ChE 415 Advanced Particle Processing

Project - Optimization of FCC unit Addressing the degradation of catalyst via attrition

Project Group 1 Catherine Ferrari Jacob Bennetts Jessica Stallard Mitchell Buzza 14868014 13955342 14283772 14286001 25% 25% 25% 25%

Executive Summary
Fluidised Catalytic Cracking (FCC) is a method of crude oil separation that aims to convert low value gas-oil feed to marketable products such as gasoline, LPG, and diesel (Ravichander et al. 2009, 115). The process was developed from thermal cracking via the addition of a catalyst. The catalyst aids in the cracking process by enabling the long hydrocarbon chains present in the feed to break at lower temperatures, reducing operation costs, increasing the purity of the obtained light hydrocarbon products, and increasing the flexibility of the process.

The main components of a typical FCC plant are the riser, where the catalyst is contacted with the feed oil to facilitate the cracking reactions. During the adsorption process, an undesired side reaction that produces a solid carbon residue occurs, which works to deactivate the catalyst by blocking the pores and active sites. Therefore, the regeneration step is implemented to treat the catalyst and remove such impurities, restoring majority of the reactivity so the catalyst may be recirculated and reused.

Though overall the FCC process is very efficient in terms of economics and purity of products, due to the inherent complexity, many problems exist in the system. The main four problems acknowledged are: 1. Catalyst attrition the gradual degradation of catalyst particles into fines. 2. Catalyst deactivation the reduction of catalyst activity via poisoning, coking, or sintering. 3. Excessive catalyst loss Reduction in amount of catalyst present in the system due to many operational and compositional issues. 4. Catalyst circulation Issues associated with the changing of catalyst rotation due to pressure differences and other system fluctuations. Attrition was chosen as the problem in which was to be solved as it posed very substantial benefits in diverse areas of plant operation and management if it were to be resolved. In order to begin this process, a particle characterization of the process was performed, analysing the effect attrition has on five major particle characteristics; morphology, structure and composition, interfacial relationship, physico-chemical, and transport/storage. This analysis is the starting point for the development of an improvement to the FCC process that will aim to minimise or alleviate the effects of attrition.

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Table of Contents
Executive Summary .......................................................................................................................... ii 1.0 2.0 3.0
3.1 3.2 3.3 3.4

Importance of FCC Unit ..................................................................................................... 1 Process Description .............................................................................................................. 3 Problems Related to FCC ................................................................................................... 5
Catalyst Attrition ......................................................................................................................... 5 Catalyst Deactivation ................................................................................................................. 6 Excessive Catalyst Loss .............................................................................................................. 7 Catalyst Circulation..................................................................................................................... 8

4.0 5.0

Chosen Problem.................................................................................................................. 10 Particle Analysis ................................................................................................................. 11

5.1 Morphological .............................................................................................................................11 5.1.1 Size of Catalyst ...................................................................................................................................... 11 5.1.2 Shape of Catalyst................................................................................................................................... 12 5.2 Structural and Compositional ...............................................................................................14 5.3 Interfacial .....................................................................................................................................15 5.3.1 Catalyst Hydrocarbon Interface .................................................................................................... 15 5.3.2 Catalyst Catalyst Interface .............................................................................................................. 17 5.4 Physico-chemical .......................................................................................................................17 5.5 Transport and Storage.............................................................................................................20

6.0 7.0

Conclusion............................................................................................................................ 22 References ............................................................................................................................ 23

1.0

Importance of FCC Unit

Fluid Catalytic Cracking (FCC) is the most abundant hydrocarbon separation method in the petroleum refining industry (Veluswamy et al 2012, 4660). Over the last decades, the development of procedures and equipment has elevated this operation to be the most effective method for hydrocarbon separation. The FCC unit consists of two distinct units that perform two very different operations. The cracking process occurs in the riser, where the oil is contacted with a catalyst, often at elevated temperatures, to vaporize the liquid allowing for separation of the light hydrocarbons (Pandimadevi, Indumathi and Selvakumar 2010, 876). After this process, the catalyst contains valuable hydrocarbon residue, which was adsorped onto the surface in the riser, and this needs to be removed from the catalyst surface so it can be reused. This is done in the regenerator, via steam or other means.

Originally, the separation of crude oil was performed by a thermal cracking procedure, which induced the heavy oil split by the application of heat alone. This required very high temperatures and pressures, which resulted in high levels of equipment damage due to excess stress and corrosion (Decroocq 1984, 4). The efficiency of the process was very low also, producing 35% yield of low rated gasoline, which couldnt be used in many conventional engines (Decroocq 1984, 5). This led to the introduction of a homogeneous catalyst, in particular aluminium chloride, into the cracking process to enhance the separation, and produce high-octane gasoline products. Though this reduced the operating cost associated with temperature and pressure levels, the catalyst consumption and price was very high, which outweighed the benefit (Decroocq 1984, 5). Research was then developed in the area of heterogeneous catalysts, which revolutionised the FCC process used today. It improved the gasoline purity and production levels, which overall increased the capital productivity of the refining process (Sadeghbeigi 2012, 169).

