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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 . 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 . 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.
The porous structure of the zeolites enables them to accommodate a large variety of cations like Na+. 2. with 8oA being a typical value and reversibly adsorbed water .Chapter Two Typical Components of FCC Catalysts 2. Its basic units consist of silica and alumina tetrahedra. These positive ions are rather loosely held and can readily be exchanged for others especially H+ ions in a contact solution. FCC units are almost exclusively using these catalysts. Zeolites are crystalline alumino. For a given zeolite.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.silicates with a negatively charged macromolecular inorganic framework.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. The general formula used to represent the zeolites is as follows: 2. Along with it they are also synthesized by a variety of techniques as discussed in this report. These are briefly described below: .2. most notably in the petroleum and petrochemical sectors.3 Features of Zeolites suitable for catalysis There are several reasons why zeolites have become the preferred catalyst for many reactions of industrial importance. They are mined in several parts of the world for commercial purposes. etc. This is an important property which is exploited while designing catalysts. The pore diameters can vary over some limits in the different types of zeolites. 2. Ca+. Zeolites have a very well defined lattice structure.2 Zeolites The active catalytic ingredients in the FCC catalysts arez eolites. of course the pore sizes are very nearly uniform. Each tetrahedron consists of a silicon or aluminum atom at the centre of the tetrahedron with oxygen atom at the 4 corners. Natural zeolites form where volcanic rocks and volcanic ash layers react with alkaline groundwater. The first artificial synthesis was carried out in the 1960s and ever since then they have been applied extensively as industrial catalysts. The framework of the zeolites contains freely mobile and exchangeable cations and reversibly adsorbed water. The internal surface area is of the order of 600 m2/gm or even more. They are micro porous and hence are extensively used as commercial adsorbents.2.
The negatively charged aluminum atoms are sources of active sites in the zeolite . Thus they are the most suitable for a reaction scheme like fluid catalytic cracking where high temperatures and other harsh operating conditions prevail.Silicon atoms do not possess any activity. 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 ). The nature or type of the acid sites 2. The Lewis acid sites are formed upon heating the proton forms above 500oC where cleavage of water from the zeolite surface occurs. measured in Ao  . 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. Most of the zeolites remain unaffected by temperatures as high as 650oC. The strength distribution of the acid sites 4. The structural collapse of the specially prepared high silica zeolites becomes significant only at temperatures as high as 1000oC. The density or concentration of the acid sites 3.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. The maximum density of these acid sites is related to silicon to aluminum ratio in the zeolite. The solid state acidity of zeolites is described by parameters like the following : 1. b) Acidity: Zeolites exhibit much higher acidity than the earlier amorphous silica-alumina catalysts. The location of the acid sites within the zeolite framework 5. 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 . As the density of the aluminum ions increases the acid site density decreases. The acidity of the zeolites is due to the presence of both Bronsted as well as Lewis acid sites. The Bronsted acid sites are generated in the zeolites by ion exchange.
ZSM-5 is a versatile zeolite that helps in increasing the yield of olefins from FCC. 2. Now-a-days as the demand for gasoline of higher and higher octane rating is increasing. In the majority of the FCC catalysts the zeolites is embedded in the matrix. This protects the acid sites and also makes the zeolites hydrothermally stable.4 Zeolites used as FCC catalysts The zeolites typically applied as FCC catalysts are Type X. 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 . These properties can be fine-tuned while synthesizing zeolites and therefore zeolites suitable for very specific purposes can be created.g.the sizes of the molecules participating in the reactions catalyzed by them. This creates a strong influence on the selectivity of such reactions. Types X and Y possess similar crystal structures but the X zeolite has a lower silica-alumina ratio. product shape selectivity and transition state shape selectivity. acid leached clays and synthetic alumina-silica gels. 2. There may be reactant shape selectivity. 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. Very often it does possess sufficient catalytic activity towards some components of the feedstock and in this case they are described by the term µactive matrix¶.3 Matrix The matrix in the FCC catalyst is often considered to be that part of the catalyst other than the zeolites. 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. Type Y and ZSM-5. 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. Usually the matrix consists of substances that were used as FCC catalysts before the development of zeolites e.2. 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. The first two kinds of selectivity are usually based on 8 the mass transfer effects rather than on chemical kinetics while the last category is based on the intrinsic features of a reaction mechanism. It may or may not have catalytic activity. which makes it less stable.
