Fluid catalytic cracking

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A typical fluid catalytic cracking unit in a petroleum refinery.

Fluid catalytic cracking (FCC) is one of the most important conversion processes used in
petroleum refineries. It is widely used to convert the high-boiling, high-molecular weight
hydrocarbon fractions of petroleum crude oils to more valuable gasoline, olefinic gases, and other
products.[1][2][3] Cracking of petroleum hydrocarbons was originally done by thermal cracking, which
has been almost completely replaced by catalytic cracking because it produces more gasoline with a
higher octane rating. It also produces byproduct gases that are more olefinic, and hence more
valuable, than those produced by thermal cracking.

The feedstock to an FCC is usually that portion of the crude oil that has an initial boiling point of
340 °C or higher at atmospheric pressure and an average molecular weight ranging from about 200
to 600 or higher. This portion of crude oil is often referred to as heavy gas oil or vacuum gas oil
(HVGO). The FCC process vaporizes and breaks the long-chain molecules of the high-boiling
hydrocarbon liquids into much shorter molecules by contacting the feedstock, at high temperature
and moderate pressure, with a fluidized powdered catalyst.

In effect, refineries use fluid catalytic cracking to correct the imbalance between the market demand
for gasoline and the excess of heavy, high boiling range products resulting from the distillation of
crude oil.

As of 2006, FCC units were in operation at 400 petroleum refineries worldwide and about one-third
of the crude oil refined in those refineries is processed in an FCC to produce high-octane gasoline
and fuel oils.[2][4] During 2007, the FCC units in the United States processed a total of 5,300,000
barrels (840,000 m3) per day of feedstock[5] and FCC units worldwide processed about twice that
amount.
Contents
 1 Flow diagram and process description
o 1.1 Reactor and Regenerator
o 1.2 Distillation column
o 1.3 Regenerator flue gas
 2 Chemistry
o 2.1 Catalysts
 3 History
 4 See also
 5 References
 6 External links

Flow diagram and process description

The modern FCC units are all continuous processes which operate 24 hours a day for as long as 2 to
3 years between scheduled shutdowns for routine maintenance.

There are several different proprietary designs that have been developed for modern FCC units.
Each design is available under a license that must be purchased from the design developer by any
petroleum refining company desiring to construct and operate an FCC of a given design.

There are two different configurations for an FCC unit: the "stacked" type where the reactor and the
catalyst regenerator are contained in a single vessel with the reactor above the catalyst regenerator
and the "side-by-side" type where the reactor and catalyst regenerator are in two separate vessels.
These are the major FCC designers and licensors:[1][3][4][6]

Side-by-side configuration:

 CB&I
 ExxonMobil Research and Engineering (EMRE)
 Shell Global Solutions
 Stone & Webster Process Technology — currently owned by Technip
 Universal Oil Products (UOP) — currently fully owned subsidiary of Honeywell

Stacked configuration:

 Kellogg Brown & Root (KBR)

Each of the proprietary design licensors claims to have unique features and advantages. A complete
discussion of the relative advantages of each of the processes is beyond the scope of this article.
Suffice it to say that all of the licensors have designed and constructed FCC units that have operated
quite satisfactorily.

Reactor and Regenerator

The reactor and regenerator are considered to be the heart of the fluid catalytic cracking unit. The
schematic flow diagram of a typical modern FCC unit in Figure 1 below is based upon the "side-by-
side" configuration. The preheated high-boiling petroleum feedstock (at about 315 to 430 °C)
consisting of long-chain hydrocarbon molecules is combined with recycle slurry oil from the
bottom of the distillation column and injected into the catalyst riser where it is vaporized and
cracked into smaller molecules of vapor by contact and mixing with the very hot powdered catalyst
from the regenerator. All of the cracking reactions take place in the catalyst riser within a period of
2–4 seconds. The hydrocarbon vapors "fluidize" the powdered catalyst and the mixture of
hydrocarbon vapors and catalyst flows upward to enter the reactor at a temperature of about 535 °C
and a pressure of about 1.72 barg.

