Chapter 6

KINETICS AND MECHANISMS OF FLUID CATALYTIC CRACKING

P. OConnor
Albemarle Catalysts Stationsplein 4, P.O.Box 247, 3800AE Amersfoort, The Netherlands

1.

INTRODUCTION

Catalytic cracking is a very flexible process to reduce the molecular weight of hydrocarbons. Today fluid catalytic cracking (FCC) remains the dominant conversion process in petroleum refineries. Prior to 1925, the higher boiling heavy crude oil molecules were chemically changed to smaller naphtha (gasoline) molecules by thermal decomposition using a process called thermal cracking. In the late twenties Eugene Jules Houdry demonstrated that a catalytic cracking process yields more gasoline of a higher octane. The first full-scale commercial fixed bed catalytic cracking unit began production in 1937.

2.

PROCESS DEVELOPMENT

During the catalytic cracking process the catalysts are after a short time covered by a deactivating layer of coke. This coke can be removed and regenerated by burning, but the regeneration time is relatively slow compared to the reaction time. An efficient way to solve this problem is to move the catalyst from one reactor (for hydrocarbon cracking) to another reactor (for catalyst regeneration). The first continuous circulating catalyst process using a bucket elevator thermofor catalytic cracking (TCC) was started up in Paulsboro, NJ in 1941.

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The moving-bed solved the problem of moving the catalyst between efficient contact zones. However the catalyst beads used still were too large, limiting the regenerator temperatures to avoid intra particle temperature excursions and therefore requiring a large regenerator and catalyst hold up.1 Moving the solid catalyst in this way remains a challenge, which was solved by making use of the invention that it is possible to make a powder to flow in a manner similar to a liquid if enough gas flows through it. This phenomenon is called fluidization and the FCC process was introduced which uses fine powdered catalysts which can be fluidized. The first commercial circulating fluid bed process went on stream in 1942 in Baton Rouge, Louisiana.2 By the 1970s FCC units replaced most of the fixed and movingbed crackers. Generally FCC units operate in a heat balanced mode whereby the heat generated by the burning of coke is equal to heat needed for the vaporization of the feed plus the heat of cracking. Also the pressure balance of an FCC unit is very important in order to ensure proper catalyst circulation and to prevent the contact between hydrocarbons (reactor) and air (regenerator). Overall this makes the optimal operation of a unit a very interesting challenge. The FCC process hardware and operation have continued to co-evolve with the catalyst and the changing economical and environmental requirements. Key development in FCC process and hardware are:1,3 Short contact time riser reactor. Feed distribution, atomization. Feed pre vaporization or supercritical injection. Multiple feed injection. Quick product disengaging and separation from catalyst. Quick product quench. More efficient stripping. Downer (downflow) reactor. Improved regenerator efficiency, lower inventory. Improved control of combustion (CO, CO2, SOx, NOx). Improved airgrid designs. Catalyst coolers (internal and external heat-removal). Power recovery from fluegas. Improved high flux standpipes. High efficiency cyclone separators. Cyclones without diplegs. Third-, Fourth- and Fifth- stage particulate capture systems. Errosion and high temperature resistant metallurgy. These developments have led to dramatic reductions in the size (elevation, volume, catalyst inventory) and hence costs of a FCC unit required per barrel of feed charged and converted.

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3.

CHEMISTRY AND KINETICS

The catalytic cracking of hydrocarbons is a chain reaction that is believed to follow the carbonium ion theory involving three steps: Initiation, propagation and termination. The initiation step is represented by the attack of an active site on a reactant molecule to produce the active complex that corresponds to the formation of a carbocation. The chain propagation is represented by the transfer of a hydride ion from a reactant molecule to an adsorbed carbenium ion. Finally the termination step corresponds to the desorption of the adsorbed carbenium ion to give an olefin whilst restoring the initial active site.4 Carbenium-ion cracking mechanism produces a higher yield of a much more desirable gasoline than thermal cracking. While thermally cracked gasoline is quite olefinic, cat cracked gasoline contains a large amount of aromatics and branched compounds which is beneficial for the gasoline octane numbers (RON and MON). The following table illustrates the differences in the kinetics of thermal and catalytic cracking at about equal conversion.
Table 1. Catalytic vs. thermal cracking Conversion iC5/nC5 ratio Thermal 0 Activated Carbon 0.06 Alumina 0.2 Silica-Alumina 3.8 (C1+C2)/iC4 ratio 66 27 14 0.6 Fuel gas, mol/mol cracked 2 0.54 2.72 0.41

The above data indicate that also for catalytic cracking strong differences in are possible. Only carbenium-ion cracking involving a tertiary carbeniumion will produce branched compounds. A second type of cracking, protolytic cracking,5 can be assumed to yield more radical-cracking like products such as methane and ethane (fuel gas).

4.

