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Know More about F.C.C.

Catalysts

Seminar Report
Submitted as part of coursework for
CL 618 (Catalysis and Surface Chemistry)
By
Rupsha Bhattacharyya
Roll No.: 09302009
M. Tech 1st Year

Department of Chemical Engineering


Indian Institute of Technology, Bombay
2010
Abstract

Fluidized Catalytic Cracking (FCC) is the principle gasoline upgradation technology practiced in

oil refineries round the world. The catalysts used in this process are zeolites of various kinds, tailor-made

for a particular application. The report describes the various interesting physical and chemical features of

these catalysts that have made them irreplaceable in the FCC applications. The catalytic reaction

mechanisms are also briefly discussed. The hundreds of varieties of zeolites commercially available and

used in refineries all over the world make it necessary to understand the relation between the

composition, structure and properties of these catalysts. As these catalysts are quite expensive and they

also have special additives mixed with them for accomplishing special functions, it is important to

provide a proper catalyst management system that takes care of catalyst recovery, replacement and loss

minimization. The major catalyst developers of the world have come up with various interesting catalyst

formulations for meeting the demands of refiners. Some of these proprietary catalysts are also mentioned

in this report. The current research being carried to gain deeper understanding of these catalysts and

predicting their performance is also alluded to in this work.

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Table of Contents

Abstract 2
Chapter 1: Introduction 5
Chapter 2: Typical Components of FCC Catalysts
2.1: Introduction 6
2.2: Zeolites 6
2.2.1: Zeolite Structure and Chemistry 7
2.2.2: Zeolite nomenclature 8
2.2.3: Features of Zeolites suitable for catalysis
2.2.4: Zeolites used as FCC catalysts 9
2.3: Matrix 9
2.4: Fillers and Binders 10
Chapter 3: Major Physical Characteristics of FCC Catalysts
3.1: Introduction 11
3.2: Attrition resistance 11
3.3: Pore Size Distribution and Pore Volume 11
3.4: Surface Area 11
3.5: Particle Size Distribution 12
3.6: Thermal and Hydrothermal Stability 12
3.7: Crystallinity 12
3.8: Microactivity test (MAT) for FCC Catalysts 12
Chapter 4: Synthesis of FCC Catalysts
4.1: Introduction 13
4.2: Conventional Zeolites 13
4.3: Ultrastable Zeolites (USY) 13
4.4: In-situ process 13
Chapter 5: Effects of FCC Catalyst Composition on its Properties

5.1: Introduction 14
5.2: Effect of Zeolite Content of the Catalyst 14
5.3: Effect of Additives 14
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5.3.1: ZSM-5 Additive 15
5.3.2: CO Promoter 15
5.3.3: SOx Additive 15
5.3.4: Metal Passivators 15
Chapter 6: Catalytic Cracking Reaction Mechanisms
6.1: Introduction 16
6.2: Mechanism of Catalytic Cracking Reactions 16
Chapter 7: Catalyst Management in FCC Units
7.1: Introduction 18
7.2: Addition of Fresh Catalyst 18
7.3: Spent Catalyst Stripping 18
7.4: Minimizing Catalyst losses 18
7.5: Preventing Excessive Coking Tendencies 19
Chapter 8: Recent Developments in FCC Catalyst Technology
8.1: Introduction 20
8.2: Demetallization Procedures 20
8.3: Modelling of FCC Catalyst Pore Structures 20
8.4: Advanced Kinetic Models 21
8.5: Special Catalysts for Short Contact Time Applications 22
8.6: Some other Special Purpose FCC Catalysts 23
Chapter 9: Conclusion 24
References 25

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Chapter One
Introduction
1.1 Background
Fluid catalytic cracking (FCC) is one of the most important operations carried out in a modern
petroleum refinery and its principle aim is the upgradation of low-value petroleum feed stock and its
conversion to more valuable liquid fuels like gasoline or petrol. Ever since the development of the
catalytic cracking processes by Eugene Houdry in the 1920s, it has become the mainstay of the refineries
as far as their economics are concerned. Today almost all the catalytic cracking practiced in refineries is
done through FCC and this goes onto show how valuable a process it is for any refinery. There are
several licensed technologies available from licensers like Shell Oil Company, UOP, ABB Lummus and
Kellogg Brown and Root [1]. The mechanical design of the FCC units vary from licenser to licenser
.The key difference in the operation of these units comes from the different FCC catalyst formulations
used by different refineries at different points of time as per the required product distribution. In the
1960s the introduction of zeolite cracking catalysts marked a revolution in the refining industry. Ever
since then several kinds of zeolites have been commercially synthesized and applied as FCC catalysts.
Today such catalysts are used in all FCC units. They have increased the profitability of the FCC units
dramatically and have led to the diversification of the catalyst as well as the major products from the
FCC unit.
Catalytic cracking demands the use of acid catalysts. In the initial stages of the history of catalytic
cracking acid-leached clays and artificial or natural silica-alumina catalysts were used [2]. In the 1960s
they were replaced almost entirely by the zeolite catalysts and this led to great increase in the conversion
of the feedstock to gasoline as well as lowered the formation of coke and dry gas. Presently about 140
kinds of zeolites have been synthesized artificially along with about 40 naturally occurring types.
Several kinds of moderate to high temperature gas phase catalytic reactions are performed using them.
Several treatment operations carried out on the zeolites enable them to be used according to the
particular product (e.g. olefins like propylene, or gasoline with higher octane number rating) desired.
In this report attempt is being made to present some of the details regarding the synthesis,
characterization and use of the zeolites for FCC. In addition some modern developments and current
research pertaining to further modification and improvement of these fascinating catalysts also presented
here.