The reactor is a vessel in which the cracked product vapors are: (a) separated from the so-called
spent catalyst by flowing through a set of two-stage cyclones within the reactor and (b) the spent
catalyst flows downward through a steam stripping section to remove any hydrocarbon vapors
before the spent catalyst returns to the catalyst regenerator. The flow of spent catalyst to the
regenerator is regulated by a slide valve in the spent catalyst line.

Since the cracking reactions produce some carbonaceous material (referred to as catalyst coke) that
deposits on the catalyst and very quickly reduces the catalyst reactivity, the catalyst is regenerated
by burning off the deposited coke with air blown into the regenerator. The regenerator operates at a
temperature of about 715 °C and a pressure of about 2.41 barg. The combustion of the coke is
exothermic and it produces a large amount of heat that is partially absorbed by the regenerated
catalyst and provides the heat required for the vaporization of the feedstock and the endothermic
cracking reactions that take place in the catalyst riser. For that reason, FCC units are often referred
to as being 'heat balanced'.

The hot catalyst (at about 715 °C) leaving the regenerator flows into a catalyst withdrawal well
where any entrained combustion flue gases are allowed to escape and flow back into the upper part
to the regenerator. The flow of regenerated catalyst to the feedstock injection point below the
catalyst riser is regulated by a slide valve in the regenerated catalyst line. The hot flue gas exits the
regenerator after passing through multiple sets of two-stage cyclones that remove entrained catalyst
from the flue gas,

The amount of catalyst circulating between the regenerator and the reactor amounts to about 5 kg
per kg of feedstock, which is equivalent to about 4.66 kg per litre of feedstock.[1][7] Thus, an FCC
unit processing 75,000 barrels per day (11,900 m3/d) will circulate about 55,900 tonnes per day of
catalyst.
Figure 1: A schematic flow diagram of a Fluid Catalytic Cracking unit as used in petroleum
refineries

Distillation column

The reaction product vapors (at 535 °C and a pressure of 1.72 barg) flow from the top of the reactor
to the bottom section of the distillation column (commonly referred to as the main fractionator)
where they are distilled into the FCC end products of cracked naphtha, fuel oil, and offgas. After
further processing for removal of sulfur compounds, the cracked naphtha becomes a high-octane
component of the refinery's blended gasolines.

The main fractionator offgas is sent to what is called a gas recovery unit where it is separated into
butanes and butylenes, propane and propylene, and lower molecular weight gases (hydrogen,
methane, ethylene and ethane). Some FCC gas recovery units may also separate out some of the
ethane and ethylene.

Although the schematic flow diagram above depicts the main fractionator as having only one
sidecut stripper and one fuel oil product, many FCC main fractionators have two sidecut strippers
and produce a light fuel oil and a heavy fuel oil. Likewise, many FCC main fractionators produce a
light cracked naphtha and a heavy cracked naphtha. The terminology light and heavy in this context
refers to the product boiling ranges, with light products having a lower boiling range than heavy
products.

The bottom product oil from the main fractionator contains residual catalyst particles which were
not completely removed by the cyclones in the top of the reactor. For that reason, the bottom
product oil is referred to as a slurry oil. Part of that slurry oil is recycled back into the main
fractionator above the entry point of the hot reaction product vapors so as to cool and partially
condense the reaction product vapors as they enter the main fractionator. The remainder of the
slurry oil is pumped through a slurry settler. The bottom oil from the slurry settler contains most of
the slurry oil catalyst particles and is recycled back into the catalyst riser by combining it with the
FCC feedstock oil. The so-called clarified slurry oil or decant oil is withdrawn from the top of
slurry settler for use elsewhere in the refinery, as a heavy fuel oil blending component, or as carbon
black feedstock.