The FCC process is also considered to be a flexible operation, as it allows for the modification of a variety of process parameters to control the conversions of oil to its different products. Depending on a variety of conditions, the heavy crude oil can be split to produce high quantities of certain hydrocarbons as opposed to others, depending on the market demand. This is very important for the refining sector as the market conditions are

constantly changing, altering the supply and demand for certain products (Sadeghbeigi 2012, 169). In particular, gasoline and LPG were the original desired products, though diesel has now emerged as a product in demand. Such parameters as catalyst types and combinations, contact time, and operating temperatures and pressures can be adjusted accordingly to maximise the production of any number of products.

Overall, the FCC process is an integral part of the majority of petroleum refineries. Its capability to reduce the capital outlay that was originally involved in the separation of crude oil has improved the industry profitability significantly. Equally as important, the grade of the products produced via FCC are unparalleled by any other separation process available, improving overall efficiency and usability of the natural resources. Lastly, the flexibility of the overall process to mould to the changing market allows FCC to remain current and updated.

2.0

Process Description

Figure 1: Schematic of a Fluidised Catalytic Cracker (SET Laboratories Inc., 2008)

In a society that is so dependent on petrol and diesel, the straight-run products from the distillation of crude oil are not adequate. Therefore, it is with the implementation of additional process equipment such as a Fluid Catalytic Cracker (FCC) that more value can be taken from crude oil.

The FCC is responsible for converting the heavy, low-end products from crude oil distillation into petrol and diesel, by cracking long hydrocarbon chains into shorter chains by means of a catalyst. The shorter hydrocarbon chains such as diesel and petrol give far more economic return, particularly in Australia where the demand for these products is high. This is done by first injecting the feed into the riser of the reactor, as shown in Figure 1, where the fuel immediately vaporises upon entry and then comes in contact with the catalyst and the reactions occur. The temperature at which this occurs determines how long the fuel is in contact with the catalyst, which also determines how much cracking takes place. The amount of cracking affects the products of the reaction; more cracking produces lighter products like LPG and less cracking produces heavier products like petrol and diesel. Generally, the optimum temperature for the riser is 500-550C, as this is a good balance between controlled thermo-cracking and catalytic cracking (Montgomery 2013). Thermo-cracking occurs at higher temperatures and is generally an unwanted side effect of the process as it is far less

controlled and can produce short-chained hydrocarbons, which is essentially LPG and is far less profitable than producing longer-chained hydrocarbons such as diesel or petrol (Montgomery 2013).

Once the reactions have taken place, the hydrocarbon product is separated from the catalyst by a series of two cyclones in the separation vessel, as shown in Figure 1. The hydrocarbon travels up the cyclone and out into the fractionation unit for separation into diesel, petrol and into a gas recovery unit for separation into propane, butane and LPG. The spent catalyst travels down the cyclone, into a stripper where entrained hydrocarbons in the pores of the catalyst are removed, and then moves into the catalyst regenerator (Sadegheigi 2012, 17). While the reactions take place between the feed and the catalyst, coke, a solid carbon residue, is formed on the catalyst, which works to deactivate the catalyst. Catalyst deactivation will ultimately reduce the efficiency of the process. The catalyst regenerator works by burning off the coke on the catalyst by using air at approximately 650-800C. From this, a flue gas is produced which is then sent to a carbon monoxide burner (Sadeghbeigi 2012, 20). The regenerated catalyst then flows down a standpipe, which produces enough pressure head to circulate the catalyst around the unit, creating a pressure balance within the FCC process. This enables the catalyst to come into contact with fresh feed and the process repeats itself (Sadegheigi 2012, 26). The heat generated by regenerating the catalyst is sufficient to vaporise the feed on entry to the riser and even compensates for the endothermic reaction of cracking the hydrocarbons. Therefore, no external heat sources such as furnaces are required, which creates a complete heat balance within the FCC process (Sadegheigi 2012, 26).

3.0

Problems Related to FCC

3.1

Catalyst Attrition

In the FCC unit catalyst particles can be exposed to vigorous turbulent motion, especially in the regenerator where they are exposed to high velocity air jets (Sun and Grace 1992, 716). These particles will be exposed to mechanical stresses due to inter-particle collisions and wall-to-particle impacts. This mechanical stress leads to a gradual degradation of individual particles, which is termed attrition. Attrition can also further be described to include particle abrasion and fragmentation (Yang 2003, 203). More specifically, abrasion is the wearing away of a particle, producing extremely fine material whereas fragmentation refers more to particles splitting to form more particles of relatively similar size.

According to Boerefijn, Gudde, and Ghadiri (2000, 147), catalysts used in the FCC process are generally produced in the form of fine powders with particle sizes below 180m. Catalyst particles used in FCC units commonly experience attrition due to the high circulation rates that the particles experience. Attrition creates unwanted fines circulating in the system, however most FCC units have a method for fines recovery, such as multi-stage cyclones and electrostatic precipitators. An increase in catalyst fines places an additional burden on the recovery systems, which may result in and need to upsize the existing equipment, thus increasing capital costs (Yang 2003, 217).