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Chapter Two
Typical Components of FCC Catalysts
2.1 Introduction
The catalysts typically used in FCC units consist of fine powders with an average particle size of 75
microns. The major components of these catalysts are discussed in the following sections.
2.2 Zeolites
The active catalytic ingredients in the FCC catalysts are zeolites. Zeolites are crystalline alumino-
silicates with a negatively charged macromolecular inorganic framework. They are micro porous and
hence are extensively used as commercial adsorbents. The first artificial synthesis was carried out in the
1960s and ever since then they have been applied extensively as industrial catalysts, most notably in the
petroleum and petrochemical sectors. FCC units are almost exclusively using these catalysts. The porous
structure of the zeolites enables them to accommodate a large variety of cations like Na +, Ca+, etc. These
positive ions are rather loosely held and can readily be exchanged for others especially H+ ions in a
contact solution. Natural zeolites form where volcanic rocks and volcanic ash layers react with alkaline
groundwater. They are mined in several parts of the world for commercial purposes. Along with it they
are also synthesized by a variety of techniques as discussed in this report.
2.2.1 Zeolite Structure and Chemistry
An enormous variety of zeolites have been identified and categorized and understanding their
structures and its relation to their properties is essential for selecting the right kind of zeolite for a given
purpose. Zeolites have a very well defined lattice structure. Its basic units consist of silica and alumina
tetrahedra. Each tetrahedron consists of a silicon or aluminum atom at the centre of the tetrahedron with
oxygen atom at the 4 corners. The pore diameters can vary over some limits in the different types of
zeolites, with 8 oA being a typical value and reversibly adsorbed water [1]. For a given zeolite, of course
the pore sizes are very nearly uniform. This is an important property which is exploited while designing
catalysts. The internal surface area is of the order of 600 m2/gm or even more. The framework of the
zeolites contains freely mobile and exchangeable cations and reversibly adsorbed water. The general
formula used to represent the zeolites is as follows:
Mex/z [(AlO2) x (SiO2) y]. nH2O
where Me stands for a cation with a positive charge z. Silicon is in a +4 oxidation state and hence a
tetrahedron consisting of silicon has neutral charge [2]. But aluminum is in +3 oxidation state and so
each tetrahedron containing aluminum has -1 negative charge .To compensate for the charge there are
other cations found in the zeolite structure and these are mainly obtained when the zeolite is being

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synthesized using some alkaline solution. Often the sodium ions from the sodium hydroxide solution are
used in the balancing of the charges but the zeolite made by this route is not hydrothermally stable. The
ammonium ion is frequently used to replace the sodium ions which on drying leaves behind H+ ions
which provide the acid sites( both Bronsted acid and Lewis acid sites) necessary for cracking reactions.
The Bronsted sites can further be exchanged with rare earth elements like lanthanum and cerium in order
to further tailor their properties.

(a) (b) (c)


Fig 1: Different types of Zeolites-(a) Commercially synthesized Zeolites, (b) Naturally occurring
Zeolites, (c) Computer generated structure of a typical Zeolite
(Source: (a) www.himfr.com, (b) and (c) www.wikipedia.org)
2.2.2 Zeolite nomenclature
A large variety of zeolites are already known and many more with interesting properties are being
synthesized. Hence it is necessary to follow a systematic procedure of naming them. 98 structures were
included in the 1996 issue of the Atlas of zeolite Structure Types and several more have been approved
by the Structure Commission of the International Zeolite Association (IZA). Some synthetic zeolites
have been named after the isostructural natural minerals like Faujasite, Mordenite or Ferrierite while
some others are known by the academic or industrial laboratories where they were first synthesized (e.g.
ZSM from Mobil or EU from Edinburgh University). For a common nomenclature policy each zeolite
framework has been assigned a three letter mnemonic. Some examples are provided below:

Fig 2: Mnemonics for different Zeolites


(Source: Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier, 2001)

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2.2.3 Features of Zeolites suitable for catalysis
There are several reasons why zeolites have become the preferred catalyst for many reactions of
industrial importance. These are briefly described below:
a) Thermal Stability: One of the most important reasons behind the selection of zeolites as catalysts
for high temperature reactions is their good thermal stability. Most of the zeolites remain unaffected by
temperatures as high as 650oC. The structural collapse of the specially prepared high silica zeolites
becomes significant only at temperatures as high as 1000oC. Thus they are the most suitable for a
reaction scheme like fluid catalytic cracking where high temperatures and other harsh operating
conditions prevail.
b) Acidity: Zeolites exhibit much higher acidity than the earlier amorphous silica-alumina catalysts.
The acidity of the zeolites is due to the presence of both Bronsted as well as Lewis acid sites. The
Bronsted acid sites develop as the bridging hydroxyl groups consisting of hydroxyl protons associated
with the framework oxygen ions bonded to negatively charged tetrahedrally coordinated framework
aluminum. The maximum density of these acid sites is related to silicon to aluminum ratio in the zeolite.
As the density of the aluminum ions increases the acid site density decreases. The Bronsted acid sites are
generated in the zeolites by ion exchange.
The Lewis acid sites are formed upon heating the proton forms above 500 oC where cleavage of
water from the zeolite surface occurs.
The solid state acidity of zeolites is described by parameters like the following [2]:
1. The nature or type of the acid sites
2. The density or concentration of the acid sites
3. The strength distribution of the acid sites
4. The location of the acid sites within the zeolite framework
5. The geometric distribution of the acid sites over the zeolite crystals
An important parameter governing the total potential acidity per unit cell in the zeolite framework is
the Unit Cell Size (UCS), measured in Ao [1] .The negatively charged aluminum atoms are sources of
active sites in the zeolite .Silicon atoms do not possess any activity. The UCS is related to the number of
aluminum atoms per cell ( NAl) by
NAl = 111* (UCS-24.215)
c) Shape selectivity: The dimensions of the pores within the zeolite frameworks are often similar to
the sizes of the molecules participating in the reactions catalyzed by them. This creates a strong
influence on the selectivity of such reactions. There may be reactant shape selectivity, product shape
selectivity and transition state shape selectivity. The first two kinds of selectivity are usually based on

