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Catalytic Cracking

Chapters 6

Petroleum Refinery Schematic


Gasses
Polymerization Sulfur Plant

Sulfur

Gas

Sat Gas Plant

LPG Alkyl Feed


Alkylation

Butanes

Fuel Gas LPG

Gas Separation & Stabilizer

Isomerization

Polymerization Naphtha Isomerate Alkylate Aviation Gasoline Automotive Gasoline Solvents

Light Naphtha

Reformate Heavy Naphtha


Atmospheric Distillation Naphtha Hydrotreating Naphtha Reforming

Naphtha

Crude Oil

Kerosene
Desalter

Jet Fuels Kerosene


Hydrocracking

AGO LVGO
Vacuum Distillation

Distillate
Gas Oil Hydrotreating Fluidized Catallytic Cracking

Cat Naptha

Solvents
Distillate Hydrotreating Treating & Blending

Heating Oils Diesel

HVGO

Cat Distillates Fuel Oil Cycle Oils Residual Fuel Oils

DAO
Solvent Deasphalting

Coker Naphtha

SDA Bottoms

Naphtha

Asphalts

Visbreaking

Distillates Fuel Oil Bottoms Coker Gas Oil


Solvent Dewaxing

Vacuum Residuum

Lube Oil

Lubricant Greases Waxes

Waxes
Coking

Coke

Characteristics of Petroleum Products

Overview of Catalytic Cracking


FCC heart of a modern US refinery
Nearly every major fuels refinery has an FCCU

One of the most important & sophisticated contributions to petroleum refining technology Capacity usually 35% to 40% of the crude distillation capacity Contributes the highest volume to the gasoline pool
FCCU Reformer Alkylation Isomeration 35 vol% 30 vol% 20 vol% 15 vol%

Overview of Catalytic Cracking


Process gas oils using catalysts to crack the carboncarbon bonds
Cracking lowers the average molecular weight & produces higher yields of fuel products

Attractive feed characteristics


Small concentrations of contaminants Poison the catalyst Small concentrations of heavy aromatics Crack & deposit coke on catalyst

Products may be further processed


Further hydrocracked Alkylated to improve gasoline anti-knock properties

Diagram of Modern FCCU

Development of Catalytic Cracking


Cyclic fixed bed catalytic cracking commercialized in late 1930s
Houdry Process Corporation was formed with Vacuum Oil Company in 1930 First Houdry catalyst cracker started up at Sun Oils Paulsboro, New Jersey, refinery in June 1936 Three fixed bed reactors & processed 2,000 barrels/day 12,000 barrels/day commercial unit went on stream at Suns Marcus Hook Refinery in 1937 Many refiners quickly adopted the process Gulf, Sinclair, Standard Oil of Ohio, & The Texas Company

Development of Catalytic Cracking


Sun & Houdry Process Corporation started development on a moving bed process in 1936
Regeneration in fixed bed not continuous Pilot Thermofor catalytic cracker was started in 1941 Licensees were accepted in 1942 even before the first commercial 20,000-barrel/day unit was commissioned at Magnolias Beaumont Refinery in 1943 In 1947, Socony & Houdry Process Corporation parted and pursued parallel development in a pneumatic catalyst transfer process.

Development of Catalytic Cracking


Consortium investigated fluidized bed technology
Originally developed as the Winkler coal gasification process Standard Oil of New Jersey, Standard Oil of Indiana, M.W. Kellogg, Shell Oil, The Texas Company, and others

Up-flow dense phase particulate solid process


Credited to W.K. Lewis of MIT

First FCCU (Model I) started up at Standard Oil of New Jerseys Baton Rouge Refinery, 1942 Dense phase - back mixed reactor (Model II) designed even before the first Model I was operating
Dominated catalytic cracking during early years

Development of Catalytic Cracking


In 1960s catalysts based on molecular sieve were offered
Significantly higher cracking activity & gasoline yields at lower overall carbon on the catalyst

These catalysts made the new dilute phase riser reactor design practical
Utilized plug flow configuration allowing drastically reduced residence time & feed conversions to 90%.