The fine catalyst particles are undesirable due to the fact that if they are not recovered they can be lost to the environment with the flue gas leaving as the top product of the catalyst separation cyclones. This loss is often counteracted by the addition of fresh catalyst throughout the process, which results in increases operational costs. The loss of catalyst fines will lead to the deterioration of the fluidization properties of the E-Cat (equilibrium catalyst), as the average particle size increases slightly in the system. How well the particles fluidize in the regenerator is very important as it can affect the amount of coke removed and thus the regenerated catalyst activity. Fluidization of particles in the riser and reactor are also very important as it can effect yield and conversion. Albermarle, one of the worlds major FCC catalyst producers, explains that there are a number of factors that improve fluidization which are as follows (FCC Manual 5.4 2013): 5

 Low mean particle size Low particle density High fines content High density / viscosity of fluidizing gas If attrition is causing an increase in fine particles which are then being lost because the system cannot retain them fluidisation will deteriorate. On the other hand if all the fines generated by attrition are retained then mean particle size may be too low and fines content may be too high causing a disruption in the fluidisation properties.

Boerefijn, Gudde, and Ghadiri (2000, 147) suggest that the main area where attrition of catalyst occurs is in the cyclones, due to high velocity impacts with the walls of the cyclone, in conjunction with particle-particle collisions in the regenerator caused by high air jet velocities. Other problem areas for attrition in the FCC process include the riser terminating device and the transport lines between reactor and the regenerator. Furthermore, the attrition levels will also depend on the hardness of internal equipment walls that the particles collide with.

3.2

Catalyst Deactivation

Activity of the catalyst in the FCC units is a critical property since high catalyst activity will result in high yield. Fresh catalyst continuously undergoes deactivation once it is introduced into the riser of a FCC unit. As fresh catalyst deactivates, yield and conversion decrease, along with a reduction in the surface area of the catalyst particles (Ravichander et al. 2009, 115).

Catalyst particles can deactivate in a number of different ways in FCC units, by both physical and chemical mechanisms. These can be divided into three main categories, namely poisoning, coking or fouling, and sintering. Poisoning can reduce the activity of the catalyst through strong chemisorption of impurities in the feed onto catalysts active sites. This adsorption can block an active site geometrically, alter the absorptivity of the other species by an electronic effect, or chemically change the nature of the active sites, all of which will reduce the catalysts activity. Coking or fouling in the FCC unit refers to side reactions that occur on the catalyst surface which lead to the formation of carbonaceous residues that can

physically cover the active surfaces. These deposits known as coke can be as large as 20% (w/w) on the catalyst, which will dramatically reduce its activity by covering the active sites or blocking the pores (Forzatti and Luca 1999, 168). Sintering of the catalyst refers to where the hydrothermal stress placed on the particles causes their matrix structure to become disrupted to a degree where aluminium atoms are lost from the zeolite framework, which results in a surface area decrease. Thus, sintering reduces the active surface area of the catalyst, which reduces its overall activity (Cheng, Bryden and Orlicki 2008, 1). Furthermore, Forzatti and Luca (1999, 165) state other mechanisms of deactivation include masking and loss of the active elements via volatilization, erosion and attrition.

3.3

Excessive Catalyst Loss

Excessive catalyst loss is a major problem in fluid catalytic cracking as it will not only result in an increased cost of catalyst, but will also result in a detrimental impact on plant production as a whole with the introduction of catalyst particles into the heavy product stream. There will also be the potential for increased environmental impact caused by particulate material escaping to the atmosphere (Sadeghbeigi 2000, 244).

Causes of catalyst loss from the system can be simplified into four basic overlying categories. These categories are; changes in catalyst properties, operating conditions problems or changes, mechanical problems, and changes in operating practice (Sadeghbeigi 2000, 246). Changes in catalyst properties are generally caused by changing the type of catalyst used or by getting in new catalyst stock that has severely different physical properties from previous stocks. Operating condition problems or changes include higher levels of fresh catalyst addition, changes in catalyst flows in either the reactor or regenerator side of the system, cyclone pressure issues, cyclone flooding, and coking or plugging of cyclone diplegs (this can cause flooding). Mechanical problems include cyclone malfunctions, such as holes in cyclones, diplegs or cyclone outlet tubes, reduction of fines losses from one section by a newly added filter and check valves not opening (Niccum 2010, 34-37).

Attrition is one of the most major causes of catalyst loss from FCC units; it is quite a complex process, which is discussed as a separate problem. Greater attrition problems than

usual are usually caused by either a change in catalyst properties, a change in operating conditions, or a combination of both.

The overall consequences of excessive or unusual levels of catalyst lost from an FCC unit include contamination of the heavy product stream, an increase in particulate emissions, an earlier failure of the flue gas regeneration turbines, and an increase in the demand for fresh catalyst. Contamination of the heavy product stream by catalyst is a problem due to the increased cost of separating the catalyst from that stream further in the process, potential lower product value if the contaminant cannot be effectively separated, increased wear of the heavy product transport lines and pumps, and catalyst build up in the heavy product storage tanks. An increase in particulate emissions can be a problem in terms of violating particulate level emission legislation, as well as being a health risk to process operators. Premature failure of flue gas regeneration turbines is a problem as they are expensive pieces of equipment, and any down time on a regeneration turbine will mean an increase in energy costs for the down time period. Catalyst build up in the heavy product tank, or anywhere in the system, can potentially mean that the process needs to be shut down whilst the build-up is cleaned from the system (Niccum 2010, 29-34).

