Refining Overview Part 3 Processing

Chapter 17 Catalytic Cracking

CHAPTER 17
CATALYTIC CRACKING
The Essence of Catalytic Cracking
The purpose of catalytic cracking is to process gas oil to crack the carbon-carbon bonds. This is accomplished
by cracking with catalysts. Cracking lowers the average molecular weight and produce higher yields of fuel
products. Catalytic cracking is attractive for feeds with small concentrations of contaminants that would poison
the catalyst. Catalytic cracking is also attractive for feeds with small concentrations of heavy aromatics that
cannot be cracked without deposition of coke on the catalyst.
The products of catalytic cracking maybe further cracked using hydrocracking or they maybe processed with
alkylation to improve gasoline anti-knock characteristics.
The Development of Catalytic Cracking
Commercialized catalytic cracking and catalytic reforming arrived on the scene
about the same time in the late 1930s. And both were developed in their earlier
stages as cyclic processes. Catalytic cracking using the fluidized bed for continuous
regeneration of the catalyst reached commercial fulfillment slightly ahead of the
ultimate catalytic reforming using platinum catalyst for extended runs between
regenerations.

Eugene J. Houdry
1892 1962
Reprinted by permission from
Petroleum Refiner, January
1959, Copyright 1959, Gulf
Publishing Co, All Rights
Reserved

Catalytic cracking had been a dream for a decade. In 1930 Houdry Process
Corporation was formed with Vacuum Oil Company, but development stalled with
the East Texas glut of petroleum and the economic depression of the 1930s.
Houdry was able to interest Sun Oil to enter the agreement and on June 6, 1936, the
first Houdry catalyst cracker started up at Paulsboro, New Jersey. It had three fixed
bed reactors and processed 2,000
barrels/day. The next year 1937, a
12,000 barrels/day commercial unit
went on stream at Suns Marcus Hook
Refinery.

Many refiners quickly adopted the process, including Gulf, Sinclair,

Standard Oil of Ohio and The Texas Company. Simultaneously,
realizing that the fixed bed process was not really a continuous
regeneration process, Sun and Houdry Process Corporation started
development in 1936 on a moving bed process. A 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 and Houdry Process Corporation parted and pursued
parallel development in a pneumatic catalyst transfer process.
Meanwhile another consortium investigated a more imaginative
process involving fluidized bed technology originally developed as
the Winkler coal gasification process.
Page 17-1

First Houdry catalytic cracker,

Paulsboro, Sun Oil, 1936
Reprinted by permission from Oil and Gas Journal,
January 1959, Copyright 1959, PennWell Corp, All
Rights Reserved