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the mass transfer effects rather than on chemical kinetics while the last category is based on the intrinsic
features of a reaction mechanism.
d) Concentration effects: The catalytic reactions are often involved with an adsorption step
whereby the reactants get attached to specific sites on the zeolites and then participate in the reaction.
The pore size distribution the specific pore volumes and the hydrophilicity or the hydrophobicity of the
zeolites can all affect the reactions and their selectivity. These properties can be fine-tuned while
synthesizing zeolites and therefore zeolites suitable for very specific purposes can be created.
2.2.4 Zeolites used as FCC catalysts
The zeolites typically applied as FCC catalysts are Type X, Type Y and ZSM-5. Types X and Y
possess similar crystal structures but the X zeolite has a lower silica-alumina ratio, which makes it less
stable. ZSM-5 is a versatile zeolite that helps in increasing the yield of olefins from FCC. The NaY
zeolites that are synthesized extensively are often ion-exchanged with rare earth elements like lanthanum
or cerium that form bridges with two or three acid sites in the zeolite framework. This protects the acid
sites and also makes the zeolites hydrothermally stable. Now-a-days as the demand for gasoline of
higher and higher octane rating is increasing, ultrastable Y or USY zeolites are being used to enhance
olefinicity and hence the octane number of gasoline. These catalysts have higher silica to alumina ratios
than the conventional Y zeolites.
2.3 Matrix
The matrix in the FCC catalyst is often considered to be that part of the catalyst other than the
zeolites. It may or may not have catalytic activity. Very often it does possess sufficient catalytic activity
towards some components of the feedstock and in this case they are described by the term ‘active
matrix’. Usually the matrix consists of substances that were used as FCC catalysts before the
development of zeolites e.g. acid leached clays and synthetic alumina-silica gels. In the majority of the
FCC catalysts the zeolites is embedded in the matrix.
The matrix serves several important physical functions such as:
A) Binding: One of the major functions of the matrix or certain components of it is to bind the zeolites
particles together in the form of microspheroidal catalyst particles after the spray drying operation.
B) Allowing diffusion: The matrix with its pore structure allows the diffusion of the required
hydrocarbons to the actual catalytic sites for reaction. A sufficiently stable pore structure of the matrix
will prevent collapse or sintering of the catalyst particles under adverse hydrothermal conditions of
operation of the FCC unit.
C) Diluting medium: This serves to moderate zeolite activity and avoids over-cracking that leads to
excessive coke formation and gas production.

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D) Heat transfer: The matrix functions as the storage of thermal energy in the FCC unit. It allows heat
transfer during cracking and regeneration operations and prevents catalyst damage due to excessive
temperatures.
The matrix consists of two main components-firstly a synthetic component like amorphous silica,
silica-alumina gels or silica-magnesia gels which serve as the binder and also exhibit catalytic properties.
The other component is some clay, natural or chemically modified, like kaolinite, halloysite or
montmorillonite. The clays provide mechanical stability.
Depending on their catalytic behaviour, the matrices may be classified as low activity, medium
activity or high activity matrices. The activity depends on the surface area of the fresh matrix the number
of acid sites and the presence of steam-stable pores in the size range of 50-150 Ao. The matrix usually
cracks some of the largest molecules in the feedstock and reduces them to such forms when thy can
easily enter the pores of the main zeolite catalysts. The highly active matrices can help in the bottoms
upgradation by enabling the cracking of the heaviest components of the residue; they can improve the
quality of light cycle oils (LCO) and also helps to increase the resistance of the zeolites towards
poisoning by metal deposition. The matrix is capable of trapping the metal contaminants and rendering
them passive [5].
A synergistic effect is often noted between the zeolite catalyst and the active matrix and this enables
us to have higher yields of the desired products.
2.4 Fillers and Binders
The functions of the fillers and binders incorporated into the FCC catalysts are often similar to those
performed by the matrix. Sometimes additional fillers like kaolin may be provided for physical integrity
and as a more efficient fluidizing medium [1]. The binder performs the all important function of holding
the catalyst, the matrix and the filler glued together. This is especially important when the catalyst
contains a higher amount of zeolites. The filler and binder minimize the production of catalyst fines in
the reactor-regenerator system and help to control the catalyst losses.

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Chapter Three
Major Physical Characteristics of FCC Catalysts
3.1 Introduction:
Several properties of zeolites have to be considered when selecting them as catalysts for FCC. Some
of these properties govern the catalytic behaviour of the zeolites while some others affect the mechanical
design and operation of the FCC unit itself [3]. These properties are briefly discussed below:
3.2 Attrition Resistance:
During the operation of the FCC unit the high gas flow rates and the harsh temperature often cause the
attrition of the catalyst particles and produce fines. Not all of the fines may be recovered by the cyclone
separators before the products can be separated. This leads to catalyst losses and causes emission of
particulate matter into the environment [3]. It also governs the rate at which fresh catalyst make-up must
be provided to the unit. As the particle size distribution is affected by this, the conditions of fluidization
itself might change.
An increase in the zeolite content of the catalyst, reduction of the zeolite crystal size and better
dispersion of the zeolite within the matrix leads to improved attrition resistance. The nature and quantity of
the binder provided to the catalyst also affects the attrition resistance. For example the boehmite form of
alumina is more effective in reducing attrition than gibbsite or bayerite. The type, particle size and the
morphology of the clay used as filler has a role to play in the attrition of the catalyst. Kaolin has been
found to increase the attrition resistance. The conditions maintained during spray drying of the catalyst
affects its future attrition resistance.
Catalyst attrition resistance is indicated by the value of the attrition index which is obtained from
standard methods.
3.3 Pore Size Distribution and Pore Volumes:
The pore size distribution has a major role to play in the catalyst properties of zeolites. If the pores are
too small, then they have a greater tendency to get clogged by coke and they also exhibit greater
diffusional resistance. If the pores are too large they provide a lower surface area for a given volume and
hence lower the efficacy of the catalyst and lead to enhanced attrition. The pore size distribution is also an
important parameter for the catalyst matrix as well. The shape of the pores is the most important property
governing the shape selectivity of the catalyst which is the most important characteristic used in many
applications.
3.4 Surface Area:

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The surface area of the catalyst comes from the zeolite and also the matrix. It ranges from over 800
m2/gm for conventional Y zeolites and is around 600 m 2/gm for USY zeolites. The reduction in surface
area is due to the hydrothermal treatment given to the zeolites to enhance their stability which affects their
crystallinity and brings about changes in their pore structure. During the steam stripping step carried out
before regeneration of these catalysts the pore structure might collapse and thereby there is loss of surface
area. Catalysts in which the matrix is also active generally have higher surface areas.
3.5 Particle Size Distribution:
Most of the FCC catalysts have particle size ranging from 60 to 80 µm. The actual size distribution
depends heavily on the conditions prevailing in the spray drying step of catalyst manufacture. Fines
generated during the fluidized catalytic cracking often change the size distribution of the catalyst. This
might call for changes in the gas velocities to enhance good fluidization in the riser section and might also
make it necessary to make the operation of the cyclone separators somewhat flexible. Particulate emission
might also result from the fines.
3.6 Thermal and hydrothermal stability
The chemical nature of the zeolites, especially the silica-to-alumina ratio, crystallinity, ion-exchange
and residual sodium ions in the zeolite affect its stability. Maintaining the catalyst stability is essential to
maintaining its activity and selectivity. Rare earth exchanged zeolites are exceptionally stable. Stable
catalysts retain their pore structure during regeneration also.
3.7 Crystallinity
The crystalline nature of the FCC catalysts as determined from X-ray diffraction studies is an
indication of the zeolite content. The X-ray studies of the fresh catalyst and the equilibrium catalyst can
provide information about structural loss and the catalyst stability.
3.8 Microactivity Test (MAT) for FCC Catalysts:
The standard Microactivity test of the FCC catalysts is a valuable tool to evaluate the properties of
equilibrium catalysts from the FCC unit [4]. Since the operation of FCC units are cyclic the catalysts
undergo major changes in their properties from their fresh state and all these evaluations are carried out
after they have stabilized i.e. they have become equilibrium catalysts [6]. At the heart of this test lies a
fixed bed reactor into which the hot gas oil sample is injected. The catalyst activity is reported as the
conversion of the 2210C material. The conversion depends on the catalyst-to-oil ratio, feed space velocity
and other factors. The coke forming and gas forming tendencies of the catalyst as well as the above
mentioned physico-chemical properties of the catalysts cam be obtained from this useful test. It helps in
ascertaining the conditions to which the catalyst has been exposed. This test is simple and not much time
consuming.

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Chapter Four
Synthesis of FCC Catalysts
4.1 Introduction:
Modern processes used to manufacture FCC catalysts are of two types- (a) Incorporation method in
which the catalyst and the matrix are synthesized separately and then mixed with the fillers and binders,
and (b) ‘in-situ’ processes whereby the zeolite catalytic component is allowed to grow within preformed
microspheres of some kaolin type of particles. A general description of the processes is presented in the
following paragraphs.
4.2 Conventional Zeolites:
To prepare ordinary catalysts like REY, REHY or HY, firstly NaY zeolite is produced by the
digestion of a mixture consisting of silica, alumina and caustic soda for about 10 hours at prescribed
temperatures till crystallites start forming. After separating the crystals rare earth exchange of the
zeolites may be carried out either before or after its incorporation into the matrix element. The sodium
level of the zeolites is generally reduced to improve their hydrothermal stability by rare earth exchange
or by treatment with ammonium salt solutions to impart H+ ions into the matrix. The rare earth
exchanged catalysts are generally more active in increasing the yield of gasoline from the gas oils or the
resid fractions if their content in the catalyst is over 10 % by weight.
4.3 Ultrastable Zeolites (USY):
The preparation of these catalysts is accomplished by replacing some of the aluminum ions in the
framework by silicon. Steam calcination of the zeolite at a temperature of 700-800 oC is generally carried
out for this purpose. Apart from this acid leaching, chemical extraction and chemical substitution are
also employed to reduce the alumina content of zeolites. All the components of the catalyst are mixed to
form slurry and that is finally spray-dried to obtain USY zeolite catalyst. The residual alumina
precipitated within the pores of the zeolite during the synthesis can affect the catalyst properties
significantly. Octane boosting catalyst additives like ZSM-5 zeolites are also incorporated within the
catalyst matrix before the spray drying operation. The preparation of ZSM-5 is done in a manner similar
to that of any general zeolite material.
4.4 In-situ processes:
In this method the slurries of various grades of kaolin are first spray dried to form microspheres
which are then hardened at 700OC. These spheres are then digested with caustic soda or sodium silicate.
Thus the catalyst, the active matrix and the filler and binding agents develop simultaneously within the
microspheres. This process was developed by Engelhard.