3.4

Catalyst Circulation

Correctly controlling the circulation of the catalyst in the FCC unit is essential to achieving the required conversion of reactants to products. In general there are two main situations that are best to avoid with catalyst circulation, these are limited circulation, and fluctuating circulation.

Limited circulation can be caused by a mechanical fault, such as a problem with the slide valve, or by low pressure on the regenerator side of the regenerator standpipe slide valve, or high pressure on the catalyst riser side of the regenerator standpipe slide valve. Low pressure on the regenerator side of the regenerator standpipe valve can be caused by plugging of the standpipe, or by incorrect standpipe catalyst density due to problems with the catalyst aeration inside the standpipe. High pressure on the catalyst riser side of the regenerator standpipe valve can be caused by a high vapour velocity or low/no fluidisation in the bottom of the riser. Fluctuating circulation can be caused by fluctuating catalyst properties, incorrect rate of aeration, incorrect orientation or mechanical design of aeration equipment, or by a

partially or fully blocked regenerator standpipe by non-stream material (broken metal or unit lining) (Sadeghbeigi 2000, 246).

The main consequence of limited circulation is that the conversion of the feed is limited, which decreases profits. Fluctuating circulation can cause high levels of vibration within the equipment, inconsistent product purity and loss of catalyst.

4.0

Chosen Problem

It is hard to specifically identify what is the most problematic issue in the FCC process relating to particle processes, as each specific setup of an FCC unit will have its own weaknesses. Though, catalyst attrition is a problem that all units face from the moment the particles are injected into the system, to when they are removed or lost. The attainment of a catalyst feed requires a large capital outlay for any industrial company running a FCC unit, and wastage or inefficient utilization of catalyst can result in large-scale economic losses. Attrition can cause catalyst particles to be ground to the extent that they are not able to be recovered or regenerated, requiring fresh catalyst feed to be injected to maintain an appropriate level of activity. Attrition can also affect the fluidization balance of the unit through changes to the particle size distribution, which effects catalyst activity, proving to be another source of economic loss for the company. As well as these problems, catalyst attrition can trigger many other problems within the process, such as erosion of equipment. This being the case, if a company can prevent or minimize the effects of attrition, the cumulative economic benefit can be substantial.

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5.0

Particle Analysis
5.1 Morphological 5.1.1 Size of Catalyst

As mentioned in Section 3.1, FCC catalyst particles typically have size range of between 0 and 180m. The size of the catalyst particles can be an important factor with respect to what type and amount of attrition that occurs. The attrition of catalyst particles generally takes two forms, being either fragmentation or abrasion. Increased particle collision or impact force will increase the probability of particle fragmentation over abrasion. Studies have shown that most attrition in fluidized beds is due to abrasion, where a mother particle is disintegrated into two parts: the fines and a single son particle, which is only slightly smaller than the mother particle. Therefore, the amount of fines produced is a direct indication of the degree of attrition (Ray, Jiang and Wen 1987, 194). The different modes of attrition and the effects on particle size distribution can be seen below in Figure 2:

Figure 2: Attrition modes and their effect on the particle size distribution (q 3=mass density distribution of particle sizes dp) (Yang 2003, 203)

Figure 2 above shows how abrasion changes the particle size distribution so that the mean particle size is similar but there is a greater amount of fines in the system. Fragmentation on the other hand shifts the mean particle size so it reduces, but there are also less fines produced.

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It should also be noted that there is a difference in how much attrition occurs on the fresh catalyst (F-cat) compared to the catalyst particles at equilibrium, which are typically smaller in size. In Figure 3 below, Boerefijn, Gudde, and Ghadiri (2000, 157) used these trends obtained experimentally to display how the fractional particle mass of F-cat and E-cat particles lost from attrition was greater with increased particle size and velocity.

Figure 3: Attrition of F-cat and E-cat respectively as a function of particle size. () 14.7m/s; (o) 23.4m/s; ()33.1 m/s; ([]) 40.5 m/s (Boerefijin, Gudde, and Ghadiri 2000, 157)

Comparing both graphs, however, shows that the fractional particle mass lost from E-cat is about 100% less than that of the F-cat particles.

In a FCC unit, the catalyst particle size distribution (PSD) is a good indicator of the fluidization characteristics of the catalyst, cyclone performance, and the attrition resistance of the catalyst (Sadeghbeigi 2012, 99). It should be noted that a drop in fines content indicates the loss of cyclone efficiency. This can be confirmed by the particle size of fines collected downstream of the cyclones. An increase in fines content of the E-cat indicates increased catalyst attrition (Sadeghbeigi 2012, 106).

Smaller particles tend to contain fewer faults in the form of micro cracks or imperfections, which make them more difficult to break than larger particles (Yang 2003, 204). 5.1.2 Shape of Catalyst

Shape is an important parameter as most fresh catalyst particles that are introduced into the system have an irregular shape, and are therefore not perfectly spherical. These particles

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usually have their corners or rough surfaces smoothed in the event of continuous collisions, and are worn down to smaller, more rounded particles. Particle surfaces that are smooth on a macroscopic level are less likely to endure breakages (Yang 2003, 205). However, any ruggedness present on the particle surface at a microscopic level may still lead to abrasion. The images in Figure 4 below display how the shape of fresh catalyst and equilibrium catalyst differ, with respect to the roundness.

