Refinery and Petrochemical Processing Catalytic Cracking

Dr. Philip Holmes Department for Chemical and Process Engineering University of Surrey

Introduction
Catalytic cracking is the most important process for converting low value, bottom of the barrel, heavy oils into high value lighter products, in particular gasoline. Catalytic cracking is a conversion process whereby large hydrocarbon molecules are cracked into smaller molecules using a catalyst at high temperature and low pressure. Development of process:
- Cyclic fixed bed (Houdry design). - Moving bed (Thermafor catalytic cracking TCC) - Fluidised bed (fluid catalytic cracking FCC).

FCCU first commercialised in 1942 by Standard Oil of New Jersey (now ExxonMobil) at their Baton Rouge Refinery using a powdered alumina clay catalyst from Davison (now Grace Davison) to produce gasoline for World War II. Subsequent developments include zeolite catalysts, high temperature catalyst regeneration, all-riser reactors, etc.
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Typical Feeds
From atmospheric distillation:
- Atmospheric gas oil (AGO) light material, low conversion, low coke. - Atmospheric residue (atmos resid/topped crude) heavy material, low conversion, high coke, contains contaminants (metals and nitrogen are catalyst poisons, sulphur adversely affects product quality).

From vacuum distillation:

- Vacuum gas oil (VGO) ideal feed high conversion, moderate coke, minimal contaminants. - Vacuum residue (vac resid) worst feed - very heavy material, very low conversion, very high coke, very high contaminants (metals and nitrogen, sulphur).

Hydrotreated streams from above:

- Gives improved hydrocarbon feed quality with removal of contaminants.

Cracked gas oils from thermal conversion processes:

- Poorer quality feeds than virgin gas oils since already cracked once.

Others e.g. lube extracts of poor quality due high aromatics, deasphalted oils of good quality due removal of asphaltenes.
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Feed and Products

221 C

400 C

C2

C4

FEED

Wt% FF
Gas LPG

PRODUCTS

Naphtha

LCO

Slurry

Feedstock

Boiling Point, C
Source: Grace Davison, 2004

Thermal Cracking Mechanism

Thermal Cracking Reactions

Occurs at high temperature. Involves homolytic scission of carbon-carbon covalent bond to produce two free radicals (odd or unpaired electron molecules). Beta-scission of free radical gives ethylene plus new radical with two fewer carbon atoms. Continues until methyl radical formed which abstracts a hydrogen atom producing a secondary or tertiary free radical for further cracking. Reactions are endothermic. Yields:
- High ethylene. - High methane. - Significant long chain olefins. - Low branching of products.

Rate of cracking:
Paraffins and olefins > naphthenes and alkylaromatics

Catalytic Cracking Mechanism

Catalytic Cracking Role of Catalyst

Catalytic Cracking Reactions

Catalyst lowers activation energy of reactions, thus increasing the rate. Heat of reaction and position of equilibrium are unchanged. Involves heterolytic scission of carbon-carbon covalent bond to produce electron deficient carbenium ion. Beta-scission of carbenium ion gives olefin and shorter carbenium ion. Deprotonation of carbenium ion gives paraffin. Reactions are endothermic. Yields:
- Low C2 minus. - High C3 and C4 olefins. - High branching of products.

Rate of cracking:
Olefins > naphthenes and alkylaromatics > paraffins. Alkylaromatic side chains cracked but not possible to crack benzene rings.

Thermal vs. Catalytic Cracking Reactions of n-Hexadecane

Source: Greensfelder at al., 1949

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Hydrogen Transfer Mechanism

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Hydrogen Transfer Reactions

Catalyst properties influence extent to which hydrogen transfer reactions occur. Favoured by:
- High rare earth content which gives high unit cell size of zeolite. - Inert matrix.