Regenerator flue gas

Depending on the choice of FCC design, the combustion in the regenerator of the coke on the spent
catalyst may or may not be complete combustion to carbon dioxide CO2. The combustion air flow is
controlled so as to provide the desired ratio of carbon monoxide (CO) to carbon dioxide for each
specific FCC design.[1][4]

In the design shown in Figure 1, the coke has only been partially combusted to CO2. The
combustion flue gas (containing CO and CO2) at 715 °C and at a pressure of 2.41 barg is routed
through a secondary catalyst separator containing swirl tubes designed to remove 70 to 90 percent
of the particulates in the flue gas leaving the regenerator.[8] This is required to prevent erosion
damage to the blades in the turbo-expander that the flue gas is next routed through.

The expansion of flue gas through a turbo-expander provides sufficient power to drive the
regenerator's combustion air compressor. The electrical motor-generator can consume or produce
electrical power. If the expansion of the flue gas does not provide enough power to drive the air
compressor, the electric motor/generator provides the needed additional power. If the flue gas
expansion provides more power than needed to drive the air compressor, than the electric
motor/generator converts the excess power into electric power and exports it to the refinery's
electrical system.[3]

The expanded flue gas is then routed through a steam-generating boiler (referred to as a CO boiler)
where the carbon monoxide in the flue gas is burned as fuel to provide steam for use in the refinery
as well as to comply with any applicable environmental regulatory limits on carbon monoxide
emissions.[3]

The flue gas is finally processed through an electrostatic precipitator (ESP) to remove residual
particulate matter to comply with any applicable environmental regulations regarding particulate
emissions. The ESP removes particulates in the size range of 2 to 20 µm from the flue gas.[3]

The steam turbine in the flue gas processing system (shown in the above diagram) is used to drive
the regenerator's combustion air compressor during start-ups of the FCC unit until there is sufficient
combustion flue gas to take over that task.

Chemistry
Before delving into the chemistry involved in catalytic cracking, it will be helpful to briefly discuss
the composition of petroleum crude oil.
Petroleum crude oil consists primarily of a mixture of hydrocarbons with small amounts of other
organic compounds containing sulfur, nitrogen and oxygen. The crude oil also contains small
amounts of metals such as copper, iron, nickel and vanadium.[2]

Table 1
Carbon 83-87%
Hydrogen 10-14%
Nitrogen 0.1-2%
Oxygen 0.1-1.5%
Sulfur 0.5-6%
Metals < 0.1%

The elemental composition ranges of crude oil are summarized in Table 1 and the hydrocarbons in
the crude oil can be classified into three types:[1][2]

 Paraffins or alkanes: saturated straight-chain or branched hydrocarbons, without any ring

structures
 Naphthenes or cycloalkanes: saturated hydrocarbons having one or more ring structures with
one or more side-chain paraffins
 Aromatics: hydrocarbons having one or more unsaturated ring structures such as benzene or
unsaturated polycyclic ring structures such as naphthalene or phenanthrene, any of which
may also have one or more side-chain paraffins.

Olefins or alkenes, which are unsaturated straight-chain or branched hydrocarbons, do not occur
naturally in crude oil.

Figure 2: Diagrammatic example of the catalytic cracking of petroleum hydrocarbons

In plain language, the fluid catalytic cracking process breaks large hydrocarbon molecules into
smaller molecules by contacting them with powdered catalyst at a high temperature and moderate
pressure which first vaporizes the hydrocarbons and then breaks them. The cracking reactions occur
in the vapor phase and start immediately when the feedstock is vaporized in the catalyst riser.
Figure 2 is a very simplified schematic diagram that exemplifies how the process breaks high
boiling, straight-chain alkane (paraffin) hydrocarbons into smaller straight-chain alkanes as well as
branched-chain alkanes, branched alkenes (olefins) and cycloalkanes (naphthenes). The breaking of
the large hydrocarbon molecules into smaller molecules is more technically referred to by organic
chemists as scission of the carbon-to-carbon bonds.

As depicted in Figure 2, some of the smaller alkanes are then broken and converted into even
smaller alkenes and branched alkenes such as the gases ethylene, propylene, butylenes, and
isobutylenes. Those olefinic gases are valuable for use as petrochemical feedstocks. The propylene,
butylene and isobutylene are also valuable feedstocks for certain petroleum refining processes that
convert them into high-octane gasoline blending components.