Figure 4: SEM images of an equilibrium catalyst and the corresponding fresh material (Yang 2003, 206)

With equilibrium catalyst particles having less ruggedness and irregular shapes they are significantly more attrition resistant than the freshly fed catalyst particles.

Yang (2003, 205) references an experiment by Reppenhagen and Werther, where two types of catalyst particles were compared, with identical chemical compositions and similar mean particle diameters, but the surface structure and particle shape was different. The images of these two catalysts can be seen in Figure 5 below.

Figure 5: SEM images of two catalyst materials. The surface mean diameter was 112 microns in the case of "97-R(fresh)" and 103 microns in the case of "97-G(fresh)" (Yang 2003, 205)

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The result of this experiment was that the more irregular shaped catalyst, 97-G(fresh), experienced twice as much attrition as the smoother more round catalyst, 97-R(fresh). This shows that the shape of the catalyst particle that one chooses to use can heavily impact attrition levels.

5.2

Structural and Compositional

Attrition of the catalyst in a FCC process generally leads to the production of fines as a result of the high circulation rate of the catalyst throughout the system, surface burrs, cracks and shells formed during production, or as a result of the age of the catalyst (Boerfijn, Gudde and Ghadin 2000, 145). A typical FCC catalyst has a diameter of about 75m and has four components: zeolite, matrix, filler and binder (Sadegheigi 2012, 87).

The zeolite component of the catalyst determines the selectivity and provides most of the catalytic activity, though the active matrix contributes also. Zeolite is a tetrahedral lattice structure, with a silicon or aluminium atom at the centre of the tetrahedron, and an oxygen atom on each of the four corners, as shown in Figure 6 below (Sadegheigi 2012, 88). The pores on the zeolite lattice are relatively small and generally only admit hydrocarbon molecules with a diameter of >8.0-10.0 (Sadegheigi 2012, 88). The zeolite must also be suitable to maintain its catalytic properties under the harsh temperature and pressure conditions present in the FCC process. Zeolites are manufactured with sodium hydroxide to balance out the negative charge of the aluminium present, which in turn leaves behind acid pore sites that are ultimately responsible for the activity of the catalyst (Sadegheigi 2012, 89). Unfortunately, sodium is a soft ingredient, so if more of it is present on the catalyst, the ability of the catalyst to resist attrition is reduced (Rawlence and Gosling 1988, 220).

The matrix of the catalyst generally refers to the components in the catalyst other than zeolite, whereas the active matrix, such as alumina, refers to the components of the catalyst other than zeolite that have catalytic properties. As the zeolite is relatively small, the active matrix of the catalyst is able to break the larger hydrocarbon chains. The filler of the catalyst is added to dilute the activity of the catalyst and the binder acts to hold the zeolite, matrix and filler together. The binder and filler provide physical integrity to the catalyst and contribute to attrition resistance as a result of this (Sadegheigi 2012, 96).

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Figure 6: Structure of Zeolite (Sadegheigi 2012, 88)

There are two main mechanisms of the attrition of catalyst particles: abrasive removal of the outer crystallite layers and disintegration of the matrix (Boerfijn, Gudde and Ghadin 2000, 147). The removal of the crystallite layer typically results in a larger particle that is significantly smaller than the original particle and many very fine particles, which can be controlled by the hardness of the crystallites (Welt, Lee and Krambeck 1977, 1211). The matrix disintegration generally results in a varying range of particles and can be controlled by the impact elasticity of the matrix and the reduction of imperfections in the structure (Welt, Lee and Krambeck 1977, 1211). It has been found that the size of the catalyst particles can greatly influence the rate of attrition in that the larger the particle, the greater the attrition (Welt, Lee and Krambeck 1977, 1211). Therefore, it could be reasonable to say that a compromise needs to be found between the catalyst size in terms of the surface area available and the size in terms of ensuring the smallest possible amount of attrition occurs. Attrition rate can be reduced by increasing the strength of the internal matrix, as this will ensure that impact is spread throughout the entire particle as opposed to being concentrated on the surface, as in the case of forming a shell around the catalyst particle, which would dramatically increase the amount of attrition by the mechanism of removal of outer crystallite layers (Welt, Lee and Krambeck 1977, 1218).

5.3

Interfacial 5.3.1 Catalyst Hydrocarbon Interface

The interfacial properties of a catalyst represent the way a particle will react with its surroundings (Darmawan 2013). The surface of the catalyst particle represents the area of

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contact present between the solid catalyst and the hydrocarbons in either liquid or vapour phase. As described in previous sections, the oil stream is combined with a heated catalyst flow to induce vaporisation of the hydrocarbons, facilitating the cracking of the long-chain hydrocarbons into smaller, more valuable products (Huq 1998, 13). This process consists of two major parts; the primary cracking of crude oil molecules, and the secondary recracking and rearrangement of the primary products (Sadeghbeigi 2012, 128). Both steps contain complex reactions as a result of adsorption of the hydrocarbons onto the active sites of the catalyst.