Involves protonation of olefin giving carbenium ion that undergoes hydrogen transfer with naphthene molecule forming a paraffin and naphthenic carbenium ion. Proton loss then gives cyclo-olefin that with continued hydrogen transfer becomes a cyclo-diolefin and ultimately an aromatic molecule. Reactions are exothermic. Basically: Olefins + Naphthenes Paraffins + Aromatics

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Overall Reactions
Paraffins Olefins Cracking Cracking Isomerisation H Transfer Cyclisation Naphthenes Cracking Isomerisation other Naphthenes Dehydrogenation Side-chain Cracking Transalkylation other Aromatics Dehydrogenation Condensation
Source: Grace Davison, 1993

Paraffins + Olefins Light Olefins Branched Olefins Paraffins Naphthenes Olefins Dehydrogenation

H Transfer

Branched Paraffins

Dehydrogenation Coke Condensation

cyclo-Olefins

Aromatics

Aromatics

unsubstituted Aromatics + Olefins Dehydrogenation poly-Aromatics Condensation

Coke
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Catalyst
Catalyst particle is composed of zeolite and matrix components: Zeolite
- Porous crystalline aluminosilicates provide selective cracking activity.

Matrix all non-zeolite material: - Porous silica-alumina can be active ingredient.

- Clay is filler to reduce zeolite activity that provides optimum fluidisation properties and serves as sink for heat transfer. - Binder is adhesive that holds all ingredients together as catalyst particle. It can provide some cracking activity. - Some components for combustion promotion, metals resistance, etc.

Additives
- Separate particles can be added for combustion promotion, metals resistance, SOx reduction, increased LPG olefinicity and naphtha octanes, etc.
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Catalyst Zeolite Structure

Many different zeolites - Y Zeolite or faujasite used in FCC catalyst. Structure:
- Commercially made from sodium silicate and sodium aluminate. - SiO4 and AlO4 tetrahedra, cross-linked with shared O atoms. - Tetrahedra form rings. Faujasite has 12 member rings that form truncated octahedras (sodalite cages) connected by hexagonal prisms. - Results in supercage with pore opening of 8-9 A and unit cell size of about 24.25 A. - Regular structure of uniform pores of controllable size gave rise to alternative name of molecular sieves for zeolites.

hexagonal prism truncated octahedra 24 Si or Al ions; 36 O anions; 8 hexagonal and 6 square faces

pore opening for hydrocarbon molecules to enter faujasite supercage

tetrahedra

Si or Al atoms at junctions with shared O atoms forming links

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Catalyst Zeolite Activity

Acid sites for activity: - Si tetrahedra is electrically balanced.
- However, Al atom is trivalent (e.g. Al2O3) but tetracoordinated and thus deficient by one electron i.e. (AlO4)-. - Electrical neutrality of anionic framework maintained by compensating cations e.g. Na+ for Na-Y zeolite. - Ion exchange with NH4+ followed by calcination gives H+ acid sites. Al/Si ratio affects zeolite performance. - Rare earth exchange also affects zeolite performance.

ion exchange NH4

calcination 16

Catalyst Particle

naphtha molecules at 4-7 A

vacuum residue molecules at 25-150 A

oil droplets at 200

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ZSM-5 Catalyst Zeolite Structure

ZSM-5 is shape selective small pore zeolite catalyst developed by Mobil. Structure:
- SiO4 and AlO4 tetrahedra form 10 member rings. - Resulting 3-D structure has two types of pores of 5-5.5 A: - Straight vertical with elliptical cross section. - Zig-zag horizontal with circular cross-section. - Only small straight chain molecules can enter the structure and react.

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ZSM-5 Catalyst Reactions

molecular diameter A paraffin, olefin, naphthene and aromatic molecules in naphtha boiling range

additional C3= and C4=, and i-C4 to LPG

loss of n-paraffins and n-olefins from naphtha gives increased naphtha octane but reduced yield

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Example of Fluid Solids Section Exxon Model IV

Flue Gas Reactor Products

Reactor Regenerator
690-750 C 0.5-2 % O2 or 2-9 % CO 500-550 C 1-2 barg

Control Air Main Air

Stripping Steam

Feed

FCCU capacities range over 100-650 t/hr feed

4-8 catalyst:oil ratio

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Features of FCCU Reactor

Oil is preheated upto 400 C (heat exchange and furnace) and injected into hot fluidised catalyst flowing at 690-740 C.
- 4-8 catalyst:oil mass ratio (about 50 t/min catalyst circulation for 500 m3/hr FCCU). - Oil droplets at about 200 and catalyst at 65 .