halloysite or montmorillonite. The binder performs the all important function of holding the catalyst. Depending on their catalytic behaviour. The clays provide mechanical stability. B) Allowing diffusion: The matrix with its pore structure allows the diffusion of the required hydrocarbons to the actual catalytic sites for reaction. like kaolinite. C) Diluting medium: This serves to moderate zeolite activity and avoids over-cracking that leads to excessive coke formation and gas production. 9 D) Heat transfer: The matrix functions as the storage of thermal energy in the FCC unit. 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. silicaalumina gels or silica-magnesia gels which serve as the binder and also exhibit catalytic properties. the . The highly active matrices can help in the bottoms upgradation by enabling the cracking of the heaviest components of the residue. The matrix consists of two main components-firstly a synthetic component like amorphous silica. natural or chemically modified. 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 matrices may be classified as low activity.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. The matrix is capable of trapping the metal contaminants and rendering them passive . Sometimes additional fillers like kaolin may be provided for physical integrity and as a more efficient fluidizing medium . medium activity or high activity matrices. 2. 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.particles together in the form of microspheroidal catalyst particles after the spray drying operation. The other component is some clay. It allows heat transfer during cracking and regeneration operations and prevents catalyst damage due to excessive temperatures. 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. 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 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.matrix and the filler glued together. This is especially important when the catalyst contains a higher amount of zeolites. This leads to catalyst losses and causes emission of particulate matter into the environment . Not all of the fines may be recovered by the cyclone separators before the products can be separated. An increase in the zeolite content of the catalyst.3 Pore Size Distribution and Pore Volumes: The pore size distribution has a major role to play in the catalyst properties of zeolites. Kaolin has been found to increase the attrition resistance. then they have a greater tendency to get clogged by coke and they also exhibit greater diffusional resistance. 3. 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 . . As the particle size distribution is affected by this. Catalyst attrition resistance is indicated by the value of the attrition index which is obtained from standard methods. These properties are briefly discussed below: 3. 10 Chapter Three Major Physical Characteristics of FCC Catalysts 3. particle size and the morphology of the clay used as filler has a role to play in the attrition of the catalyst. the conditions of fluidization itself might change. The type. reduction of the zeolite crystal size and better dispersion of the zeolite within the matrix leads to improved attrition resistance.1 Introduction: Several properties of zeolites have to be considered when selecting them as catalysts for FCC. The conditions maintained during spray drying of the catalyst affects its future attrition resistance. The filler and binder minimize the production of catalyst fines in the reactor-regenerator system and help to control the catalyst losses. For example the boehmite form of alumina is more effective in reducing attrition than gibbsite or bayerite. It also governs the rate at which fresh catalyst make-up must be provided to the unit. The nature and quantity of the binder provided to the catalyst also affects the attrition resistance. If the pores are too small.
crystallinity. 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. 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.4 Surface Area: 11 The surface area of the catalyst comes from the zeolite and also the matrix. 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. ion-exchange and residual sodium ions in the zeolite affect its stability.5 Particle Size Distribution: Most of the FCC catalysts have particle size ranging from 60 to 80 m. especially the silica-to-alumina ratio. It ranges from over 800 m2/gm for conventional Y zeolites and is around 600 m2/gm for USY zeolites.7 Crystallinity . Catalysts in which the matrix is also active generally have higher surface areas.6 Thermal and hydrothermal stability The chemical nature of the zeolites. 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. Stable catalysts retain their pore structure during regeneration also. 3.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. Rare earth exchanged zeolites are exceptionally stable. 3. 3. 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. Particulate emission might also result from the fines. Maintaining the catalyst stability is essential to maintaining its activity and selectivity.
(a) Incorporation method in which the catalyst and the matrix are synthesized separately and then mixed with the fillers and binders. The X-ray studies of the fresh catalyst and the equilibrium catalyst can provide information about structural loss and the catalyst stability. 12 Chapter Four Synthesis of FCC Catalysts 4.e. 3. At the heart of this test lies a fixed bed reactor into which the hot gas oil sample is injected.The crystalline nature of the FCC catalysts as determined from X-ray diffraction studies is an indication of the zeolite content. A general description of the processes is presented in the following paragraphs.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 . The catalyst activity is reported as the conversion of the 2210C material. After separating the crystals rare earth exchange of the zeolites may be carried out either before or after its incorporation into the matrix element. alumina and caustic soda for about 10 hours at prescribed temperatures till crystallites start forming. feed space velocity and other factors. and (b) µin-situ¶ processes whereby the zeolite catalytic component is allowed to grow within preformed microspheres of some kaolin type of particles. 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. 4. This test is simple and not much time consuming.1 Introduction: Modern processes used to manufacture FCC catalysts are of two types. It helps in ascertaining the conditions to which the catalyst has been exposed. they have become equilibrium catalysts . 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. firstly NaY zeolite is produced by the digestion of a mixture consisting of silica. REHY or HY.2 Conventional Zeolites: To prepare ordinary catalysts like REY. The conversion depends on the catalyst-to-oil ratio. 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 .
4. The preparation of ZSM-5 is done in a manner similar to that of any general zeolite material. 4. These spheres are then digested with caustic soda or sodium silicate.the matrix. .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. This process was developed by Engelhard. All the components of the catalyst are mixed to form slurry and that is finally spraydried to obtain USY zeolite catalyst. chemical extraction and chemical substitution are also employed to reduce the alumina content of zeolites. Octane boosting catalyst additives like ZSM-5 zeolites are also incorporated within the catalyst matrix before the spray drying operation. 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. Apart from this acid leaching. the active matrix and the filler and binding agents develop simultaneously within the microspheres.3 Ultrastable Zeolites (USY): The preparation of these catalysts is accomplished by replacing some of the aluminum ions in the framework by silicon. The residual alumina precipitated within the pores of the zeolite during the synthesis can affect the catalyst properties significantly. Steam calcination of the zeolite at a temperature of 700-800oC is generally carried out for this purpose. Thus the catalyst.