Selecting Feeds for the Catalytic Cracker


General feed characteristics
Catalytic cracking does not process aromatic rings well without coking Hydrogen not used to minimize condensation of polynuclear aromatics Catalysts are sensitive to poisoning by heteroatoms Sulfur & metals (nickel, vanadium, & iron) Feeds normally pretreated via gas oil hydrotreating Feeds normally limited to Conradson Carbon Number (CCR) of approximately 3-7 wt%

Selecting Feeds for the Catalytic Cracker


Atmospheric & vacuum gas oils are primary feeds
Could be routed to the hydrocracker for diesel production; not economic with low diesel & high gasoline demand

Not often used


Visbreaker gas oils Contain aromatics Delayed coker gas oils Contain aromatics, olefins, & sulfur Vacuum resids High aromatics; could be diluted with gas oils

Selecting Feeds for the Catalytic Cracker


Amount of coke formed correlates to carbon residue of the feed, formed during destructive distillation
Correlates well with hydrogen/carbon atomic ratios & indicates coking tendencies Two main tests: Conradson Carbon (ASTM D-189) & Ramsbottom (ASTM D-524) methods Useful for screening feeds Also depends upon distribution of aromatic, naphthenic, and paraffinic structures in the feed

Products from the Catalytic Cracker


Primary goal to make gasoline & diesel
Minimize the production of heavy fuel oil Gasoline most important product in the U.S

Not as expensive as hydrocracking Coke production small but very important


Burned in regenerator & provides heat for process

Light ends contain large amounts of olefins


Good for chemical feedstock Can recover chemical grade propylene & ethylene Propylene, butylene, & C5 olefins can be alkylated for higher yields of high-octane gasoline

Products from the Catalytic Cracker


Cat gasoline contributes largest volume to the gasoline pool
Front end rich in olefins & sulfur Back end highly aromatic, high in sulfur, with some olefins Does not contain much C-6 & C-7 olefins Very reactive & form lighter olefins & aromatics

Little cat kerosene or jet fuel


High sulfur content

Cat diesel fraction


Low centane number because of aromatics Lowers quality diesel pool because of low cetane number & high concentrations of sulfur

Products from the Catalytic Cracker


Bottoms (cycle oil)
Contains sulfur, small ring & polynuclear aromatics, & catalyst fines; usually has high viscosity Ultimate products Generally hydrocracked to high yields of jet fuel, kerosene, diesel, & heating oil May also be blended into the heavy fuel oil pool

Product Yields
Produces high yields of liquids & small amounts of gas & coke
Mass liquid yields are usually 90%-93%; liquid volume yields are often more than 100% (Rule of thumb) Remaining mass yield split between gas & coke

The yield pattern is determined by complex interaction of feed characteristics & reactor conditions that determine severity of operation
Rough yield estimation charts given in text pp. 117-130

Use of Yield Charts


Vol% Fuel Gas C3 C3= LPG IC4 NC4 C4=s Gasoline Cycle Oils Coke Total LCO HCO Wt% Density

Use of Yield Charts


Vol% Fuel Gas C3 C3= LPG IC4 NC4 C4=s Gasoline Cycle Oils Coke Total 100% 100% LCO HCO 100% Conv Pure Pure Pure Pure Pure Wt% Density

Use of Yield Charts


Vol% Fuel Gas C3 C3= LPG IC4 NC4 C4=s Gasoline Cycle Oils Coke Total LCO HCO 6.23 100% Conv 6.27 6.18 100% 100% 6.20 6.21 6.21 6.22 6.22 6.22 6.27 Wt% 6.19 Pure Pure Pure Pure Pure Density

6.24/25

6.27

Use of Yield Charts


Vol% Fuel Gas C3 C3= LPG IC4 NC4 C4=s Gasoline Cycle Oils Coke Total LCO HCO 6.23 100% Conv 6.20 6.21 6.21 6.22 6.22 6.22 Wt% 6.19 Ratio Ratio Ratio Ratio Ratio Ratio? Ratio? 6.27 6.27 Pure Pure Pure Pure Pure Density

6.24/25

Ratio?