Oil rapidly vaporised and absorbed by catalyst. Catalytic (and thermal) cracking reactions occur with co-current flow up riser.
- Riser outlet temperature of 500-550 C and pressure of 1-2 barg. - Vapour residence time in riser of 4-6 sec.

Cracked vapour rapidly separated from coked catalyst by cyclones to minimise thermal cracking.
- Reactor vapour to fractionator. - Coked (spent) catalyst stripped of entrained hydrocarbon vapours in steam stripper.

Catalyst type important.

- Yields. - Fluidisation characteristics.
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Features of FCCU Regenerator

Coke is reaction product that is deposited on catalyst and must be removed.
- Causes loss of catalyst activity. - Is fuel for providing necessary heat input to reactor via catalyst (feed preheat is minor).

Stripped spent catayst is processed in regenerator.

- Air fluidises catalyst bed where combustion of coke takes place. - Bed at 690-740 C and 1-2 barg. - Combustion is either full or partial burn:
- Full burn operates with excess oxygen at 0.5-2 % and is highly exothermic. - Partial burn has carbon monoxide at 2-9 % permitting increased coke burn with less heat released.

Flue gas separated from regenerated catalyst by cyclones.

- Flue gas to heat recovery and clean-up before discharge to atmosphere. - Hot regenerated catalyst circulated back to reactor.

Spent and regenerated catalyst at about 1.1 and 0.1 wt % coke respectively.

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Example of Fluid Solids and Fractionation Sections

Tertiary cyclones, electrostatic precipitator or wet gas scrubber

Flue gas cooler or CO boiler

Exxon Flexicracker

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Features of FCCU Fractionator

Reactor vapour passes to fractionator where cooling and condensation occurs to separate the different fractions.
- Naphtha, C4 minus and steam go overhead. - First side stream can be heavy naphtha or kerosene. - Second side stream can be light distillate or light cracked gas oil (LCGO). - Third side stream can be heavy distillate of heavy cracked gas oil (HCGO). - Bottoms is slurry or heavy fuel oil.

Overhead product is cooled/condensed to separate out sour water (condensed steam with dissolved H2S) and naphtha. Wet gas and naphtha fed to Light Ends. Some naphtha returned as reflux to the fractionator. Typically, three pumparounds (top, mid and bottom or slurry) installed.
- Provide additional reflux to improve fractionation. - Cooling and condensation provided by heat exchange with feed preheat and light ends.

Internals used to be sieve trays with sheds in the bottom section. Modern designs have structured packing and open grids. Side streams are steam stripped to remove light material. Ammonium chloride fouling can be a problem.
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Example of Light Ends Section

MEA Sponge Oil Sponge Absorber MEA Gas From Cat Fractionator Rich Oil Absorber Deethanizer Merox & Caustic & Water Wash Fuel Gas Naphtha From Cat Fractionator

C3/C4 Splitter

Propanes & Propylenes (110F)

Butanes & Butylenes (110F)

Naphtha Splitter Debutanizer

Merox

Light Naphtha (110F)

Lean Oil

Merox

Heavy Naphtha (110F)

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Features of Light Ends

Wet gas from fractionator is H2, C1, C2, C3 and C4 that is initially compressed. First main column is deethaniser that separates C2 minus (top product) from naphtha and LPG (bottom product). Sponge absorber is used to recover LPG from C2 minus; the latter after scrubbing with monoethanolamine (MEA) becomes refinery fuel gas (RFG). Second main column is debutaniser that separates LPG (top product) from naphtha (bottom product). After MEA treatment, LPG splitter separates C3/C3= from C4/C4=4. Olefins used for Chemicals or Alkylation and paraffins sold as LPG or used for Isomerisation/Alkylation. Naphtha splitter produces light and heavy cracked naphthas (LCN and HCN) that are treated by Merox to convert/remove mercapton sulphur then used as gasoline components.
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FCCU Carbon and Heat Balance Full Burn Regenerator - 1

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FCCU Carbon and Heat Balance Full Burn Regenerator - 2

Change to poorer quality feed (increased coke making tendency) + coke causes - O2 in Flue Gas, thus + Feed Preheat T by ARC. Resulting + Reactor T so Catalyst Circulation Rate by TRC. This results in Catalyst:Oil and Conversion/Coke. Hence, + O2 in Flue Gas. Overall: + Feed Coke /- Catalytic Coke (constant O2 in Flue Gas) - Catalyst Circulation Rate /+ Feed Preheat T (constant Reactor T) + Regenerator T (constant coke burn but less heat removed by catalyst).