The surface structure of a catalyst is imperative in evaluating the overall reactivity. The most effective catalyst present in the industry is a zeolite catalyst, which has a unique structure. The catalyst is composed of the zeolite, a matrix, and often a filler, where the zeolite and matrix affect the overall performance of the FCC catalyst (Sadeghbeigi 2012, 95). The zeolite has an extensive pore structure of small openings that run perpendicular to each other (Tonetto, Atias and de Lasa 2004, 9). The average diameter of the pores is 8 angstroms ( , with an internal surface area of 600 m2/g (Sadeghbeigi 2012, 88). The locations where the hydrocarbon chain can react with the catalyst, known as active sites, are found on both the matrix and zeolite, with majority residing in the zeolite pores (Tonetto, Atias and de Lasa 2004, 9). These sites are identified as either Brnsted or Lewis acid sites. A Brnsted catalyst site has the ability to donate a proton to the hydrocarbon chain, whereas a Lewis site accepts a pair of electrons (Sadeghbeigi 2012, 129). This enables the formation of carbocations when the long-chain hydrocarbons contact the catalyst, beginning the cracking process. The purpose of the matrix active sites are to facilitate the breaking of the original, long chain hydrocarbons so they are small enough to diffuse into the small zeolite pore (Sadeghbeigi 2012, 95).

When the acidic active sites exchange protons and electrons with olefin or paraffin type hydrocarbons respectively, this facilitates the production of a charged molecule called carbenium. Once this intermediate has formed, three main reactions are made possible; the cracking of the carbon-carbon bond, isomerization, or hydrogen bonding (Sadeghbeigi 2012, 130-131). These are examples of the secondary recracking and rearrangement, where the molecules split, recombine, and alter their structure to form the desired short chain hydrocarbons, consisting in majority of gasoline. Though this is a simple explanation of the

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chemistry of cracking, it is possible to ascertain that the adsorption process relies wholly on the presence of these active sites, and therefore the more active sites present the greater the conversion observed.

When the catalyst particles experience deactivation via attrition, fines are produced that are removed from the bulk particle due to collisions (Boerefijn, Gudde and Ghardiri 2000, 145). The breakages and fines result in a smaller average size distribution of the catalyst in the system, which can result in catalyst loss via separation (Reppenhagen and Werther 2000, 56). This is important in evaluating the effectiveness of the catalytic process because surface area and pore size are directly proportional to the particle size. It can then be inferred that as attrition begins and the particles begin to downsize, the number of available catalyst sites is reduced. This limits the degree of adsorption that can be achieved, as limited acidic site availability may be present. The overall conversion of the process may be reduced as a result, therefore measures must be implemented to manage the mechanical degradation via attrition.

5.3.2

Catalyst Catalyst Interface

The solid-solid interfacial interactions are an integral part of the FCC process, due to the presence of the fluidised bed. The cohesive forces between particles contribute to the degree of catalyst fluidisation achievable (Massimilla and Donsi 1976, 253), along with aiding the propagation of degradation via attrition. These interfacial phenomena must be discussed closely with the particle chemistry of transport via fluidisation.

5.4

Physico-chemical

The chemical activity or reactivity of a catalyst is usually given as a measure of the current activity of the used catalyst comparatively to new catalyst particles. The deactivation of a catalyst can happen in many different ways, however the cause of deactivation is always either the blinding of an active sight by a fouling agent, or the destruction of an active sight. Attrition causes the destruction of active sights both through abrasion and fragmentation. Abrasion decreases the activity of catalyst particles by smoothing their surface from the initially rough state. Catalyst particles are designed to have a high surface area or a rough surface since this increases the amount of active sights which are available per unit volume of catalyst, hence reducing the catalyst volume required. Thus abrasion attrition severely

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decreases the catalyst activity. Fragmentation decreases catalyst activity through reducing the particle size to such a state that the active sights are no longer useable.

Optimising the physical characteristics of catalyst particles is extremely important in minimising attrition in a FCC unit. Each individual particle contains cracks or flaws in the structure of the particle; these flaws are points of weakness. Failure or breaking of a particle along these weak points can be described by the value of:

Once this value becomes too large the particle will fail along that stress point (the flaw). If however the particle reaches its yield strength before the failure value then the particle will not break, but rather continue plastic deformation. Each catalyst particle is slightly different from all others, which means that each particle is flawed in a different way; this adds to the complexity of preventing particle attrition (Bemrose and Bridgewater 1987, 102-103). The failure value presents the importance of particle size in attrition. With decreasing particle size, the size of cracks ( ) that are possible decreases. This means that in order to have failure there is a larger amount of stress required, hence smaller particles are less likely to be subject to attrition. In fact it has even been proposed that there is a limiting particle size for which attrition can occur (Bemrose and Bridgewater 1987, 102-103).

This property of small particles to resist attrition may well be the reason why FCC units are generally able to have such high catalyst recovery rates. When small particles are formed as a result of attrition they become attached to other small particles and to larger particles. This happens due to electrostatic attraction, van der Waals forces, and through getting physically stuck in the pores of larger particles. There is also some evidence to suggest that energies of collision may be high enough to form bonds between particles through physically melting them together (Bemrose and Bridgewater 1987, 100-101). These small particles bonding to the larger particles may form a sort of shield which protects the larger particles from collisions. Below, in Figure 7, is a scanning electron micrograph from Boerefijn, Gudde, and Ghadiri (2000, 161) of a particle which has many smaller particle fragments bonded to it.

