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Troubleshooting FCCU operating problems

Important FCC catalyst properties and the way they affect unit performance are described in this article, which also reviews operating problems that can be corrected, based on analysis and adjustment of the catalysts properties

Jack R Wilcox Dennis C Kowalczyk Robert J Campagna Refining Process Services Inc

he addition of fresh catalyst to the FCC unit is maintained continuously for two reasons: first to maintain optimum catalytic performance, and second to maintain the appropriate physical properties and quantity of the circulating inventory. This article highlights the key catalyst properties that should be monitored and can be used for troubleshooting of FCC operating problems caused by changes in catalyst physical properties or catalytic performance. The article also provides new FCC process engineers and operating personnel with an understanding of the impact of catalyst properties on FCC unit performance. Maintaining the appropriate catalytic activity and selectivity factors is largely determined by the addition rate of fresh catalyst and withdrawal rate of equilibrium catalyst. The following factors will establish the proper catalyst management programs: Yield and product quality objectives Contaminant metals levels to be tolerated Optimum equilibrium catalyst activity level as determined by feed quality and cracking severity Response of unit conversion to fresh catalyst additions Response of unit conversion to equilibrium catalyst activity level The optimum equilibrium catalyst activity level must be established for any specific unit operation. In order to optimise the performance of the FCC unit, the properties of the FCC catalyst such as activity and physical structure must be monitored on an ongoing basis. Microactivity testing (MAT) is a laboratory procedure which measures the degree to which a catalyst sample can crack or convert an FCC feedstock sample. This procedure is used to determine the cracking activity of the catalyst independent of the specific unit operating conditions and feedstock. Equilibrium FCC catalyst samples are collected from commercial FCC

operations and subjected to microactivity testing after calcination to remove residual carbon. MAT results are reported on a comprehensive equilibrium catalyst reporting sheet. This information sheet, along with chemical composition and physical properties, often called an ECat sheet, is a critical tool in the optimisation of a fluid catalytic cracking unit. It is important to note that there can be wide variation in the equilibrium activity numbers. Therefore, in addition to looking at individual data points, it is recommended that catalyst activity be monitored on the basis of a three- to four-week moving average to observe trends. The same microactivity procedure can be used to monitor the cracking activity of the fresh FCC catalyst delivered to the refinery. Equilibrium catalyst activity is a function of many independent and dependent parameters in both the catalyst manufacturing process and commercial cracking operation. First and foremost, catalyst activity is a function of the properties of the fresh catalyst delivered from the manufacturer. FCC catalyst provides cracking activity via two mechanisms zeolitic cracking and matrix cracking. Zeolitic cracking is a function of many factors, including zeolite type, zeolite level in the formulation and the type of treatment (rare earth or alternative) provided to stabilise the zeolite. Matrix cracking is a function of the amount of active alumina component present in the matrix, the matrix surface area, and accessibility of large molecules provided by the pore structure. The relative amounts of zeolitic and matrix activity can be determined and monitored via surface area measurements. Total surface area in an FCC catalyst increases with both increasing zeolite content and matrix activity. Total catalyst surface area is routinely reported on the equilibrium catalyst data sheet. In order to

separate the individual contributions of zeolite and matrix structures to catalyst surface area, it is necessary to employ a more rigorous surface analysis technique. Refiners should verify that either the matrix surface area or the zeolite-to-matrix (Z/M) ratio is reported on a routine basis. Either of these figures will provide the information required to calculate both the zeolite and matrix contributions to catalyst surface area. Matrix surface area is often used as an indicator of matrix activity. While high fresh catalyst matrix surface area (125 to 175m2/gram) generally indicates the presence of active matrix, it can be deceiving to use this value as the only measure of relative matrix activity. FCC catalyst matrix contains many components, including binders, clay, fillers, active matrix materials and additives such as metals traps, and SOx reduction agents. All of these materials contribute to matrix surface area, but only one component crystalline eta or gamma alumina contributes to matrix activity, as it is most often discussed. However, since many catalyst components contain alumina, including zeolite, obtaining reliable values for eta and gamma alumina content is not possible. Impact of FCCU operation on catalyst activity Second, equilibrium FCC catalyst activity is a function of the daily replacement (and withdrawal) rate of catalyst and the catalyst deactivation rate. Key FCCU factors which affect catalyst deactivation rate are listed below. These factors are interrelated and essentially encompass the combined effects of temperature, time, metals contamination and the presence of steam. 1.Vanadium in FCC feedstock deposits itself on the surface of cracking catalyst and migrates to zeolite, where it destroys the crystalline structure. This results in a permanent loss of a portion of the zeolite cracking activity. 2.Regenerator temperature influences the rate of zeolite activity loss via both