6.27

6.18 100% 100%

Use of Yield Charts


Vol% Fuel Gas C3 C3= LPG IC4 NC4 C4=s Gasoline Cycle Oils Coke Total LCO HCO 6.23 100% Conv 6.20 6.21 6.21 6.22 6.22 6.22 Ratio Wt% 6.19 Ratio Ratio Ratio Ratio Ratio 6.27 Pure Pure Pure Pure Pure Density

6.24/25

6.18 100%

Ratio

Ratio

Ratio 6.27

100%

Catalytic Cracking Catalysis & Chemistry


Catalysts
FCCUs originally used powdered silica alumina catalysts Continual replacement to maintain activity Decline caused by accumulation of metals on the active sites & by binding of surface metal by unregenerated carbon Today, zeolite catalysts dominant High activity, good fluidization properties, & high gasoline & low coke yields

Catalytic Cracking Catalysis & Chemistry


Fundamental reactions acid site catalyzed cracking & hydrogen transfer via carbonium mechanism (6.3 6.7)
Basic reaction carbon-carbon scission of paraffins, cycloparaffins & aromatics to form olefins & lower molecular weight paraffins, cycloparaffins & aromatics Olefins exhibit carbon-carbon scission & isomerization with alkyl paraffins to form branched paraffins Cycloparaffins will dehydrogenate (condense) to form aromatics Small amount of aromatics & olefins will condense to ultimately form coke The coke is burned off during catalyst regeneration.

Olefin, aromatic, & coke production are characteristic of the FCC process

Catalytic Cracking Catalysis & Chemistry


Research continues by catalyst suppliers & licensors
Recognition that both crackability of feed & severity of operations are factors Led to use of zeolites as catalyst base Theoretical basis has been developed for describing the cracking reactions leading to more precise definition of catalytic effects

Catalyst can be tailored to maximize gasoline yield or increase olefin production

Diagram of Modern FCCU

Effects of Process Variables (6.10)


Prediction of yields starts with prediction of conversion to diesel & gasoline
Cycle oil & heavy fuel oil are excluded from what is typically called conversion Numerically a function of the crackability of feed & severity of the operation.

Crackability of Feed
Crackability depends on the type of components Paraffins are highly crackable Cycloparaffins (naphthenes) are intermediate Aromatics are difficult to crack without coking

Severity of the Operation


Severity: intensity of the operating conditions Severity affected by:
Temperature catalyst/oil ratio catalyst activity Pressure space velocity

Severity of the Operation


Increasing reactor temperature increases conversion
Reactions endothermic Temperature easily measured but only implicitly controlled Heat to the reactor is controlled by: catalyst circulation rate, regenerated catalyst temperature, & feed preheat Increasing feed preheat reduces the need for catalyst circulation for the same reactor temperature However, this lowers catalyst/oil ratio, decreasing conversion

Severity of the Operation


Catalyst/oil ratio is a primary variable controlled by changing catalyst circulation rate
Increasing catalyst/oil ratio increases conversion Raising catalyst circulation also increases catalytic cracking activity & increases reactor temperature Since cracking reactions are endothermic, additional cracking moderates the temperature increase from increased catalyst circulation

Severity of the Operation


Increasing catalyst activity increases conversion
Activity is decreased by coke deposition and deposition of heavy metals In turn, heavy metals promote coke formation The effect of carbon on the catalyst out of the reactor can be established to permit determination of catalyst activity for the regenerated catalyst Carbon on regenerated catalyst becomes a useful index for both conversion and regenerator efficiency calculations.

Severity of the Operation


Higher pressures generally do not affect conversion but do increase coke production. Increasing space velocity decreases activity & conversion

Operating Conditions and Design Features


FCCU carefully designed to provide a balance of reactor & regenerator capabilities
Once built changes can shift the balance & lead to a capacity limitation Operators can usually take advantage of the capabilities until the unit reaches a mechanical limit A common limit is capacity to burn carbon from the catalyst If air compressor capacity is limit, capacity may be increased at feasible capital cost If regenerator metallurgy is limit, design changes can be formidable.