Refining Overview Part 3 Processing

Chapter 17 Catalytic Cracking

W.K. Lewis of MIT, working with his associates and with a petroleum consortium - Standard Oil of New
Jersey, Standard Oil of Indiana, M.W. Kellogg, Shell Oil, and The Texas Company and others after
experimenting with a dilute phase reactor, conceived of an up-flow dense phase particulate solid process. The
first fluid catalytic cracking unit Model I was started up at Standard Oil of New Jerseys Baton Rouge Refinery
in 1942. But even before the first Model I was operating, the consortium was designing Model II, the dense
phase - back mixed reactor that dominated catalytic cracking during most of the catalytic age. Then in the 1960s
catalysts based on molecular sieve were offered. They had significantly higher cracking activity and gasoline
yields at lower overall carbon on the catalyst. These catalysts made practical the new dilute phase - riser reactor
design that utilized the plug flow configuration allowing drastically reduced residence time and feed
conversions to 90%.
Feeds, Products and Yields
Selecting Feeds for the Catalytic Cracker
As compared to hydrocracking, catalytic cracking does not do as good a job of processing aromatic rings
without coking since hydrogen is not utilized to minimize condensation (dehydrogenation) of polynuclear
aromatics (PNAs) that lead to coking. Moreover, the catalysts are sensitive to poisoning by heteroatoms, such
as sulfur and metals that are prevalent in polynuclear aromatics, and feeds are usually pretreated via gas oil
hydrotreating. As a result, feeds are limited to a Conradson Carbon Number (CCR) of approximately 3-7.
The primary feeds are atmospheric and vacuum gas oils to produce gasoline, diesel and heating oil, and heavy
fuel oil. Although these feeds could be routed to the hydrocracker for diesel production, it is generally not
economic with low diesel and high gasoline demand.
Gas oils from the visbreaker, which contain aromatics, and gas oils from the delayed coker, which contain
aromatics, olefins and sulfur, are generally not used as feed. These streams are more suitable for hydrocracker
feed since the use of hydrogen suppresses coke formation.
Vacuum resids are generally not used as feed unless mixed with sufficient amounts of gas oil to reduce the
concentration of aromatics.
The amount of coke formed in a cracking operation is to some extent a function of the carbon residue of the
feed, formed during destructive distillation. Since this parameter correlates well with hydrogen/carbon atomic
ratios and indicates coking tendencies, this parameter is especially useful for screening feeds. The two main
tests are the Conradson Carbon method (ASTM D-189) and the Ramsbottom method (ASTM D-524).
Feedstock selection is much more sophisticated than mere determination of the carbon residue and rests to a
large extent upon the distribution of aromatic, naphthenic and paraffinic structures in the oil.
Products from the Catalytic Cracker
The catalytic cracker is the workhorse of the U.S. refinery; every major fuels refinery has a catalytic cracking
unit. In terms of products, fluidization technology, and catalysis, fluid catalytic cracking is one of the most
important and sophisticated contributions to petroleum technology. Capacity is approximately 35% to 40% of
the crude distillation capacity. The catalytic cracker is used primarily to make gasoline and diesel. As with
hydrocracking, the intent is to minimize the production of heavy fuel oil. With gasoline the most important
product from the U.S. refinery in volume percent, the catalytic cracker contributes the highest volume to the
gasoline pool (35% vol), ahead of the reformer (30% vol), alkylation unit (20% vol) and isomerization unit
(15% vol). Catalytic cracking is not as expensive as hydrocracking and its technology is licensed.
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Coke production is not appreciable but important since it is burned in the catalyst regenerator.
The light ends contain large amounts of olefins and are good for chemical feedstock. Some refiners are
recovering chemical grade propylene and ethylene as well as hydrogen from the gas. The olefins (propylene,
butylene, and C5 olefins) can be alkylated for higher yields of high-octane gasoline.
The gasoline fraction (cat gasoline) contributes the largest volume to the gasoline pool but also contributes
by far the largest amounts of sulfur and olefins and significant amounts of aromatics. The front end of catalytic
cracker gasoline is rich in olefins and sulfur. The back end of catalytic gasoline is highly aromatic, high in
sulfur content, with some olefins. Catalytic cracker gasoline does not contain much C-6 and even less C-7
olefins since these olefins are very reactive and enter into cracking and combining reactions forming light
olefins and aromatics.