As also depicted in Figure 2, the cycloalkanes (naphthenes) formed by the initial breakup of the
large molecules are further converted to aromatics such as benzene, toluene, and xylenes, which
boil in the gasoline boiling range and have much higher octane ratings than alkanes.

In the cracking process carbon is also produced which gets deposited on the catalyst (catalyst coke).
The carbon formation tendency or amount of carbon in a crude or FCC feed is measured with
methods such as Micro Carbon Residue, Conradson Carbon Residue or Ramsbottom Carbon
Residue.

By no means does Figure 2 include all the chemistry of the primary and secondary reactions taking
place in the fluid catalytic process. There are a great many other reactions involved. However, a full
discussion of the highly technical details of the various catalytic cracking reactions is beyond the
scope of this article and can be found in the technical literature.[1][2][3][4]

Catalysts

Modern FCC catalysts are fine powders with a bulk density of 0.80 to 0.96 g/cm3 and having a
particle size distribution ranging from 10 to 150 µm and an average particle size of 60 to 100 μm.[9]
[10]
The design and operation of an FCC unit is largely dependent upon the chemical and physical
properties of the catalyst. The desirable properties of an FCC catalyst are:

 Good stability to high temperature and to steam

 High activity
 Large pore sizes
 Good resistance to attrition
 Low coke production

A modern FCC catalyst has four major components: crystalline zeolite, matrix, binder, and filler.
Zeolite is the primary active component and can range from about 15 to 50 weight percent of the
catalyst. The zeolite used in FCC catalysts is referred to as faujasite or as Type Y and is composed
of silica and alumina tetrahedra with each tetrahedron having either an aluminum or a silicon atom
at the center and four oxygen atoms at the corners. It is a molecular sieve with a distinctive lattice
structure that allows only a certain size range of hydrocarbon molecules to enter the lattice. In
general, the zeolite does not allow molecules larger than 8 to 10 nm (i.e., 80 to 90
ångströms[contradiction]) to enter the lattice.[9][10]

The catalytic sites in the zeolite are strong acids (equivalent to 90% sulfuric acid) and provide most
of the catalytic activity. The acidic sites are provided by the alumina tetrahedra. The aluminum
atom at the center of each alumina tetrahedra is at a +3 oxidation state surrounded by four oxygen
atoms at the corners which are shared by the neighboring tetrahedra. Thus, the net charge of the
alumina tetrahedra is -1 which is balanced by a sodium ion during the production of the catalyst.
The sodium ion is later replaced by an ammonium ion, which is vaporized when the catalyst is
subsequently dried, resulting in the formation of Lewis and Brønsted acidic sites. In some FCC
catalysts, the Brønsted sites may be later replaced by rare earth metals such as cerium and
lanthanum to provide alternative activity and stability levels.[9][10]

The matrix component of an FCC catalyst contains amorphous alumina which also provides
catalytic activity sites and in larger pores that allows entry for larger molecules than does the
zeolite. That enables the cracking of higher-boiling, larger feedstock molecules than are cracked by
the zeolite.

The binder and filler components provide the physical strength and integrity of the catalyst. The
binder is usually silica sol and the filler is usually a clay (kaolin).

Nickel, vanadium, iron, copper and other metal contaminants, present in FCC feedstocks in the
parts per million range, all have detrimental effects on the catalyst activity and performance. Nickel
and vanadium are particularly troublesome. There are a number of methods for mitigating the
effects of the contaminant metals:[11][12]