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hydrothermal and vanadium-induced deactivation mechanisms. Matrix activity will also deactivate in the FCC regenerator over time as a function of temperature. 3. The level of excess oxygen in the FCC regenerator can greatly influence the degree to which vanadium on the catalyst surface is oxidised. Refiners who convert to oxygen enrichment of regenerator air often report activity loss ranging as high as 4 to 5 MAT numbers. 4. The presence of contaminant metals other than vanadium can also add to the total deactivation profile in a commercial FCC unit. The presence of sodium at the zeolite site interacts with vanadium to greatly exacerbate the destructive tendency of both of these metal contaminants. Certain contaminant metals can also interact with the active matrix sites in the catalyst and render them inaccessible. 5. The presence of steam in the catalyst particles will greatly enhance zeolite deactivation resulting from dealumination. FCC regenerator steam is present from a number of sources, including humidity in the regenerator air, entrained steam from the catalyst stripping section, and water formed via combustion of coke. Steam is also produced during combustion of unstripped hydrocarbon, and for catalyst particles containing significant amounts of unstripped oil, steam concentration in the pores can reach 25 to 35 mole%. Troubleshooting problems with catalyst activity From time to time, most FCC operations experience bouts of declining levels of feedstock conversion. This can often be attributed to factors related to deterioration in feedstock quality, such as increasing carbon residue and asphaltene content, decreasing API gravity, increasing aromatic content and increasing basic nitrogen content. However, there are other instances when unit conversion loss is related to a loss of fundamental catalytic cracking activity. A gradual decline in equilibrium catalyst activity may be difficult to diagnose in an FCC unit, given all the noise inherent in commercial operation. That is why it is important to develop a meaningful moving average trendline for catalyst activity based on the catalyst activity numbers reported by each supplier. Although there may be differences in the absolute values reported by each laboratory, the moving average trendlines should be similar. Troubleshooting catalytic activity loss If it is determined that catalyst activity as measured by MAT testing is declining, there are a number of potential root causes to be investigated: Increased catalyst deactivation date. Increased catalyst deactivation is evidenced by declining MAT activity with no corresponding decrease in catalyst addition rate or increase in catalyst vanadium and/or sodium level. It is important to observe if the equilibrium catalyst activity loss is accompanied by more fines (0 to 40 micron particles) production. Further, FCC operators may observe an increase in catalyst losses from the unit. The combination of these two conditions may indicate a new source of both deactivation and attrition. A new source of steam or some alteration in an existing source of unit steam could create conditions conducive to both catalyst breakage and zeolite deactivation. FCC unit operators should undertake a thorough inspection of all potential troublespots and look for signs of increased steam usage, steam jets such as would result from an open blast steam nozzle, and the presence of wet steam. In the FCCU, matrix activity loss results primarily from thermal mechanisms while zeolite deactivation results primarily from hydrothermal mechanisms. Therefore, increased catalyst deactivation caused by steam would typically result in decreasing zeolite surface with no corresponding change in matrix surface area. Increased thermal deactivation. If equilibrium catalyst activity loss is accompanied by both decreasing matrix and zeolite surface area, it would be reasonable to suspect some form of increased