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Chapter Five
Effects of FCC Catalyst Composition on its Properties
5.1 Introduction:
A wide variety of zeolite catalysts, having a range of useful properties are being used in different FCC
units round the world. These catalysts are tailor-made for specific purposes like selective cracking of the
feedstock to produce more olefins or more gasoline as per the requirements. Several catalysts have
additives like ZSM-5 mixed with them to enhance the octane number of the gasoline produced or to
control the emission of SOx, NOx or CO from the regenerator. In general, as the yield of gasoline
increases its octane number decreases, and this makes it necessary to add more expensive octane boosting
agents to it. As conversion of the feedstock rises, the yields of both gasoline and LCO pass through a
maximum and then decrease. But coke formation and gas production show a rising trend as conversion
rises.
5.2 Effect of Zeolite Content of the Catalyst:
An increase in the zeolite content of the catalyst leads to an increase in the catalytic activity as
expected. For a given conversion, as zeolite input increases the gasoline and LCO yields also increase
while hydrogen, C3-C4 olefins and coke yields decrease. The decrease in the unit cell size of the catalyst
arising out of the increase in the silica-to-alumina ratio leads to decrease of catalytic activity. Though the
USY catalysts are less active compared to conventional REY zeolites, they retain their activity under more
severe operating conditions. For a higher silica-to-alumina ratio there is greater production of LPG
fractions, lower formation of coke and lower gasoline selectivity [3]. The unit cell size thus has a major
role to play in dictating the selectivity exhibited by the zeolite. Apart from this the decrease in the unit cell
size of the zeolite results in an increase in the RON and MON values of the gasoline. This is predominant
at very low pore sizes in the region of highly acidic sites [3]. The presence of Na+ ions in the de-
aluminated zeolite framework inhibits the formation of high octane gasoline. This is probably due to the
neutralization of the acid sites by the residual free Na+ ions. Even the preparation method of the zeolites
has been found to have an effect on the catalytic activity and hence the final product distribution from the
FCC unit.
5.3 Effect of Additives:
Several kinds of additives are often added to the zeolite catalysts used in FCC units in order to change
the product distribution or to comply with increasingly stringent environmental regulations. Some of these
are discussed below:

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5.3.1 ZSM-5 additive: This is a special kind of high silica zeolite which is a member of the pentasil
family. It is widely used as an octane boosting additive in FCC. It may be incorporated into the catalyst
during the preparation or it may be added as separate particles. About 1-3 % of ZSM-5 added to the FCC
catalyst can raise the RON of the gasoline produced by up to 3 units [3]. The pore geometry of this
additive is such that it prevents the formation of cyclic compounds which lead to subsequent coke
formation.

Fig 3: Computer generated image of ZSM-5 showing its pore structure


(Source: www.3dchem.com)

5.3.2 CO Promoter: This additive consists of metals from the platinum group, present in the
concentration of 300 to 800 ppm and distributed over a support, and its use is to facilitate the conversion
of CO produced during catalyst regeneration to CO2. Though more uniform burning of the coke is
accomplished the additive tends to raise the temperatures during regeneration and also the production of
NOx. Typically 1 to 2.3 Kg of the promoter is added per ton of the fresh catalyst [1].
5.3.3 SOx Additive: The coke deposited on the FCC catalyst contains sulphur in the form of organic
compounds and during regeneration it forms SO2 and SO3. These acidic gases are finally discharged into
the atmosphere along with the flue gases. Keeping in mind the harmful environmental effects of the SOx it
has become necessary to control their emission from the FCC units. The additive is usually a metal oxide
which is directly mixed with the catalyst and it absorbs and bonds chemically with the SO3 in the
regenerator. This stable sulphate species is carried to the riser section where it is reduced to H2S and the
metal oxide. An excess of oxygen is needed in the regenerator so that the additive may provide the full
benefits.
5.3.4 Metal Passivators: Metals like Nickel, Vanadium and Sodium are often present in the feed to the
FCC unit and they have a detrimental effect on the FCC catalyst as they poison the active sites. To prevent
this metal passivators like Antimony are used. The passivators are injected into the feed and they form an
alloy with the nickel. This greatly reduces the dehydrogenation reactions and the resultant production of
dry gas and hydrogen.
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Chapter Six
Catalytic Cracking Reaction Mechanisms
6.1 Introduction:
FCC operations underwent a dramatic change with the introduction of zeolite catalysts and the
replacement of the conventional amorphous silica-alumina catalysts. Zeolites or artificial faujasites are
several hundreds of times more active that the conventional FCC catalysts used before 1960s and the
product distribution obtained from their usage is also quite different. With the development of newer
varieties of catalysts, greater control over catalyst selectivity and hence the main product from FCC has
been made possible. The typical reactions occurring in an FCC unit are tabulated below:

Feedstock Component Reaction Products Obtained


Paraffins Cracking Lower Paraffins and
Cracking LPG Olefins
Olefins
Cyclization Naphthenes
Olefins
Isomerization Branched Hydrocarbons
H-Transfer Paraffins
Condensation, Coke
Dehydrogenation
Cracking Olefins
Dehydrogenation Cyclo-olefins, Aromatics
Naphthenes
Isomerization A variety of Naphthenes
Side-chain Cracking Unsubstituted Aromatics
Transalkylation Different Alkyl aromatics
Aromatics
Dehydrogenation, Poly-aromatics
Condensation
6.2 Mechanism of Catalytic Cracking Reactions:
Catalytic cracking reactions generally proceed through the formation of Carbenium ions (R-CH 2+).
Another type of carbocation that may also be formed is the Carbonium ion (CH5+) by the addition of a
proton to the paraffin molecule. The proton is obtained from the catalyst Bronsted acid site. But this
species is not at all stable and the acid sites on the catalysts are usually not strong enough for the formation
of many such species.
On the other hand, a carbenium ion is formed either by the addition of a positive charge to an olefin or
by the removal of hydrogen and two electrons from a paraffin. These reactions are shown below:
(a) R-CH=CH-CH2-CH2-CH3 + H+(a proton at Bronsted site)  R-C+H-CH2-CH2-CH3
(b) R-CH2-CH2-CH2-CH3(removal of H- at Lewis acid site)  R-C+H-CH2-CH2-CH3
The tertiary carbocations are most stable, followed by the secondary and primary species. So during the
cracking process the primary and tertiary species tend to rearrange themselves into the tertiary forms and
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hence skeletal isomerization leading to the formation of branched hydrocarbons is one of the major
reactions taking place in the FCC. This gives us gasoline having higher octane numbers. Some olefins are
also produced due to typical thermal cracking mechanisms.
The main reaction is cracking which proceeds by the mechanism of Beta Scission. Here the
hydrocarbon is split at that carbon atom which is at the beta position with respect to the positive charge
bearing carbon atom. This is due to lower energy required to break this bond than the bond at the alpha
carbon. Short chained hydrocarbons have been found to be less reactive than long chained ones and hence
stable carbenium ions are not formed from the short chained species. Initially the products of beta scission
are an olefin and a new carbenium ion. The carbenium ion goes on to participate in a series of chain
reactions which lead to the cracking of the larger molecules and which stop with a typical chain
termination step. Cracking is a mono-molecular process and is favoured by high temperatures as it is an
endothermic process.
Hydrogen transfer reactions are also common during catalytic cracking. These are bimolecular
reactions which typically involve an olefin with another olefin or a naphthene. In case of two olefins, both
of them are adsorbed on active sites in the catalyst and one of them becomes the paraffin while the other is
converted to a cyclo-olefin as hydrogen is transferred from one species to another. The cyclo-olefin further
reacts to form a cyclo-di-olefin which finally rearranges to form aromatics. In case of the naphthenes, they
are the hydrogen donors and they react with olefins to produce paraffins and aromatics. The rare earth
exchanged zeolites enhance hydrogen transfer reactions as they protect adjacent acid site through the
formation of bridges. Hydrogen transfer reactions consume some of the olefins thereby increasing the
stability and yield of the gasoline produced i.e. they reduce the tendency of olefin rich gasoline to
overcrack. But hydrogen transfer reactions also have certain negative aspects like lower octane number of
the gasoline produced and higher amounts of LCO in the products from the FCC unit.
If the feed to the FCC unit contains metal poisons like nickel or vanadium they tend to promote
dehydrogenation reactions as well. This leads to the formation of compounds with increasing carbon to
hydrogen ratio which in turn leads to coke formation and deactivation of the catalyst. Unsaturated species
like olefins, di-olefins and polycondensed aromatic compounds are very reactive and they ultimately
polymerize to form coke. The amount of coke formed is crucial to the operation of the FCC unit as during
the regeneration step it is the combustion of this coke that produces the heat necessary to vaporize the feed
and allow the endothermic cracking reactions to be carried out. The riser temperature also has a role to
play in controlling the coke formation. Its optimum value is somewhere between 4500C and 5500C.

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Chapter Seven
Catalyst Management in FCC Units
7.1 Introduction:
The zeolite catalysts used in FCC is the heart of the whole operation. It is therefore necessary to
understand the effects of the catalyst on the actual operation of the unit. Catalyst management basically
involves recovery of the catalyst and minimizing losses, replacement of the spent catalyst from time to
time, ensuring proper catalyst circulation between the reactor and regenerator and stripping hydrocarbons
from it before regeneration. The importance of these operations is discussed in the following paragraphs.
7.2 Addition of fresh catalyst:
Regeneration of catalyst, no matter how efficient cannot restore its activity to the level of fresh
catalyst. Hence it is imperative to add new catalyst from time to time. It is necessary to maintain proper
activity and selectivity and compensate for catalyst losses due to some inefficiency in the recovery
cyclones. Also the metals deposited on the catalyst cannot be allowed to increase beyond some level for
which some of the catalyst must be withdrawn and replaced by fresh catalyst periodically. This will also
depend on the quality of the feedstock. The amount of catalyst added is equal to the amount lost and
withdrawn. But sometimes low activity catalyst may be provided as replacement in order to prevent
excessive activity which in turn leads to coking. Catalyst replacement is also necessary to ensure that the
particle size distribution in the FCC unit is properly maintained, as the particles tend to be reduced to fines
in the harsh operating conditions of the FCC. Replacement does not always ensure the same levels of
activity as was prevailing before the addition of new catalyst. Generally if the cyclone separators are
working properly about 80% replacement efficiency is obtained.
7.3 Spent catalyst stripping:
Before the catalyst enters the regenerator it must be freed of the hydrocarbons remaining on it.
Generally steam is used as the stripping agent. The optimum steam rate is governed by the mechanical
design of the riser, the catalyst circulation rate, the porosity and the surface area of the equilibrium
catalyst. The stripping steam rate is optimized by adjusting it to such a value for which the regeneration
temperature is minimized while maintaining the heat balance. Poor stripping leads to formation of
excessive coke in the subsequent cycles which in turn elevates the regenerator temperature.
7.4 Minimizing catalyst losses:
Catalyst losses occur when there is excessive production of fines due to attrition or when the reactor
or regenerator cyclones are not working properly. The replaced catalysts often have different physical
properties e.g. they may be softer than the older catalyst and thereby they contribute to the losses. To

18
control the losses it is necessary to monitor the performance of the cyclones. The size distribution of the
equilibrium catalyst as well as the fines needs to be considered. The typical size distribution of the catalyst
is shown in Figure 4. While smaller particles lead to easy fluidization, the requirements for preventing
excessive catalyst losses are quite the opposite. Hence there are optimum size ranges for the catalyst
particles. The cyclone performance can be affected if it has suffered some kind of mechanical damage like
the development of perforations in the diplegs or erosion of the internal lining. Sudden surges in the
vapour rates in the reactor unit could lead to entrainment of even smaller particles. Too high or too low
catalyst levels in the disengagement section of the reactor can also lead to the malfunctioning of the
cyclones, thereby leading to catalyst losses.