 Avoid feedstocks with high metals content: This seriously hampers a refinery's flexibility to
process various crude oils or purchased FCC feedstocks.
 Feedstock feed pretreatment: Hydrodesulfurization of the FCC feedstock removes some of
the metals and also reduces the sulfur content of the FCC products. However, this is quite a
costly option.
 Increasing fresh catalyst addition: All FCC units withdraw some of the circulating
equilibrium catalyst as spent catalyst and replaces it with fresh catalyst in order to maintain
a desired level of activity. Increasing the rate of such exchange lowers the level of metals in
the circulating equilibrium catalyst, but this is also quite a costly option.
 Demetallization: The commercial proprietary Demet Process removes nickel and vanadium
from the withdrawn spent catalyst. The nickel and vanadium are converted to chlorides
which are then washed out of the catalyst. After drying, the demetallized catalyst is recycled
into the circulating catalyst. Removals of about 95 percent nickel removal and 67 to 85
percent vanadium have been reported. Despite that, the use of the Demet process has not
become widespread, perhaps because of the high capital expenditure required.
 Metals passivation: Certain materials can be used as additives which can be impregnated
into the catalyst or added to the FCC feedstock in the form of metal-organic compounds.
Such materials react with the metal contaminants and passivate the contaminants by forming
less harmful compounds that remain on the catalyst. For example, antimony and bismuth are
effective in passivating nickel and tin is effective in passivating vanadium. A number of
proprietary passivation processes are available and fairly widely used.

The major suppliers of FCC catalysts worldwide include Albemarle Corporation, W.R. Grace
Company and BASF Catalysts (formerly Engelhard). The price for lanthanum oxide used in fluid
catalytic cracking has risen from $5 per kilogram in early 2010 to $140 per kilogram in June 2011.
[13]

History
The first commercial use of catalytic cracking occurred in 1915 when Almer M. McAfee of Gulf
Refining Company developed a batch process using aluminum chloride (a Friedel Crafts catalyst
known since 1877) to catalytically crack heavy petroleum oils. However, the prohibitive cost of the
catalyst prevented the widespread use of McAfee's process at that time.[2][14]

In 1922, a French mechanical engineer named Eugene Jules Houdry and a French pharmacist
named E.A. Prudhomme set up a laboratory near Paris to develop a catalytic process for converting
lignite coal to gasoline. Supported by the French government, they built a small demonstration plant
in 1929 that processed about 60 tons per day of lignite coal. The results indicated that the process
was not economically viable and it was subsequently shut down.[15][16][17]

Houdry had found that Fuller's Earth, a clay mineral containing aluminosilicate (Al2SiO6), could
convert oil derived from the lignite to gasoline. He then began to study the catalysis of petroleum
oils and had some success in converting vaporized petroleum oil to gasoline. In 1930, the Vacuum
Oil Company invited him to come to the United States and he moved his laboratory to Paulsboro,
New Jersey.

In 1931, the Vacuum Oil Company merged with Standard Oil of New York (Socony) to form the
Socony-Vacuum Oil Company. In 1933, a small Houdry process unit processing 200 barrels per day
(32 m3/d) of petroleum oil. Because of the economic depression of the early 1930s, Socony-
Vacuum was no longer able to support Houdry's work and gave him permission to seek help
elsewhere.

In 1933, Houdry and Socony-Vacuum joined with Sun Oil Company in developing the Houdry
process. Three years later, in 1936, Socony-Vacuum converted an older thermal cracking unit in
their Paulsboro refinery in New Jersey to a small demonstration unit using the Houdry process to
catalytically crack 2,000 barrels per day (320 m3/d) of petroleum oil.

In 1937, Sun Oil began operation of a new Houdry unit processing 12,000 barrels per day
(1,900 m3/d) in their Marcus Hook refinery in Pennsylvania. The Houdry process at that time used
reactors with a fixed bed of catalyst and was a semi-batch operation involving multiple reactors
with some of the reactors in operation while other reactors were in various stages of regenerating
the catalyst. Motor-driven valves were used to switch the reactors between online operation and
offline regeneration and a cycle timer managed the switching. Almost 50 percent of the cracked
product was gasoline as compared with about 25 percent from the thermal cracking processes. [15][16]
[17]

By 1938, when the Houdry process was publicly announced, Socony-Vacuum had eight additional
units under construction. Licensing the process to other companies also began and by 1940 there
were 14 Houdry units in operation processing 140,000 barrels per day (22,000 m3/d).