thermal exposure profile on the catalyst. Unit operators would first look for signs indicating some change in the regenerator operation. Potential changes which could lead to this type of situation are as follows: Disruption of the regenerator air grid could lead to pockets of excessive oxygen concentration and localised hot spots in the catalyst bed Increases in air rate to the regenerator could lead to increased circulation through the cyclones, combined with an afterburn condition which creates hotter catalyst than would be indicated by the dense bed temperature Disruptions in the catalyst stripper operation could result in increased oil carryover, resulting in catalyst internal temperatures 150C to 200C higher than the bulk bed, with little observed difference in regenerator dense bed temperature. Diagnosis would involve study of the stripper operating conditions and collection of a stripper catalyst sample for determination of free oil content. A modified version of FCC Reaction Mix Sampling can be used to observe potential problems in catalyst stripper operation. Increased vanadium damage. Decreases in FCC catalyst equilibrium activity are often accompanied by increases in vanadium level on the catalyst. In the FCC regenerator, vanadium oxidises to the pentoxide form. Some FCC regenerators operate above the melting point of vanadium pentoxide, which allows vanadium to melt and flow into the particle and reach the zeolite crystals. It has also been observed that vanadium pentoxide in the presence of steam will form a vapour-phase species which can migrate to other catalyst particles. If increasing catalyst vanadium content is causing reduced MAT activity, refiners have several options for recovering the resultant loss in catalyst activity. They can increase the addition rate of fresh FCC catalyst. A second alternative would involve modification of the current catalyst formulation to incorporate more vanadium tolerance capabilities into the catalyst. However, changing catalyst formulation may result in a shift in the product selectivity profile. There are several new tools for reducing the impact of vanadium on FCC catalyst activity which include separate particle traps and liquid phase vanadium passivation compounds. Increase in other metals contaminants. Many refiners have experienced significant increases in catalyst deactivation rate as a result of increased sodium deposition on catalyst. Increased sodium concentration typically results from upsets at the crude oil desalter or from addition of purchased feedstocks. Purchased feedstocks are often contaminated with salt water. It is important to note that sodium is present in the catalyst as a result of the manufacturing process. The level of sodium on fresh catalyst must be considered when determining changes in sodium concentration. It is well known that sodium interacts with vanadium on the FCC catalyst to exacerbate the rate of catalyst deactivation. FCC feedstocks also may contain other contaminant metals which can interact to block or destroy matrix and zeolite active sites. Inconsistency in catalyst addition quality and amount. Refiners should take steps to ensure that the quality and addition rate of fresh FCC catalyst remains constant. It is important to verify that the MAT activity and surface area, along with physical properties such as particle size distribution and catalyst attrition properties, are monitored frequently and are relatively similar for each delivery. Impact of FCC catalyst physical properties on FCC unit operation The second criterion governing catalyst management is the quantity and physical condition of the circulating inventory. The catalyst physical properties have a direct impact on fluidisation characteristics and collection system (cyclone) efficiency. Important FCC catalyst physical properties are described below. Density and particle size distribution The apparent bulk density (ABD) of fresh FCC catalysts is typically between 0.62