Because of high sulfur content, catalytic crackers generally do not usually produce a kerosene / jet fuel
product.
The diesel fraction has low centane number because of the aromatics. It may be added to the refinery diesel
pool but lowers the quality because of low cetane number and may have high concentrations of sulfur.
The bottoms or cycle oil contains sulfur, small ring aromatics and polynuclear aromatics, catalyst fines, and
usually has high viscosity. The cycle oil is generally hydrocracked to form high yields of jet fuel, kerosene,
diesel, and heating oil. Cycle oil may also be blended into the heavy fuel oil pool,
Yields
Catalytic cracking produces high yields of liquids and small amounts of gas and coke. Mass liquid yields are
usually 90%-93% although liquid volume yields are often more than 100%. As a rule of thumb, the remaining
mass yield is split between gas and coke. The yield pattern is determined by complex interaction of feed
characteristics and reactor conditions that determine the severity of the operation.
Catalytic Cracking Catalysis and Chemistry
Fluid catalytic cracking reactions are fundamentally acid site catalyzed cracking and hydrogen transfer via a
carbonium mechanism. Originally catalytic cracking units employed powdered silica alumina catalysts with a
continual replacement to maintain activity and offset the decline caused by accumulation of metals on the active
sites and by binding of surface metal by unregenerated carbon. Today, zeolite catalysts dominant due to high
activity, good fluidization properties, high gasoline and low coke yields.
Typical reactions include:
The basic reaction is carbon-carbon scission of paraffins, cycloparaffins and aromatics to form olefins and
lower molecular paraffins, cycloparaffins and aromatics. Olefin production is a significant aspect of catalytic
cracking.
Olefins will exhibit carbon-carbon scission as well as isomerization with alkyl paraffins to form branched
paraffins.
Cycloparaffins will dehydrogenation (condensation) to form aromatics. Aromatic production is a notable
aspect of catalytic cracking.
A small amount of aromatics and olefins will dehydrogenate (condense) to ultimately form coke. The coke is
burned off during catalyst regeneration.
The kinetic insights that led to recognition that both crackability of the feed and severity of operations were
factors led to investigations of chemical reactions and and the regimes in which the reactions were to take place.
This also guided catalysts research to new concepts and in particular the use of zeolites as a catalyst base. Both
catalyst suppliers and licensors have made significant advances in catalysis research. Kinetic analysis developed
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a theoretical basis for describing the cracking reactions leading to more precise definition of catalytic effects.
Catalyst can be tailored to maximize gasoline yield or increase high olefin production.
The Effects of Process Variables
The prediction of yields generally starts with prediction of conversion. Conversion is the amount of feed
converted to diesel and gasoline. Cycle oil and heavy fuel oil are excluded from conversion. Numerically,
conversion is a function of the crackability of the feed and of the severity of the operation.
Assessing Crackability of the Feed
Crackability depends on the type of components. Paraffins are highly crackable, cycloparaffins (naphthenes) are
intermediate; and aromatics are difficult to crack without coking. Catalyst vendors have tremendously improved
both the catalyst, and the ability to predict their performance on a given feedstock and under different operating
conditions. Catalyst is often tailor-made or blended to provide the optimum performance for a specific unit and
its operating constraints.
Assessing Severity of the Operation
The severity is considered to be affected by temperature, catalyst/oil ratio, catalyst activity, pressure, and space
velocity.
Increasing reactor temperature increases conversion since the reactions are endothermic. Temperature is an
easily measured variable but it cannot be implicitly controlled. Heat to the reactor is controlled by catalyst
circulation rate, regenerated catalyst temperature, and by feed preheat. Increasing feed preheat reduces the need
for catalyst circulation for the same reactor temperature, but this lowers catalyst/oil ratio, decreasing conversion.
Catalyst/oil ratio is a primary variable controlled by changing catalyst circulation rate. Increasing catalyst/oil
ratio increases conversion. Raising catalyst circulation to increase the catalyst/oil ratio and thereby increase
catalytic cracking activity also increases reactor temperature. However, since the cracking reactions are
endothermic, the additional cracking moderates the temperature increase from increased catalyst circulation.