Regenerators
Regenerators 1200 - 1500F
Limited by metallurgy or catalyst concerns

Regenerator temperature determines whether the combustion gases are primarily CO or CO2
Under 1300F usually have CO boilers generate steam High temperatures very little CO simpler waste heat recover systems

Greater cracking results in higher coke yields must be burned off in regenerator
More heat released in the regenerator & higher temperature for regenerated catalyst Also results in higher reactor temperatures

Reactors
Operate 950 - 1000F
Trend has been to increase reactor temperature to increase severity & conversion May be reversing olefin content of catalytic gasoline becomes more of a problem in the meeting gasoline formulation regulations

Reactor pressure controlled by the fractionator overhead gas compressor


Normally in the range of 10 to 30 psig May use expander on the regenerator off-gas at higher pressure Power recovered used to generate electricity and/or drive the air blower

Reactors
Expander systems may incorporate an expander, air blower, & steam turbine in a single train
Economics of electricity sales are balanced, in real time, with steam costs, etc When electricity sales value is low, the available power is used to drive the compressor, & the steam turbine idles along When electricity is more valuable, the steam turbine is loaded up & power is diverted to electricity generation.

FCC is one of the greatest achievements of chemical engineering


Application of fluid bed technology Provides an intimate reacting mixture of catalyst & petroleum vapors Continuously removes catalyst for reactivation in a second fluid bed

Process Description of Fluid Catalytic Cracking

Cracking makes lighter fractions with higher hydrogen to carbon ratio & lower molecular weight than the feed Cracking reactions produce excess carbon laid down on the catalyst as coke The catalyst & products need to be separated Coke must be removed from the catalyst
Binds the active sites & causes a reduction in catalyst activity.

Process Description of Fluid Catalytic Cracking

Rising vapors fluidize the catalyst particles creating a bed of particles that is much like quicksand Regenerator burning operation
Dense bed of catalyst with carbon on it is contacted with air at combustion temperature.

Process Description of Fluid Catalytic Cracking

Reactor & regenerator operate in a pressure balance 30 to 50 psig pressure


Catalyst flow controlled by valves & changing the density in a standpipe with steam

Catalyst & hydrocarbon vapors separated

Process Description of Fluid Catalytic Cracking

Reacted vapors disengage from the catalyst at the top of the bed Pass through multi-stage cyclone separators to reduce particulate content

Catalyst with coked surface drops to regenerator


Coke burned off Regenerated catalyst is returned for another reaction pass

Separated vapors go to the fractionator


Liquid products naphtha, distillate, & cycle oil Some cycle oil returned to the reactor Large quantity of light ends to the catalytic gas plant

The Riser Reactor


The riser reactor originated in the 1960s after the development of more active catalysts
Riser acts as a plug flow reactor

High conversions achieved at lower-than-reactoraverage carbon on the catalyst Hot regenerated catalyst is diluted with steam and the preheated feed is injected just above the bottom Dilute phase flows up the riser & discharges the hot reactants into the upper part of the reactor Vapors are disengaged from catalyst & flow through two or three stages of cyclones & then to fractionator

The Riser Reactor


Riser reactor disengaging vessel has dense particulate phase despite dilute phase reaction system Dense fluid bed phase provides hydrostatic head & seal for catalyst to proceed down through stripping system & deliver via internal standpipe to regenerator below reactor Hydraulic circulating action of the catalytic cracker is one of its engineering feats Solid catalyst particles circulated at a given solids circulation rate around the system by the action of the density differences in the phases.

The Riser Reactor


Feed throughput generally maximized to limit residence time in the reactor cyclones & minimize over-cracking Both dense bed & riser reactor designs have to contend with thermal over-cracking during the time required to separate particulates from the vapor Thermal over-cracking results in degradation of reactor product Latest designs have riser contact times of less than 250 milliseconds

The Riser Reactor


Important design point: quickly, evenly, & completely mix the feed with the catalyst
Each licensor has proprietary feed injection nozzle systems designed to accomplish this important step This is often the most overlooked area for improving the performance of an existing unit

Stripping Spent Catalyst before Regeneration


Material on the catalyst
Coke laid down on the catalyst Liquid which will coke if not stripped off Reduce the partial pressure & provide turbulence to strip off the particles

Reactor stripper performance is an important operation for low carbon-on-catalyst and therefore overall coke production Catalyst from reactor is stripped of liquid before it is transferred to the regenerator

The Regenerator for the Riser Reactor


Regenerator is a fluidized bed of particulate solids coated with carbon that is burned off by high temperature oxidation with air Objective is to remove the carbon & restore the activity of the catalyst to something approaching its fresh state Unregenerated catalyst flows down through a standpipe & lifted into regenerator dense bed Regenerated catalyst overflows and flows down through a standpipe to be lifted to the reactor by steam & fresh feed