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Equilibrium catalyst particle size as indicator of regenerator problems

A Normal operations Particle size 0.5 510 1020 2040 4080 60+ 80+ APS Unit loss#/bbl Comment Regen Precip 73.6 1.0 14.7 8.3 15.0 2.9 53.0 0.2 0.3 31.0 0 64 0.04 B Maldesigned cyclones Regen Precip 24.1 0 3.5 19.4 6 38.6 55 12.5 1.9 39 0 71.0 0.09 C Damaged cyclones Regen Precip 1.0 0 0.6 0.5 1 16.5 35 56.8 32.3 64 14.6 86.0 0.22 Dirty stack D Flooded diplegs Regen Precip 18.6 1 6.8 5.2 10 38.5 58 27.7 9.4 31 3.2 66.0 12 Puffing E Broken plenum Regen Precip 2.4 0 0.9 0.9 10 17.2 50 56.4 26.1 40 22.2 69.0 0.25 Clean stack F Catalyst attrition Regen Precip 82.5 1.0 11.7 5.4 17.0 0.4 54.2 0 0 28.8 0 62.0 0.25 Dirty stack

Table 1
and 1.0g/cc (4062lb/ft3). The fresh density is a function of the raw materials and the manufacturing procedures. Bulk density will vary inversely with pore volume. Equilibrium catalyst will usually show a bulk density that is about 0.1g/cc higher than the fresh catalyst, due to the loss of some pore volume as normal deactivation occurs. For most units, ABD is not a significant concern. Its effects on catalyst losses and circulation properties are usually small and undetectable. In some cases, however, a significant change in catalyst density can cause important changes in the operation of the unit. First, a catalyst density change will change the correlation of bed height with delta P. This means that if a lower density catalyst is added and the same delta P is maintained, the bed level will increase. This effect could be important if the distance between the cyclone inlet and the bed is close to the transport disengaging height (TDH), which is the minimum distance that should be maintained between the bed and the primary cyclone inlet. If this distance is not maintained, losses will increase. Use of lower density catalysts will also tend to slightly increase entrainment rates. This effect is small in comparison to the effect of particle size on entrainment. Thus, if a lower density catalyst is desired without increased entrainment, a small increase in the fresh average particle size is all that should be required. Also, in normal circumstances (with low to moderate superficial gas velocities in the reactor and regenerator) any changes in losses due to differences in catalyst densities will be negligible. The effects of catalyst density on catalyst circulation are more complicated. On one hand, lower density catalysts cannot generate as much potential delta P per foot of standpipe and thus one might conclude that the maximum catalyst circulation capability of the unit might be reduced by density. On the other hand, lower density catalysts are easier to fluidise and usually deliver a higher percentage of their maximum delta P generating capacity. Here again, for most units, the differences in catalyst circulation capacity for low and high density catalysts will not be significant. For units that are sensitive to circulation upsets due to sudden losses of slide valve delta P, lower density catalysts may have a slight advantage. As with entrainment, the catalyst particle size distribution plays a larger role in fluidisation than does catalyst density. Relatively small changes in particle size distribution can offset most of the effects of catalyst density on catalyst fluidisation. In general, catalysts with more fines (0 to 40 micron particles) are easier to fluidise and circulate. Of course, adding more fines or decreasing the average particle size of a catalyst will increase entrainment rates and will tend to increase losses. The particle size distribution of the fresh catalyst can be varied over a fairly wide range by all of the catalyst suppliers. The user will ordinarily specify the size by ordering a fine, regular or a coarse catalyst grade. Typically, a fine grade could have an average particle size (APS) as low as 55 microns with a fines content as high as 20wt%. The regular grades normally range in APS from 70 to 75 microns with a fines content of about 10 wt%, while coarse grades can have an APS as high as 95 microns with as few as 5wt% fines. Attrition index There are many different attrition tests that are run throughout the industry. Most attrition tests measure the amount of 0 to 20 micron fines that are produced after subjecting the catalyst to a high velocity air jet for a given period of time. Particle size distribution is measured before and after testing, and the attrition index is often equal to the increase in the concentration of particles smaller than 20 microns. Catalysts with attrition indices below 5.0 are considered to have a very high level of particle integrity. Catalysts with attrition indices between 5.0 and 10.0 are considered moderately hard and should run acceptably in most units. In a normal operation, a catalyst with an attrition index of 10.0 would be expected to show losses that are 5 to 10 per cent higher than a catalyst with an attrition index of 1.0. It should be noted that all of the catalyst manufacturers have significantly improved their ability to make hard catalysts over the past several years. In 1980, typical attrition values, as measured by this type of test, were 15 to 20. Today, most catalysts are below 10.0. Impact of physical properties on catalyst flow Maintaining smooth and uniform catalyst circulation helps ensure optimum performance of the fluid catalytic cracking unit. Catalyst circulation is maintained by the differences in density of the fluidised catalyst at various points in the flow system. Relatively high flowing densities in the catalyst standpipes essentially generate a hydrostatic head producing the circulation. This pressure head must be sufficient to overcome friction losses and pressure drops across slide/plug valves and distributors. FCC units of every design have, for various reasons, experienced catalyst circulation difficulties. Usually, the circulation can be stabilised by adjusting catalyst physical properties or catalyst standpipe operation. The usual indication of erratic catalyst circulation is a sudden decrease or fluctuation in slide valve differential pressure. These fluctuations often signal more sig-