Figure 4: Particle size distributions of equilibrium FCC catalyst


(Source: Albemarle FCC Manual-The Role of Catalyst in FCC Troubleshooting)

7.5 Preventing Excessive Coking Tendencies:


Coke formation is an important part of the FCC operation and the heat balance depends on the
exothermic reactions involving the combustion of the coke in the regenerator. But excessive coking
diminishes catalyst life and in general affects the working of the unit drastically. Coking tendencies
depend on the nature of the feed especially its metal content. To minimize these problems it is necessary
to avoid having cold spots in the system, minimizing of heat losses from the transfer lines connecting the
reactor and regenerator and improvement of the feed-catalyst mixing system by introducing high
efficiency feed nozzles.

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Chapter Eight
Recent Developments in FCC Catalyst Technology
8.1 Introduction:
As the demand for gasoline increases worldwide, the importance of FCC as the main fuel upgradation
technique will also continue to rise. Hence a lot of research work is being carried out round the world to
gain a fundamental understanding of the action of the FCC catalysts on the cracking reactions and then
synthesizing newer and improved catalysts for this process. In this section an attempt is made to describe
some of the recent work done in the field of FCC catalysts and their importance.
8.2 Demetallization Procedures:
Most of the crude being processed in refineries round the world now is heavy crude which has a high
concentration of metals like nickel, vanadium, iron, chromium, cadmium, barium etc. These elements tend
to poison the acid sites on the catalyst and thereby they lead to catalyst loss. To remove these metals from
the catalyst, pyrometallurgical and hydrometallurgical techniques are used. Recent developments in this
field have lead to more efficient techniques of demetallization. Upto 67% of the lost activity is reportedly
regained after these new demetallization techniques [4]. Effective demetallization reduces the requirement
for fresh catalyst and thereby leads to savings for the refiners.
8.3 Modelling of FCC Catalyst Pore Structures:
Designing newer and more effective FCC catalysts needs a model of the structure of the FCC
catalysts. There have been several attempts at visualizing the porous structure of the zeolites. The simplest
assumption says that the zeolite pores are uniformly distributed among the pores of the support, as
depicted in Fig. 5. But electron microscopic studies indicate that the pores form a highly entangled,
interconnected network and it is modeled as a stochastic network. This is shown in Fig. 6.

Figure 5: Simple parallel bundle model for a supported zeolite catalyst.


(Source: R Mann, Catalysis Today, 18 (1993) pg. 516)

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Figure 6: A 10 x 10 x 10 3-dimensional stochastic pore network model in an FCC catalyst
(Source: R Mann, Catalysis Today, 18 (1993) pg. 518)

These stochastic pore models can be used for the study of reaction and diffusion effects and they have
been used in the study of coking phenomena also, with the coking on the catalyst and coking on the
support being analyzed separately. Validation of these pore models can be done by the pressurized
penetration of a low melting allow into the actual catalyst sample and then allowing it to solidify,
thereby providing a measure of the volume available.
8.4 Advanced Kinetic Models:
The reactions taking place in an FCC unit are quite complex. To understand the role of the FCC
catalysts on the various reactions of such a complex network, several models have been proposed and
their validity has been checked by comparison with actual product distributions. One such study was
carried out by Hongjun et. al. [8] where the aromatization reactions of FCC gasoline were studied. A
new complex reaction network with nine lumped kinetics models was proposed for the aromatization
reaction of FCC gasoline. In the network, the aromatization reaction species were firstly lumped into n
paraffins, i-paraffins, olefins, aromatics, coke, and some lower hydrocarbons. Three main type reactions
among these lumped components were considered in the aromatization reaction network, such as
paraffin dehydrogenation and cyclization, paraffin isomerization and cracking to low carbon
hydrocarbon. All the reactions were modeled as first order, irreversible reactions and catalyst
deactivation effects were also incorporated. The performances of FCC gasoline and catalyst were
evaluated in a confined fluidized bed reactor with piston flow and its reaction is controlled by the
reaction dynamics and the effect of external diffusion. The various parameters in the material balance
equations were obtained by optimization using the Levenberg-Marquardt technique and the theoretical

21
predictions were found to be close to the actual data obtained from the refineries. The reaction network
is modeled as follows:

Figure 7: A web model of the aromatization reactions in FCC


(Source: Hongjun et. al, Catalysis Communications, 7 (2006) pg. 556)

8.5 Special Catalysts for Short Contact Time Applications:


The modern day FCC units are all designed in such a way that the maximum
cracking reactions take place in the riser section within a very short contact time.
This makes it necessary to develop catalysts for short contact time cracking (~ 1 to
3 seconds) of even the heavier fractions and resids to produce the primary
products and also olefins which are the principle feed stocks for the polymer
industries. Engelhard Corporation has developed and commercialized the NapthaMax™ catalyst
for this purpose. Studies have also been carried out at the research laboratories of Akzo Nobel Catalysts,
Amsterdam. The catalysts have been developed in such a way that they use a patented matrix technology
called Distributed Matrix Structure (DMS) with specially developed PyroChem Plus zeolites to achieve
optimized porosity and high catalytic activity. Typically the active matrix causes pre-cracking of the
heavier feedstocks which then diffuse into the pores of the zeolites to reach the actual catalytic cracking
sites. But in the DMS architecture the zeolites are highly dispersed over the matrix and hence even the
pre-cracking takes place on the zeolite surfaces. This allows for better selectivity of the catalyst and
eliminates the need for a secondary diffusion step to reach the active sites. Excessive coke and dry gas
formation are minimized. Though the overall porosity of the new and the conventional catalysts may be
the same yet their morphologies are quite different. In these proprietary catalysts the pores are located
much more uniformly thereby allowing easy diffusion of the pre-cracked species. These catalysts are
also evaluated in a manner different from the conventional Microactivity test using a fixed bed reactor.