Hence, Carbon and Heat Balance automatically maintained for feed quality change.

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FCCU Carbon and Heat Balance Partial Burn Regenerator - 1

Full and partial regenerator operation, for a given amount of air:
C + O2 2C + O2 2H2 + O2 CO2 2CO 2H2O H = - 98 kcal/mole O2 - 56 - 136 full burn partial either

Partial combustion allows more coke to be burnt and releases less heat. Good for processing heavy coke forming feed but requires more investment in terms of CO boiler for flue gas clean-up (but additional steam produced). Good stripping of spent catalyst required to avoid excessive heat release (and loss of valuable hydrocarbons). Different carbon and heat balance control scheme is required for partial burn regenerator operation.
+ coke causes + CO in Flue Gas that results in less heat release in regenerator. Since heat supplied from regenerator is much larger than that from preheat this would cause Reactor T. Hence control scheme increases Catalyst Circulation Rate causing + Conversion/Coke and ultimately carbon build-up and unplanned unit shutdown.
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FCCU Carbon and Heat Balance Partial Burn Regenerator - 2

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FCCU Carbon and Heat Balance Partial Burn Regenerator - 3

Change to poorer quality feed (increased coke making tendency) + coke causes + CO in Flue Gas, thus Catalyst Circulation Rate by ARC. Resulting - Reactor T so + Feed Preheat T by TRC. This results in Catalyst:Oil and Conversion/Coke. Hence, - CO in Flue Gas.

Overall: + Feed Coke /- Catalytic Coke (constant CO in Flue Gas) - Catalyst Circulation Rate /+ Feed Preheat T (constant Reactor T) + Regenerator T (constant coke burn but less heat removed by catalyst).

Hence, Carbon and Heat Balance maintained.

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Modern FCCU Control Schemes

First level is constraint control.
Tuned empirical model based on actual plant tests that simultaneously adjusts several manipulated variables to keep several important control variables close to constraints. E.g. slide valves (for catalyst circulation rate) and RFG to feed preheat furnace (for preheat temperature) to control reactor temperature.

Second level is optimisation.

Fundamental process model with on-line feed analyser that uses advised economics to optimise operating variables and predict yields that maximise the unit profitability. Solution is then used as input to constraint control model. E.g. identified optimum reactor temperature becomes setpoint of constraint control model.

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Predicting FCCU Yields

Early days: - Physical inspections of feed.
- Empirical data from pilot plants. - Use of correlation charts to predict commercial yields and operating conditions. - Predictions of limited general use only.

Trend Models:
- Empirical data. - Computer based correlations. - Model calibrated to actual FCCU operations. - More specific predictions but of limited range and accuracy.

Fundamental Models:
- Use of reaction lumps to describe countless chemical species. - Product yields determined by appearance/disappearance of lumps along reactor length. - Fluid solids flow, heat and mass transfer, feedstock handling, catalyst characterisation and reaction kinetics all included. - Most accurate model. Used for design and optimisation of FCCUs.

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FCCU Operating Variables

FCCUs typically operate at maximum coke make/burn under automatic carbon and heat balance control. Hence, changes in operating variables are highly interactive.

Reactor temperature immediate.

Feedrate immediate.

Catalyst circulation rate (catalyst:oil ratio) secondary variable, immediate.

Feed quality set by economics and refinery operations.

Catalyst properties hours/days for activity, weeks/months for reformulation.

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Reactor Temperature
Increased reactor temperature achieved by increased feed preheat since already at maximum catalyst:oil ratio for maximum coke make/burn:

Increased thermal vs catalytic cracking.

Thus, increased:
- Conversion. - Gas and LPG yields at expense of naphtha. Distillate at expense of heavy fuel oil. - LPG olefinicity. - Naphtha octanes (RON).