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nificant upsets which may occur if steps are not taken to stabilise the situation. As 0.7 the slide valve control becomes erratic, reactor riser temperature and spent catalyst stripper level become ragged. This can 0.6 lead to unstable main fractionator and wet gas compressor operation due to conversion changes. 0.5 Circulation difficulties usually result from changes in catalyst physical properties, mechanical equipment damage, 0.4 standpipe blockage, or standpipe aeration problems. Catalyst fines, primarily the 0-20 0.3 micron fraction either generated by attrition or supplied with fresh catalyst are essentially lost through both the reactor and regenerator collection systems. In 0.2 order to obtain the required particle size distribution for any given FCCU configuration to maintain uniform calculation, 0.1 fresh catalyst must be continuously added to the unit. Proper fluidisation of flowing 0 catalyst in the transfer lines is essential to 60 65 70 75 80 85 90 stable FCCU operation. A basic measure of the behaviour of fluAPS Microns idised FCC catalyst used to determine how changes in fluidisation media, particle size 1.4gm/cc 1.2gm/cc 1.3gm/cc distribution and particle density may affect standpipe fluidisation is described 1.5gm/cc 1.6gm/cc by the equation in the panel below The ratio of UMb/UMf is larger than one 25ft Disengaging height and, as the ratio increases, better quality 3.0ft Superficial velocity fluidisation properties are exhibited. The required level of UMb/UMf is not an absolute value, but is specific to unit configuFigure 1 Particle size vs cyclone loading: for particle densities 1.2 to 1.6gm/cc ration and operation. Meaning-ful unit operating data, combined with historical 40 microns is usually between 4 and 10 lating inventory is a function of the data for both fresh make-up and circulatper cent. Fresh catalyst will have typically cyclone performance. Frequent analysis of ing equilibrium catalyst, typically provides 2 per cent and 14 per cent for the less than the catalyst physical properties, particularsufficient input to determine if the fluidis20 and 40 microns respectively. ly equilibrium catalyst density and particle ation problem is due to mechanical or catDirectionally improving the catalyst propsize distribution, is required to monitor alyst property changes. erties improves the fluidisation charactercyclone performance. Catalyst losses from The following parameters favour istics as follows; it: the unit are generally acceptable as long as Reduces minimum fluidisation velocity smooth fluidisation: slurry oil BS&W or flue gas dust emission Lower catalyst particle density Reduces minimum bubbling velocity levels are not excessive. Lower mineral density Increases the ratio of minimum bubAn increase in losses through both reac Increased pore volume bling velocity to minimum fluidisation tor and regenerator, while the fines indi Lower average particle size velocity cated by fresh catalyst and equilibrium Increased fines content (fines = wt% less Increases time for catalyst deaeration. catalyst PSD remain constant, indicates than 45 microns) The fines level maintained in the circuthe generation of fines in the unit. A typi Higher density and viscosity of cal shift in catalyst PSD in this sitfluidising gas. uation is shown in column F in The quantity of fines in the cirTable 2. The cause is either an Equation: FCC catalyst fluidisation culating catalyst inventory has a intrinsic attrition resistance probdirect impact on the fluidisation lem with the catalyst itself or 2300pg0.126 0.523 exp(0.716 F45) UMb/UMf = and resulting circulation. The some source of attrition in the dp0.8 (g[pp pg])0.934 fines level will be established by unit. If the equilibrium catalyst cyclone design and performance, activity or surface area is decreasUMb = Superficial gas velocity at minimum bubbling, M/sec fresh catalyst fines content and ing simultaneously it can be UMf = Superficial gas velocity at minimum fluidisation, attrition resistance, and by other assumed that the attrition source M/sec factors, such as gas velocities and is causing deactivation due to pg = Gas density, kg/M catalyst entrainment rate affecthigh velocity steam. pp = Particle density, kg/M ing cyclone efficiency. An increase in catalyst losses = Gas viscosity, kg/M-sec The less than 20 microns conwhile the average particle size F45 = Fraction of fines less than 45 microns tent in the circulating inventory increases indicates a cyclone g = Gravitational constant dp = Mean particle size is typically between 0 and 30 per problem. Factors which will cause cent, while the amount less than deteriorating cyclone performance