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Figure 7: Particulate debris bonded to larger particles (Boerefijn, Gudde, and Ghadiri 2000, 161)

It is important at this point to mention the affect that temperature can have on a catalysts physical properties, and hence the affect that process temperature can have on attrition. Operating at a lower temperature than the catalyst was designed for can result in the catalyst being harder, but also brittle, making it more subject to fragmentation. Operating at temperatures above what the catalyst was designed for can result in the catalyst being more elastic, but also too soft and malleable, this can result in the loss of the catalyst structure and hence its ability to catalyse the reaction effectively. Heat transfer effects can also directly cause attrition in several ways. If there is liquid trapped within the particle which becomes vaporised the expansion and subsequent escape of the gas can occur in a high energy manner, causing the particle to break apart. Temperature gradients within the actual particles themselves can also contribute to attrition, since temperature gradients can cause internal stresses (Bemrose and Bridgewater 1987, 103-104). High thermal conductivity of a catalyst prevents this problem; however this is not always possible. Another form of thermal attrition is thermal shock, wherein a particle is moved quickly from one temperature condition to another causing massive internal stresses.

Understanding the relationship between particle flaws and attrition presents several methods of minimising attrition. Firstly, flaws in catalyst particles can be studied with the hope of producing catalysts with smaller flaws. The stress-strain properties of the catalyst can also be optimised to attempt to increase the point of failure for individual particles. Lastly the effect of the particle size on the failure mechanism can be studied and the initial particle size can be optimised to maximise the catalyst life.

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5.5

Transport and Storage

The mechanism through which attrition occurs is largely dependent on the impact velocity of the particle. Attrition occurs through either the fragmentation or abrasion of particles. The particle impact velocity will determine which of these mechanisms is the more dominant form of attrition; fragmentation is more likely to occur at a higher stress and hence a higher impact velocity, whilst abrasion will tend to be the dominant mechanism at lower velocities (Bemrose and Bridgewater 1987, 101-102).

The fluidisation regime is an important factor in how attrition is likely to proceed; if the flow regime involves turbulence then the individual particles will naturally be travelling at higher velocities, and hence attrition is more likely to proceed by fragmentation. The viscosity of the transport fluid is also an important factor in determining the attrition mechanism, since impacts will be slowed in a more viscous medium (Bemrose and Bridgewater 1987, 102). The size and shape of catalyst particles is very important in terms of the adsorption and desorption of hydrocarbons on the catalyst surface (Barrie, Lee and Gladden 2003, 1141). Catalysts are designed with very specific structures in order to maximise reactant conversion, attrition causes this structure to become less efficient than it was designed to be. In FCC this problem of reduced diffusion and hence reactivity of the catalyst is dealt with (along with other issues) by having a large amount of catalyst circulating through the system. As mentioned in Section 3.4 (catalyst circulation), attrition can cause major circulation disruption issues if it is excessive. If there is a high loss of catalyst through attrition then the result can be a change in fluidisation regime in certain areas of the FCC unit. For example with the high drop in mass due to attrition there will be a high flow of new catalyst to the process, this could cause a high pressure in the catalyst riser, which would prevent the regenerator standpipe slide valve from opening. This would likely cause build-up of catalyst in the regenerator stand pipe which would block it and cause a lack of pressure on that side of the valve, causing the problem to become even worse.

Attrition can also change the nature in which the particles interact with each other in the FCC unit and hence change the fluidisation regime caused by certain air rates. The decrease in particle size that attrition causes means that there is an increase in particle agglomerates in the system caused by groups of small particles bonding together with electrostatic

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interactions and van Der Waals forces. Larger particles will also become covered in fine particles, which will allow stronger bonds between particles in a particle bed situation. Rather than having particles bonded to each other with large spaces in-between where there is no bonding, there will be packing of smaller particles clinging both to the larger particles and to each other, bonding groups of particles together with a larger force than the initial catalyst feed. This will mean that higher aeration or more turbulent flow may be required to rip particles apart. There will be a high tendency for furrows to form since there will now be a higher bonding between particles keeping them from fluidising at low fluid rates.

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6.0

Conclusion

Though the FCC process is very beneficial in terms of producing high quality products that are considered valuable in the current market, there are unresolved issues present that may be hindering the full capabilities of the process. Attrition is a phenomena that presents in all areas of the FCC process, either in deterioration of particle size and structure to the effect the particle size distribution has on the fluidisation transport. The benefits of producing a solution to prevent the presence of attrition would have a large significance in the overall efficiency of the FCC process. Therefore, with the knowledge of the effect attrition has on the particulate system, a solution may be developed to further improve this already revolutionary process.