22
A fixed fluid bed unit is used for these tests with which a reasonable simulation of the short contact time
riser reactors can be achieved.

a) b)

Figure 8: SEM images of two kinds of FCC catalysts-(a) DMS Matrix, (b) Conventional Zeolite
(Source: Mc Lean J B and Stockwell D M, NaphthaMaxTM Breakthrough FCC Catalyst
Technology for Short Contact Time Applications, NPRA 2001 Annual Meeting, New Orleans)
The figures above illustrate the differences in the structure of the short contact time catalyst and the
conventional zeolites catalyst.
8.6 Some other Special Purpose FCC Catalysts:
The demand for reformulated gasoline is on the rise worldwide. Octane boosting additives
(oxygenates) like methyl-tertiary-butyl ether (MTBE) or TAME are synthesized using iso-olefins
(isobutylene and iso-amylene respectively) and the main source of these hydrocarbons is the FCC unit of
a refinery. Catalyst manufacturers like Engelhard Corporation has come up with special varieties of
catalyst to maximize the production of specific hydrocarbons like the iso-olefins through the use of
proprietary catalyst formulations like IsoPlus™ catalyst. It is claimed that more than 50 % increase in
the yield of iso-olefins have been obtained by using these catalysts over that from conventional catalysts.

Figure 9: Relative Increase in the yield of Iso-butylene with the use of IsoPlus catalysts in FCC

23
(Source: Mc Lean J B and Witoshkin A, Isoolefins for Oxygenate Production using IsoPlus™ , NPRA
1993 Annual Meeting, Texas )

Chapter Nine
Conclusion
FCC technology is the most important gasoline upgradation technology that refiners round the world
have at their disposal and they are continually seeking to improve the performance of these units by
incorporating newer and better catalyst formulations in their operations along with modifications in the
process design. A large variety of catalyst formulations are available from Engelhard Corporation (now
BASF), UOP, Akzo Nobel, Lummus etc to suit specific purposes like coke and gas yield minimization,
enhanced production of olefins or rise in the octane number of the gasoline produced. Though it appears
that none of these new catalysts have had as dramatic an impact on the economics of the petroleum
refineries in general and the FCC process in particular as had happened with the introduction of zeolites
as the hydrocarbon cracking catalysts, yet each of the new variety of catalyst has enhanced the
profitability of the refining operations to some extent. Further developments in this field are possible.
As environmental regulations become more and more stringent the emission of SO x, NOx and CO
along with the FCC regenerator flue gases also needs to be controlled. This has given a boost to the
development of FCC co-catalysts and catalyst additives.
Various new procedures of catalyst synthesis have also developed and sometimes minor changes in
the processing methodology can yield catalysts with very different properties and hence final product
distribution is influenced by this factor as well. Catalyst properties are continually improving with
greater silica-to-alumina ratio in the zeolites and better control over the distribution of the acidity and
crystallinity. There has been increased emphasis on the development of FCC catalysts for resids
upgradation and bottoms product cracking without too much of the problem of catalyst fouling. The use
of additives like ZSM-5 is expected to increase steadily because of their inherent ability to crack or
isomerize low octane straight chain paraffins, even more so after the patent on this additive expires. In
brief customized FCC catalysts will continue to be developed to meet the various requirements of
refiners.
Catalyst evaluation techniques also need to be modified and several improved versions of the
conventional Microactivity test are already in place. While MAT used a fixed bed pilot plant reactor,
these newer tests evaluate the equilibrium FCC catalysts in fluidized or partially fluidized beds which

24
produce more realistic results. The modeling of cracking reactions and theoretical prediction of catalyst
behaviour is also an area of active research now.
FCC catalysts have witnessed a long history of progress and the trend will hopefully continue in the
future as well.

References
[1] Fluid Catalytic Cracking Handbook, Reza Sadeghbeigi, 2nd Edition, Gulf Publishing Company,
Houston, Texas, 2000
[2] Basic Principles in Applied Catalysis (edited by M Baerns), Springer-Verlag, 2004
[3] Octane enhancing Zeolite FCC Catalysts (Scientific and Technical Aspects), Julius Scherzer, Marcel
Dekker.Inc, New York and Basel, 1990
[4] Fluid Cracking Catalysts (edited by Mario L. Occelli and Paul O’Connor), Marcel Dekker .Inc, New
York, 1998
[5] Matrix Effects in Catalytic Cracking, Lance D. Silverman et.al, Engelhard Corporation, Edison, New
Jersey, paper presented at the 1986 NPRA Annual Meeting at Los Angeles, California
[6] Passamonti et. al., Catalysis Today, 133–135 (2008) 314–318
[7] Mann R, Catalysis Today, 18 (1993) 509-528
[8] Hongjun et. al. Catalysis Communications, 7 (2006) 554–558
[9] Mc Lean J B and Stockwell D M, NaphthaMaxTM Breakthrough FCC Catalyst Technology For Short
Contact Time Applications, NPRA 2001 Annual Meeting, New Orleans
[10] Mc Lean J B and Witoshkin A, Isoolefins for Oxygenate Production using IsoPlus™ , NPRA 1993
Annual Meeting, Texas
[11] www.himfr.com
[12] www.wikipedia.org
[13] www.3dchem.com
[14] www.catalysts.basf.com
[15] www.thefccnetwork.com

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