Densty at cyclone lb/ft3

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include: misdesigned cyclones; increased solids loading; increased gas loading; damaged cyclones due to holes in cyclone body, gas tube or diplegs; loss of dipleg seal; stuck trickle/flapper value, and erosion of internal lining. Though possible, it is not likely that conformance to current design criteria followed by cyclone designers would lead to gross design errors. If a design error did occur, a shift in catalyst PSD would appear as shown in column B in Table 1. Increased solids and gas loadings are a result of higher actual vessel velocity. The entrainment of catalyst will increase with increased superficial gas velocity. An increased load can also result from poor air distribution causing localised high velocities. This also causes higher cyclone outlet temperatures due to afterburning. Increasing the degenerator dense bed level sometimes helps alleviate this situation. Once the cyclones are badly eroded, losses become increasingly higher and the unit must be shut down to repair the damage. Indications of damage to the cyclone will result in an increase in average particle size of the circulating catalyst as shown in column C in Table 1. Flooding cyclone diplegs or damaged dipleg outlet values will lead to higher losses. A shift in catalyst PSD as well as visual inspection of the regenerator stack will indicate dipleg problems as shown in column D. A high catalyst level in the regenerator dense bed will cause a backup of catalyst in the cyclone dipleg and can cause the dipleg to flood. In order to accurately determine the bed level, two separate differential pressure transmitters for measuring the height and resulting density of the catalyst bed are required. A change in catalyst type may cause a change in catalyst bed level, due to a difference in catalyst bulk density. Typically, cyclone secondary diplegs are oversized in the event that the primary cyclones will, through excessive erosion or other damage, lose efficiency, resulting in increased carryover of catalyst to the secondary cyclone. However, this is generally not a large problem as the increase in fines level and lower average particle size to the secondary cyclone normally improves fluidisation in the secondary cyclone dipleg. The impact of particle size and particle density on catalyst entrainment to the cyclone is shown in Figure 1. Cyclone operation will change with these catalyst physical properties. Operating the unit while utilising a high particle density catalyst has the following effect: high particle density catalyst reduces entrainment of catalyst to the cyclone inlet, resulting in lower solids loading to the first stage cyclone and subsequently to the second stage cyclone. Reduced solids loading to the second stage cyclones increases catalyst residence time in the diplegs and increases the possibility of de-aerating the catalyst before it leaves the dipleg. The longer the dipleg and the greater the submergence of the dipleg into the dense bed will result in increased gas compression and catalyst residence time. Both of these factors will directionally increase defluidisation of catalyst in the dipleg and produce stick-slip flow.

Jack Wilcox is vice president, catalytic cracking technology, with Refining Process Services Inc, Cheswick, Pennsylvania, USA. He provides FCC optimisation, troubleshooting and technology evaluation services to refiners around the world. Dennis Kowalczyk is vice president, operations. He coordinates FCC reaction mix sampling test runs and is responsible for MagnaCat and MVP vanadium passivation commercialisation licensing activities. Robert Campagna is president of Refining Process Services Inc. He serves as director of technical services and is involved in FCC catalyst evaluation and optimisation studies and refinery technical services, and also provides FCC technical training.

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