The Regenerator for the Riser Reactor


Carbon burning usually limits unit capacity
Either the air blower capacity limited Or maximum temperature determined by materials of construction

Carbon on the catalyst is burned off to a mix of CO & CO2


Raising temperature shifts toward near complete CO2

Temperature can be raised by increasing air rate


Some cat units now use oxygen enrichment for increased coke burning capacity

The Regenerator for the Riser Reactor


FCCU is producer of heat in the form of steam
At lower regenerator temperatures may have CO boiler on regenerator off-gas At very high temperatures and low CO concentration will still have waste heat boilers on the off gas

May install power recovery turbines on the off-gas in addition to heat recovery

The Riser Reactor Regenerator Heat Balance


Reactor & regenerator have to operate in heat balance
Reactor & regenerator as two interconnected boxes, one of which generates heat & the other which consumes it Balance includes reactor & regenerator in one envelope Heat moved by catalyst circulation

Increasing catalyst circulation rate raises reactor temperature


Hot catalyst heats & vaporizes the feed & provides the heat of cracking reactions Catalyst circulation rate commonly controlled with plug or slide valves as well as by varying density in the standpipes by steam injection

The Riser Reactor Regenerator Heat Balance


The second biggest enthalpy term, after heat of combustion of coke, is the heat content of the vapors out to the fractionator Catalyst slurry boilers or other heat exchange at the fractionator bottom mostly removes that heat

Fractionation of the Riser Reactor Product


Reactor outlet vapors about 900F flow to fractionator
Superheated vapor, not a vapor in equilibrium with liquid Contains some particulates

The pump-around and shed deck contactor at bottom of the fractionator


Designed for cooling & initial condensation Washing of the particulates out the bottom

Fractionator overhead vapors and & reflux liquid directed to the catalytic gas plant
Usually integral part of the catalytic cracking unit

Catalytic gasoline either overhead or top sidestream

Fractionation of the Riser Reactor Product


Light cycle oil
Lower sidestream Used in diesel & heating oil

Heavy cycle oil


Withdrawn for recycle or diversion to fuels

Bottoms steam contains catalyst fines


Directed to reactor recycle with heavy gas oil Decanted to concentrate the fines & produce a clarified slurry decant oil which is used in carbon black manufacture (via coking)

Fractionation of the Riser Reactor Product


Some refiners drawing more LCO by increasing the initial boiling point to include some of the heavier cat gasoline
This tends to lower sulfur and aromatics in catalytic gasoline desirable to reduce emissions

Economics favoring use of heavier crudes Goal is to minimize bottoms product Heavier material to the FCCU, including atmospheric bottoms of some crudes
Requires heat removal equipment in the regenerator to accommodate the much higher heat release from burning carbon off the catalyst Instead of a normal 5-8% coke yield, it can reach 15% with resid feeds

Trends For Catalytic Cracking of Heavier Stocks

External catalyst coolers on regenerator to produce high-pressure steam


Specially designed vertical shell & tube heat exchangers easier to control than the previous steam coils in the regenerator designs

Trends For Catalytic Cracking of Heavier Stocks

These specialized mechanical designs are proprietary & available only with the license of the technology.

Heavier feeds also contain more heavy metals (vanadium, nickel, iron) which poison the active cracking sites on the catalyst
Nickel has about 4 times effect as vanadium

Trends For Catalytic Cracking of Heavier Stocks

Adverse effects of these catalyst poisons


Higher hydrogen & light gas yields Dry gas yields will usually load up the wet gas compressor & gas recovery system to limit the operation Lower catalyst activity Much higher catalyst make-up costs

The bad effects of the additional heavy metals deposited on the catalyst can be reduced sharply by using metals passivation technology
Phillips offers metal passivation process for license Uses antimony-containing compounds injected into the feed Passivation is effective for a variety of catalyst types including zeolites The cost of equipment for injection of passivation chemicals is small, but on-going costs for the chemicals are significant have to be evaluated in the overall economics

Trends For Catalytic Cracking of Heavier Stocks

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