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.
Higher pressures generally do not affect conversion but do increase coke production.
Increasing space velocity decreases activity and conversion.
Operating Conditions and Design Features
The fluid catalytic cracking unit is carefully designed to provide a balance of reactor and regenerator
capabilities. But once the unit is built changes can shift the balance and lead to a capacity limitation. A
common example is the use of a new zeolite catalyst that increases conversion. Operators can usually take
advantage of the capabilities until the unit reaches a mechanical limit. A common limit is the capacity to burn
carbon from the catalyst. If air compressor capacity is the limit, capacity may be increased at feasible capital
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cost. On the other hand if regenerator metallurgy is limiting the temperature of regeneration, the design changes
can be formidable.
Regenerators. The regenerators usually run at temperatures as high as 1,500F or as limited by metallurgy or
catalyst concerns. Regenerator temperature determines whether the combustion gases are primarily carbon
monoxide or carbon dioxide. Those operating at lower temperatures under 1,300F must usually have carbon
monoxide boilers attached to burn the carbon monoxide gas and generate steam. High temperature operations
usually have very little carbon monoxide and therefore employ a much simpler waste heat boiler to recover heat.
Greater cracking results in higher coke yields, which must be burned off in the regenerator. This results in more
heat release in the regenerator and higher temperature for the regenerated catalyst, resulting in higher reactor
temperatures.
Reactors. In general catalytic cracking unit reactors operate in the range of 950F. But the tendency over the
years has been to increase reactor temperature to increase severity and conversion. That may be reversing in
recent experience, as the olefin content of catalytic gasoline becomes more of a problem in the meeting of
gasoline formulation regulations.
Reactor pressure is a design feature but is controlled by the fractionator overhead gas compressor. Pressure
ordinarily is in the range of 10 to 30 psig. Higher pressure sometimes makes an expander on the regenerator
off-gas economic. Both one stage and two stage expanders have been installed, and all expander installations
include some type of fines removal from the hot gas to prevent erosion of the blades in the expander. The
power recovered is used to generate electricity and/or drive the air blower. The most complicated expander
systems incorporate an expander, air blower, and steam turbine in a single train. Economics of electricity sales
are balanced, in real time, with steam costs, etc. to provide the highest revenue at the time. When electricity
sales value is low, the available power is used to drive the compressor, and the steam turbine idles along. When
electricity is more valuable, the steam turbine is loaded up and power is diverted to electricity generation.
Process Description of Fluid Catalytic Cracking
Cracking of petroleum fractions to make lighter fractions in general leads to products of a higher hydrogen to
carbon ratio and lower molecular weight than the feed. This means that cracking reactions produce excess
carbon laid down on the catalyst as coke. In thermal cracking the carbon is laid down on the piping and
equipment walls. The catalyst and products need to be separated and eventually the coke must be removed from
the catalyst since it binds the active sites and causes a reduction in catalyst activity.
Catalytic cracking processes have been devised to separate and regenerate the catalyst. For cracking units using
pelletized catalyst the process is referred to as a moving bed process, involving mechanical transport of the
pellets. The moving bed process has its proponents. This presentation will be confined to the fluid bed
cracking process.
One of the greatest achievements of chemical engineering is the application of fluid bed technology to provide
an intimate reacting mixture of catalyst and petroleum vapors and to continuously remove catalyst for
reactivation in a second fluid bed.
Fluidized Dense Bed Back-mixed Reactor
The Fluidized Dense Bed Reactor was the standard for much of the catalytic age. Rising vapors fluidize the
catalyst particles creating a bed of particles that is much like quicksand. The regenerator conducts a burning
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operation wherein the dense bed of catalyst with carbon on it is contacted with air at combustion temperature.
Both the reactor and regenerator operate in a balance pressure regime normally of 30 to 50 psig pressure.
Catalytic Cracking Unit
Dense Phase Reactor
Cat Products to Fractionation