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7.0

References

Barrie, P. J., C. K. Lee and L. F. Gladden. 2003. Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations. Chemical Engineering Science 59(5): 1139-1151. doi: 10.1016/j.ces.2004.01.008 Bemrose, C. R., and J. Bridgewater. 1987. A review of Attrition and Attrition Test Methods. Powder Technology 49(5): 97-126. doi: 10.1016/0032-5910(87)80054-2 Boerefijn, R., N. J. Gudde, and M. Ghadiri. 2000. A review of attrition of the fluid cracking catalyst particles. Advanced Powder Technology 11(2): 145-174. doi: 10.1163/156855200750172286 Bryden, Kenneth, Wu-Cheng Cheng and Dariusz S. Orlicki. 2008. Understanding of FCC Catalyst Deactivation: Cyclic Thermostress Sintering Mechanism. Grace Davison Refining Technologies. Accessed April 8, http://cage.ugent.be/~dc/mackie-

workshops/mackie-2009/20081202-Orlicki.pdf Darmawan, Nina. 2013. Interfacial Characterization. PowerPoint lecture notes. https://lms.curtin.edu.au/bbcswebdav/pid-2501302-dt-content-rid7599721_1/courses/313836-FacSciEng-399804838/14.03.2013%20APP.pdf

Decroocq, David. 1984. Catalytic Cracking of Heavy Petroleum Fractions. Paris, France: Technip. FCC Manual 5.4: The Role of Catalyst in FCC Troubleshooting. 2013. Albemarle. Accessed May 18th. http://s3.amazonaws.com/zanran_storage/www.albemarle.com/ContentPages/191670 94.pdf Forzatti, Pio and Luca Lietti. 1999. "Catalyst deactivation". Catalysis Today 52 (2): 165-181. doi: 10.1016/S0920-5861(99)00074-7 Huq, Iftikhar. 1998. Design and control studies on the fluid catalytic cracking process. PhD diss., California Institute of Technology. http://thesis.library.caltech.edu/446/

23

Massimilla, Leopoldo and Giorgio Donsi. 1976. Cohesive forces between particles of FluidBed Catalysts. Powder Technology 15(2): 253-260. doi: 10.1016/00325910(76)80054-X

Montgomery, David. 2013. Petroleum Processing 475 Lecture Notes: Fluidised Catalytic Cracking Unit. Kwinana, Western Australia: BP Australia.

Niccum, P. K. 2010. 20 questions: Identify probable causes for high FCC catalyst loss. Hydrocarbon Processing 29-38. Accessed April 15, http://www.kbr.com/Newsroom/Publications/Articles/20-Questions-IdentifyProbable-Causes-for-High-FCC-Catalyst-Loss.pdf Pandimadevi, G., P. Indumathi, and V. Selvakumar. 2010. Design of Controllers for the Fluidized Catalytic Cracking Process. Chemical Engineering Research and Design 88 (7): 875-880. doi: 10.1016/j.cherd.2009.11.021

Ravichander, N., T. Chiranjeevi, D. T. Gokak, R. K. Voolapalli, and N. V. Choudary. 2009. "FCC catalyst and additive evaluationA case study". Catalysis Today 141(1): 115119. doi: 10.1016/j.cattod.2008.04.022 Rawlence, D.J and K. Gosling. 1988. FCC catalyst performance evaluation. Applied Catalysis. 43(2): 213-237. doi: 10.1016/S0166-9834(00)82729-3

Ray, Yia-Ching, Tsung-Shann Jiang, and C. Y. Wen. 1987. "Particle attrition phenomena in a fluidized bed". Powder Technology 49(3):193-206. doi: 10.1016/0032-

5910(87)80128-6 Reppenhagen, J., and J. Werther. 2000. Catalyst attrition in cyclones Powder Technology 113(1): 55-69. doi: 10.1016/S0032-5910(99)00290-9

Sadeghbeigi, Reza. 2012. Fluid catalytic cracking handbook: an expert guide to the practical operation, design, and optimization of FCC units. Oxford, United Kingdom: Butterworth-Heinmann. 24

SET Laboratories Inc. 2008. Catalytic Cracking. http://www.setlaboratories.com/cat/tabid/106/Default.aspx

Sun, Guanglin, and John R. Grace. "Effect of particle size distribution in different fluidization regimes." AIChE journal 38, no. 5 (1992): 716-722. http://onlinelibrary.wiley.com.dbgw.lis.curtin.edu.au/doi/10.1002/aic.690380508/pdf

Tonetto, G., K. Atias, and H. de Lasa. 2004. FCC catalysts with different zeolite crystallite sizes: acidity, structural properties and reactivity. Applied Catalysis A:General 207(1): 9-25. doi:10.1016/j.apcata.2004.03.042 Veluswamy, Ganesh K., Rajesh K. Upadhyay, Ranjeet P. Utikar, Moses O. Tade, Geoffrey Evans, Michael E. Glenny, Shantanu Roy, and Vishni K. Pareek. 2013. Hydrodynamic Study of Fluid Catalytic Cracker Unit Stripper. Ind. Chem. Eng. Res. 52 (12): 4660-4671. doi: 10.1021/ie300828n Welt, James, Wooyoung Lee, and Fred J. Krambeck. 1977. Catalyst attrition and deactivation in fluid catalytic cracking system. Chemical Engineering Science. 32(10): 1211-1218. doi: 10.1016/0009-2509(77)80054-7

Yang, Wen-Ching. 2003. Handbook of fluidization and fluid-particle systems. New York, New York: Marcel Dekker Inc.

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