The next major step was to develop a continuous process rather than the semi-batch Houdry
process. That step was implemented by advent of the moving-bed process known as the Thermofor
Catalytic Cracking (TCC) process which used a bucket conveyor-elevator to move the catalyst from
the regeneration kiln to the separate reactor section. A small semicommercial demonstration TCC
unit was built in Socony-Vacuum's Paulsboro refinery in 1941 and operated successfully, producing
500 barrels per day (79 m3/d). Then a full-scale commercial TCC unit processing 10,000 barrels per
day (1,600 m3/d) began operation in 1943 at the Beaumont, Texas refinery of Magnolia Oil
Company, an affiliate of Socony-Vacuum. By the end of World War II in 1945, the processing
capacity of the TCC units in operation was about 300,000 barrels per day (48,000 m3/d).
It is said that the Houdry and TCC units were a major factor in the winning of World War II by
supplying the high-octane gasoline needed by the air forces of Great Britain and the United States.
[15][16][17]

In the years immediately after World War II, the Houdriflow process and the air-lift TCC process
were developed as improved variations on the moving-bed theme. Just like Houdry's fixed-bed
reactors, the moving-bed designs were prime examples of good engineering by developing a
method of continuously moving the catalyst between the reactor and regeneration sections. The first
air-lift TCC unit began operation in October 1950 at the Beaumont, Texas refinery.

This fluid catalytic cracking process had first been investigated in the 1920s by Standard Oil of
New Jersey, but research on it was abandoned during the economic depression years of 1929 to
1939. In 1938, when the success of Houdry’s process had become apparent, Standard Oil of New
Jersey resumed the project as part of a consortium of that include five oil companies (Standard Oil
of New Jersey, Standard Oil of Indiana, Anglo-Iranian Oil, Texas Oil and Dutch Shell), two
engineering-construction companies (M.W. Kellogg and Universal Oil Products) and a German
chemical company (I.G. Farben). The consortium was called Catalytic Research Associates (CRA)
and its purpose was to develop a catalytic cracking process which would not impinge on Houdry's
patents.[15][16][17]

Chemical engineering professors Warren K. Lewis and Edwin R. Gilliland of the Massachusetts
Institute of Technology (MIT) suggested to the CRA researchers that a low velocity gas flow
through a powder might "lift" it enough to cause it to flow in a manner similar to a liquid. Focused
on that idea of a fluidized catalyst, researchers Donald Campbell, Homer Martin, Eger Murphree
and Charles Tyson of the Standard Oil of New Jersey (now Exxon-Mobil Company) developed the
first fluidized catalytic cracking unit. Their U.S. Patent No. 2,451,804, A Method of and Apparatus
for Contacting Solids and Gases, describes their milestone invention. Based on their work, M. W.
Kellogg Company constructed a large pilot plant in the Baton Rouge, Louisiana refinery of the
Standard Oil of New Jersey. The pilot plant began operation in May 1940.

Based on the success of the pilot plant, the first commercial fluid catalytic cracking plant (known as
the Model I FCC) began processing 13,000 barrels per day (2,100 m3/d) of petroleum oil in the
Baton Rouge refinery on May 25, 1942, just four years after the CRA consortium was formed and
in the midst of World War II. A little more than a month later, in July 1942, it was processing
17,000 barrels per day (2,700 m3/d). In 1963, that first Model I FCC unit was shut down after 21
years of operation and subsequently dismantled.[15][16][17][18]

In the many decades since the Model I FCC unit began operation, the fixed bed Houdry units have
all been shut down as have most of the moving bed units (such as the TCC units) while hundreds of
FCC units have been built. During those decades, many improved FCC designs have evolved and
cracking catalysts have been greatly improved, but the modern FCC units are essentially the same
as that first Model I FCC unit.

Note: All of the refinery and company names in this history section (with the exception of Universal
Oil Products) have changed over time by mergers and buyouts. Some have changed a number of
times.

See also
 Oil refinery
 Petroleum
 Cracking (chemistry)
 Catalysis