Increased reaction coke but improved stripping performance. Thus, catalyst circulation rate would be automatically adjusted (slightly) to maintain constant coke make/burn.
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Feedrate
Increased feedrate requires decrease in catalyst:oil ratio since already at maximum coke make/burn:

Decreased catalytic cracking.

Thus, decreased:
- Conversion. - Gas, LPG and naphtha yields with increased distillate and heavy fuel oil yields.

But, increased amounts of all products (except coke that is constant).

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Catalyst:Oil Ratio
For case of FCCU not at maximum coke make/burn, increased catalyst:oil ratio achieved by increased air rate:

Increased catalytic vs thermal cracking.

Thus, increased:
- Conversion. - Gas, LPG naphtha yields at expense of distillate and heavy fuel oil. - Coke.

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Feed Quality - 1
Feedstock Analyses

Source: Grace Davison, 1993

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Feed Quality - 2
Pilot plant yields at constant operating conditions

Source: Grace Davison, 1993

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Catalyst Routine Analyses

Fresh catalyst added continuously to maintain activity of circulating equilibrium catalyst. Although some losses from reactor and regenerator (captured by downstream equipment) there is the need to withdraw catalyst to maintain constant inventory. Equilibrium catalyst samples regularly taken for analysis by vendor to monitor catalyst performance and properties. Typically two weeks for results.

Microactivity Test (MAT) Reactor

Gas Chromatograph for analysing MAT Reactor products

Source: Grace Davison, 1996

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Catalyst - Optimisation
Fresh catalyst addition rate of 110 t/day (at $2500-3500/t) controls hour-byhour catalyst activity of circulating inventory at 50-500 t. Hydrothermal deactivation and metals poisoning are main causes of deactivation. Catalyst formulation can be adjusted by catalyst vendor:
- Zeolite content for conversion of distillate to naphtha, LPG, gas and coke. - Zeolite composition (rare earth content). Reduce for LPG olefinicity and naphtha octanes and increase for stability. - Matrix content for bottoms cracking to distillate and coke. - Binder for attrition resistance. - Manufacturing conditions for particle size distribution.

Typically catalyst manufactured in 100 t batches and delivered in 25 t trucks. On-site storage 50-200 t. Thus, several weeks/months to effect a catalyst change from when decision made. Catalyst additives:
- Total upto 10 % of catalyst to minimise dilution. - ZSM-5 for additional LPG olefins is main additive, also SOx transfer agent and combustion promoter can be added separately. - Combustion promoter, metals trap can be pre-mixed with fresh catalyst.
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Catalyst - Poisoning
Vanadium (V) in atmos or vac resid feed as porphyrins (V+3, V+4) deposited on catalyst surface in reactor. Oxidised in regenerator and in presence of steam forms vanadic acid (H3VO4, V+5). Acid migrates from particle to particle destroying zeolite activity by hydrolysis of SiO2/Al2O3 framework. + 3000 wppm V - 6 to 9 MAT activity (vol % conversion) Traps can be used to capture V and prevent migration. Nickel (Ni) in atmos or vac resid feed as porphyrins deposited on catalyst surface in reactor. No loss of catalyst activity but metal acts as dehdrogenation catalyst giving increased yields of H2 and coke. Antimony (Sb) can be used as feed additive to deposit on catalyst surface and form an alloy with Ni to reduce the dehydrogenation activity. Sodium (Na) from salt water contamination of feed forms a eutectic with catalyst causing loss of activity even structural collapse at extreme regenerator conditions. Basic nitrogen (N) from feed neutralises the zeolite acid sites causing loss of activity. However, recovery occurs when feed N reduced/eliminated.
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References
Freensfelder, B.S., H.H. Voge and G.M. Good, 1949: Catalytic and Thermal Cracking of Pure Hydrocarbons. Industrial and Engineering Chemistry, 49, p 2573-2584. Grace Davison, 1993: Guide to Fluid Catalytic Cracking Part One. Grace Davison, Baltimore, Maryland, USA. Grace Davison, 1993: Guide to Fluid Catalytic Cracking Part Two. Grace Davison, Baltimore, Maryland, USA. Grace Davison, 2004: Catalytic Cracking Mechanism. GRACE Davison Refining Technologies Europe, Worms, Germany.

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