivate the catalyst
• Catalyst regeneration:
• Reactivation is possible by oxidation of coke which is exothermic; known as regeneration
• Early fixed bed units (by Houdry) went on stream in 1936
• These units employed a 10min make-clean cycle, and using expensive
tubular reactors
• In the reactors, molten salts circulated in the shell side
• Reactors were constructed of expensive alloys to withstand alternate
reducing and oxidizing conditions
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• Fixed bed design was obsolete within 10 years and was replaced by moving with large pellet catalyst and fluid
bed reactors with catalyst
• In both of these designs, catalyst is moved from cracking to regenerating section
• Thus, these designs eliminated the disadvantages of cyclic operation with heat control
(b) Selection of catalyst: Composition, form, regenerative properties, poisoning, aging, etc.
• Composition:
• Acid-treated silica-alumina
• Natural clays of bentonite and kaolin are being replaced by high purity synthetic oxides (13-15% Al2O3,
87-85% SiO2)
• Form:
• 3-4mm pellets for moving beds
• 20-80mesh micro spherical synthetic catalyst for fluidized bed
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• Regenerative properties:
• Burning rate must be high and CO2/CO rates low for better heat control in fluidized beds
• Poisoning:
• Permanently poisoned by metals, particularly Group III-IV of reducible-oxide type such as Fe, Ni, V, Cu
• Catalyst should have high tolerance to Sulphur if steam (reactivated) ,
• Aging:
• Reduction in surface area from continued steam reactivation causes catalyst reactivity loss
• However, high SiO2 compositions are more susceptible to aging
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(c) Process variables: conversion, temperature, pressure, catalyst-to-oil ratio, catalyst activity
• Conversion:
• Flexible, depends on petrol/ gas oil product rates desired
• Once through up to 50%, recycle above 50% is standard to give highest petrol yield
• Temperature:
• Balance between cracking and coking rates should be carried out to decide the appropriate temperature,
(500°C) best average
• Pressure:
• Increasing pressure reduces unsaturation and octane no, increases coke production, but increases reactor
throughput
• 0.4-1atm. gage best range
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• Catalyst-to-oil ratios:
• Possible to recycle catalyst faster with less coke deactivation, but it increases recirculation costs
• 5-20wt. ratio used with 0.3-0.6% coke levels in reactor
• Catalyst activity:
• Balanced at a constant value dependent on mechanical catalyst losses and additions, dropping to 10-25% of
initial value
• Deliberate additional discard is practiced where cracking capacity is tight
• Produces high quality (80-90 octane no.) petrol from any crude
• More selective cracking and less light ends
(d) Process characteristics
• More isomerization
Distinctive features of catalytic • Less polymerization
versus thermal cracking as a
conversion operation are: • Greater portion of aromatics
• Relatively little coke
• Greater ability to tolerate high sulphur feedstock
• Uniformity of temperature and pressure control 11
• (e) Equipment design: fluidized bed and moving bed
• Fluidized bed
• By using dense phase (liquid-like) fluidization, a compact design is possible in which regenerative heat is
transferred as sensible heat a of clean catalyst to reactor section
• With low rates of dusting in dense phase operation, the cyclones are small enough to place inside the shell
• Short lengths of straight standpipes reduce erosion
• Moving bed
• Catalyst pellets move at fixed rate by gravity flow downward through the reactor- regenerator in
succession, elevated to reactor again by a gas lift
• Uniform liquid and vapor-liquid feed distribution are necessary
• Other design drawbacks compared to fluidized units are: excessive steam requirements, poorer heat
economy
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In FCC, a fluidized-bed (or fluid-bed) of catalyst particles is brought into contact with the gas oil feed along
with injected steam at the entrance (called the riser) of the reactor. The hot catalyst particles coming from
the regenerator unit evaporate the feed gas oil upon contact in the riser, and the cracking starts as the gas oil
vapors and the catalyst particles move upward in the reactor. The temperature of the catalyst particles drops
as the evaporation of gas oil and endothermic cracking reactions proceed during the upward movement.
Cracking reactions also deposit a significant amount of coke on the catalysts, leading to the deactivation of
the catalyst. After removing the adsorbed hydrocarbons by steam stripping, the coked catalyst is sent to the
regeneration unit to burn off the coke with air. Heat released from burning the coke deposit increases the
temperature of the catalyst particles that are returned to the riser to complete the cycle. Burning off the
rejected carbon (coke) in the regenerator provides the energy necessary for cracking without much loss, thus
increasing the thermal efficiency of the process. The cracking products are sent to the fractionator for
recovery after they are separated from the catalyst particles in the upper section of the reactor
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In a moving bed catalytic cracking process, a continuous stream of catalyst pellets is moved through a reactor where heavy
hydrocarbon feedstock is cracked into lighter products, with the catalyst particles continuously circulated between the
reaction zone (cracking) and a regeneration zone to remove deposited coke, allowing for sustained catalytic activity;
essentially, the catalyst particles "move" through the system while facilitating the cracking reaction as they travel.
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5. Petroleum coking process design and operation
Introduction:
Residual petroleum or heavy end fractions from refineries can also be pyrolyzed to upgrade values. Typical yields from a
complete coking operation are:
Light ends 5 wt.%
Petrol 20 Wt.%
Gas oil 60 -65 wt.%
Coke 10-15 wt.%
Process variables: temperature and pressure
Temperature:
• Increasing T results in higher yields of gas, petrol and coke where gases are more olefinic
• Petrol required hydrogenation for stability
• 500°C best
Pressure:
• Higher pressure yields more gas and coke
• 1-3.5atm. gage
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Equipment design for coking process:
Three types of coking units: delayed coking, fluid bed and moving bed coking units
(a) Delayed coking: Rapid heating in pipe stills followed by coke formation and settling in large coke drums. Units are cleaned
by cutting with high-speed water jets
(b) Fluid bed: Similar to fluid bed catalytic cracking unit. Product coke is circulated to an air-fluidized burner and then to the
reactor where steam is the fluidizing agent. Coke particles increase in size in the units, So a portion is removed, ground, and
returned for average particle size control
(c) Moving bed: Similar to moving bed catalytic cracking unit
References
C.L. Dryden, Outlines of Chemical Technology, Edited and Revised by M. Gopala Rao and S. Marshali, 3rd Edition, Affiliated
East West, New Delhi, 1997.
[Link] and S. Shreve, Chemical Process Industries, 5th Edition, McGraw Hill, New Delhi, 1984.
R.E. Kirk and D.F. Othmer, Encyclopaedia of Chemical Technology, 4'h Edition, Interscience, New York, 1991.
P.H. Groggins, Unit Processes in Organic Synthesis, 5th Edition, McGraw Hill, 1984.
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