Flue Gas (CO, CO2, N2)

Spent
Catalyst

Regenerator

Reaction Chamber
(backmix)
Air
Gas Oil
Feed from
Hydrotreating

riser
Fresh Catalyst

Cycle Oil from catalytic cracker

fractionator bottoms

The schematic shows the reactor, regenerator and the fractionator. The cracking reaction is carried out in a
catalyst bed fluidized by the feed. After separation, the catalyst with its coked surface is conveyed to a
regenerator where the coke is burned off and the regenerated catalyst is returned for another reaction pass. The
vapors separated from the catalyst in the reactor go to the fractionator that makes liquid products and sends the
large quantity of light ends produced to the catalytic gas plant. The fractionator makes naphtha and distillate
streams and a stream commonly called cycle oil. Some cycle oil is returned to the reactor.
The foregoing simplified representation is for a dense bed reactor / dense bed regenerator. As shown in the
sketch, the regenerated catalyst flows down a standpipe from the regenerator where it is mixed with the fresh
and recycle feed for admittance to the reactor. Catalyst flow in the various standpipes and transfer lines is
controlled by valves and to some extent by changing the density in a standpipe with steam. There is some
cracking of oil after it is mixed with the catalyst in the transfer line from the regenerator to the reactor fluid bed.
Because of the relatively low catalyst activity prior to 1965, the dense bed reactor was required to provide
sufficient residence time for even a 50% conversion. Reacted vapors disengage from the catalyst at the top of
the bed and pass through multi-stage cyclone separators to further reduce particulate content.
The Riser Reactor
he riser reactor originated in the 1960s after the development of more active catalysts that permitted the riser to
be utilized as a plug flow reactor. As opposed to the back mixed reactor these designs enables higher
conversions achieved at lower-than-reactor-average carbon on the catalyst.
There are a number of riser reactor designs; one typical arrangement is presented in the schematic.
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The riser is at least 60 feet high. The hot regenerated catalyst is diluted with steam and the preheated feed is
injected just above the bottom. The dilute phase flows up the riser that extends beside the reactor and
discharges the hot reactants into the upper part of the reactor. The vapors are disengaged from catalyst and then
flow through two or three stages of cyclones after which they flow to the fractionator.
Catalytic Cracking Unit
Riser Reactor
Riser Reactor
(plug flow)

Cat Products to Fractionation

Disengager

Spent Catalyst
Flue Gas (CO, CO2, N2)
Gas Oil
Feed from
Hydrotreating

Fresh Catalyst

Regenerator
Air

Cycle Oil from catalytic cracker

fractionator bottoms

The riser reactor disengaging vessel still has a dense particulate phase despite the dilute phase reaction system.
That dense fluid bed phase provides hydrostatic head and seal for catalyst to proceed down through a stepwise
stripping system to remove hydrocarbons from the interstices between catalyst particles before it is delivered via
the internal standpipe to the regenerator below the reactor.
The hydraulic circulating action of the catalytic cracker is one of its engineering feats. The solid catalyst
particles are circulated at a given solids circulation rate around the system by the action of the density
differences in the phases.
Feed throughput is generally maximized to limit residence time in the reactor cyclones and thereby minimize
thermal after-cracking. Both dense bed and riser reactor designs have to contend with thermal after-cracking
during the time required to separate particulates from the vapor and transmit that vapor to the fractionator.
Thermal after-cracking results in degradation of reactor product. Modern licensed technology incorporates
rough cut cyclones right at the top of the riser to minimize contact time. Latest technology designs have riser
contact times of less than 250 milliseconds. An important design point is how to quickly, evenly, and
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.
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Chapter 17 Catalytic Cracking

Riser Reactor Hydraulics

Cat Products
to Fractionator
10 30 psig
Catalyst Dense
Phase in Cyclone
Catalyst Dilute
Phase in Plug
Flow Riser
950F

Combustion Flue Gases

to Waste Heat Recovery

1200F to 1300F
Stripping Steam Injection
to strip oil from catalyst
Catalyst Dilute Phase
in Regenerator
Air

Injection
Fluidization
Steam

Catalyst Dense
Phase Downflow

Liquid Gas Oil

~ 200F preheated

Stripping Spent Catalyst before Regeneration

Specialists define coke in terms of different mechanisms but the material on the catalyst is basically of two
sorts: carbon laid down on the catalyst which must be burned off, and the liquid which will carbonize if not
stripped off. Adsorbed material will carbonize but reducing the partial pressure and providing turbulence can
strip the liquid around the particles. Reactor stripper performance is an important operation for low carbon-oncatalyst and therefore overall coke production. Regardless of the reactor design, dense bed or riser, catalyst
from the reactor is stripped of liquid before it is transferred to the regenerator.
The Regenerator for the Riser Reactor
The regenerator is a fluidized bed of particulate solids coated with carbon that is burned off by high temperature
oxidation with air. The objective is to remove the carbon and restore the activity of the catalyst to something
approaching its fresh state. The unregenerated catalyst flows down through a standpipe and is then lifted into
the regenerator dense bed. Regenerated catalyst overflows and flows down through a standpipe to be lifted to
the reactor by steam and fresh feed. It is frequently said that carbon burning limits unit capacity. The
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regenerator is generally run to a limitation of either the air blower capacity or a maximum temperature
determined by materials of construction.
Carbon on the catalyst is burned off, either to a mix of carbon
monoxide and carbon dioxide or completely to carbon dioxide
by elevating the temperature. The temperature can be raised by
increasing air rate (some cat units now use oxygen enrichment
for increased coke burning capacity), converting more carbon to
the oxides and pushing the equilibrium to carbon dioxide.
If the owners choose to operate at a lower regenerator
temperature, it is not uncommon for them to install a CO boiler
on the regenerator off gas. If the unit operates at very high
temperatures and low carbon monoxide concentration the
owners will frequently install waste heat boilers on the off gas.
In any event the cat unit is a producer of heat in the form of
steam. It should be noted that some refiners install power
recovery turbines on the offgas in addition to heat recovery.
The Riser Reactor Regenerator Heat Balance

Fluid catalytic cracker with riser reactor,

Shell Oil, circa middle 1950s
Reprinted by permission from Oil and Gas Journal January
1959, Copyright 1959, PennWell Publishing Co, All Rights
Reserved

The reactor and regenerator have to operate in heat balance.

Increasing catalyst circulation rate of hot regenerated catalyst
from the regenerator to the reactor raises reactor temperature.
The hot catalyst heats and vaporizes the feed and provides the
heat of cracking reactions, which are endothermic. Catalyst
circulation rate is commonly controlled with plug or slide
valves as well as by varying density in the standpipes by steam
injection.

Visualize the reactor and regenerator as two interconnected boxes, one of which generates heat and the other
which consumes it. The balance includes the reactor and the regenerator in one envelope and the heat moved by
catalyst circulation is within that envelope. 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. Installing a feed preheater before the riser inlet can increase
sometimes feed rate.
Fractionation of the Riser Reactor Product
The reactor outlet vapors at approximately 900F flow to the fractionator. This is a superheated vapor, not a
vapor in equilibrium with liquid, and it contains some particulates as well. The pump-around and shed deck
contactor at the bottom of the fractionator are designed for cooling and initial condensation plus washing of the
particulates out the bottom as well. Fractionator overhead vapors and excess reflux liquid are directed to the
catalytic gas plant, which usually is an integral part of the catalytic cracking unit.
Catalytic gasoline is taken overhead or as a top sidestream. Light cycle oil used in diesel and heating oil is a
lower sidestream below which heavy cycle oil is withdrawn for recycle or diversion to fuels. The bottoms steam
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contains catalyst fines. They can be directed to reactor recycle with heavy gas oil or they can be decanted to
concentrate the fines and produce a clarified slurry decant oil which is used in carbon black manufacture.
Some refiners are drawing more light cycle by increasing the initial boiling point, to include some of the heavier
cat gasoline. This tends to lower sulfur and aromatics in catalytic gasoline, which is desirable to reduce
emissions.
Trends For Catalytic Cracking of Heavier Stocks
Refiners find economics favor using heavier crudes as time goes by. Profitability rests on minimizing the
bottoms product of those crudes. This has led to programs that feed heavier material to the cat unit, including
atmospheric bottoms from some crudes.
One major design change required for processing heavy oils is the addition of heat removal equipment in or on
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. Modern technology uses external catalyst coolers
on the regenerator to produce high-pressure steam. These specially designed vertical shell and tube heat
exchangers have proven much easier to control than the previous steam coils in the regenerator designs. The
special mechanical details for these catalyst cooler systems are proprietary and available only with the license of
the technology.
These heavier feeds also contain more heavy metals, such as vanadium, nickel, and, iron, which all poison the
active cracking sites on the catalyst. Per pound, vanadium usually is twice as bad, as nickel and iron. Adverse
effects of these catalyst poisons include much higher hydrogen and light gas yields, lower catalyst activity, and
much higher catalyst make-up costs. The dry gas yields will usually load up the wet gas compressor and gas
recovery system and limit the operation.
The bad effects of the additional heavy metals deposited on the catalyst can be reduced sharply by using metals
passivation technology. Phillips offers the metal passivation process for license. The technology 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 and have to be evaluated in the overall economics.

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