CATALYSTS

Table 2 gives the types and forms of cracking catalysts developed and used over the years. The way in which catalysts are built up from the separate components (catalyst assembly) and catalyst form, have an important impact.6 The first FCC catalyst, the Super Fitrol, were produced by activating clays with acid these materials were originally used for bleaching edible oils and decolorizing hydrocarbons. Synthetic mixed oxide catalysts followed, some of which were 2 to 3 times more active than the activated clay based types. The Al2O3 of the SiO2Al2O3 was optimized impregnating dry SiO2 gels in the 10 to 25% Al2O3 range. The high Al2O3 catalysts (HA, 25% Al2O3) exceeded the low Al2O3 catalysts (LA) and Super Filtrol steamed activity level. Later on

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clay was added in the preparation of synthetic SiO2Al2O3 catalysts to provide additional macro porosity.
Table 2. Early days of cracking catalysts Year Process Reactor System 1920 McAfee Batch 1939 Houdry Fixed bed 1940 1942 1945 1942 1946 1965 Suspensoid FCC TCC Housdry Flow FCC FCC FCC Liquid phase Fluid bed Moving bed Fluid bed Fluid bed Fluid bed Catalyst type AlCl3 Clay Clay Clay Clay Synthetic SiO2Al2O Synthetic SiO2Al2O X, Y Zeolites Catalyst form Granulated Acid treated Granulated Ex-luboil decolorizing. Powdered Super Filtrol Acid treated Powdered Acid treated Pellets Ground Microspheres Microspheres

Co-currently micro spheroidal (MS) catalysts were developed, recognizing the advantages for a higher alumina content catalyst and improvements in impregnation efficiency with small particles compared to the traditional lumps of silica hydro-gel. The original process was quite burdensome and involved an emulsion process which was replaced soon by spray drying of the impregnated gel. Spray drying still is today the way all FCC manufacturers compound and form their MS catalysts. In the 1950s zeolites were invented along with their potential application in catalysis.7 In the 1960s Mobil introduced zeolites into FCC catalysts leading to very substantial increases in conversion and gasoline production,8 as shown in the following example:
Table 3. Improvements in zeolite cracking catalysts Catalyst Conversion (vol.%) Silica-Alumina gel 56 REHX 68 REHY 75 Gasoline (vol.%) 40 52 58

The first generation zeolite catalysts were based predominately on SiO2Al2O3 gels (matrix) in which the zeolite is added at some point prior to spray drying. In the In-situ crystallization method as applied by Engelhard, kaolin based microspheres are prepared and calcined, where after zeolites are crystallized in the microsphere, leaving zeolite in an Al2O3enriched matrix. In the early 1970 s Grace Davison introduced the use of a silica hydro-sol based binder for the incorporation of zeolites. Silica hydro sol is a polymerized silica dispersed in water to form a clear continuos phase, which

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is a binder giving dramatic improvements in attrition resistance and density. The result is the creation of particles which are encased in a hard resilient shell of a vitreous material. The low activity of the silica hydro-sol relative to the SiO2Al2O3 based systems enabled the selectivities of nearly pure zeolite cracking, resulting in further improvements in gasoline and coke yields. Nevertheless, alternate routes of using Al2 O3 gel and/or SiO 2Al 2O3 gels as binders and as catalytic functional materials are also still pursued, because of the significance of porosity and permeability of the microsphere. The importance of diffusion restrictions in FCC catalysis is often questioned. Short contact time pilot riser experiments confirm that combining zeolites with a diffusion enhancing matrices can result in significant product selectivity and product property improvements. The industrial benefits of non-zeolite matrix on bottoms cracking in Heavy VGO and resid FCC have also been confirmed in practice. Recently new methods are used to measure the accessibility of FCC catalysts.6,11 Besides faujasite (Y) zeolites, todays catalysts contain several additional functional materials such as metal traps, nickel resistant matrices, bottoms cracking matrices and small pore zeolites as for instance ZSM-5.9 These zeolites are often added in separate (additive) particles with the intention of boosting the gasoline octane numbers and/or the production of light olefins (propylene) Also various FCC additives are produced usually consisting of metals (Pt, Pd, Ce, V, Cu, Co, Zn) on alumina and or alumina-magnesia supports for CO2, CO, SOx and NOx control of the regenerator off-gas 10 and for Sulfur reduction of gasoline. 5. CATALYST AGING AND DEACTIVATION

FCC catalysts are deactivated via several mechanisms,11 which all result in a loss in activity and a change in yield selectivity: Catalyst will age, meaning change chemical and physical structure due to the (hydro) thermal conditions during the 10,000 to 50,000 reaction and regeneration cycles it will endure. The catalysts can also be poisoned, whereby the active sites are covered by coke and/or polars (nitrogen) that neutralize the catalytic activity or by metals (vanadium, nickel, sodium) which can destroy or alter the activity. Catalysts can also be deactivated by fouling whereby coke and/or metals deposits and block the catalyst pores and thereby limit the mass transfer. Reversible deposits (nitrogen, coke) are removed during regeneration. If we assume that the poisoning effect will increase with the concentration, then the poisoning effect will be inversely proportional to the catalyst-to-oil ratio (CTO), and therefore will be dependent on the coke selectivity of the catalyst. Irreversible catalyst poisons (metals), on the other hand, will build up and continue to interact with the catalyst.

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The very detrimental effects of contaminants like Iron and calcium on the accessibility and performance of catalysts has been reported.6,12,13 Apparently these contaminants can result in (liquid) eutectic melts on the surface of the catalyst particles, which can block the important entrance pores and even glaze catalyst surface completely.

6.

FEEDSTOCKS, PRODUCTS AND THE ENVIRONMENT

To strike a balance between product demand and refinery feed composition, more residue (high metals, concarbon) is being included in FCC feedstocks. Improvements in process and catalyst technology has resulted in a further opening of the feedstock processability window (Fig. 1).

Figure 1. Resid properties and processability (from Ref. 9)

Environmental regulations are a becoming more a key driving force for reducing FCC process air-pollutant emissions 10 and for changing the composition of fuel products 9. This is affecting the design and operation of the FCC and is providing new opportunities for the development of catalyst and additive technology.

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7.

FUTURE CHALLENGES

Although FCC is sometimes considered to be a fully matured process, new challenges and opportunities in its application and a continuing stream of innovations in the process and catalyst field ensure that it will remain an important and dynamic process in the future of refining.

8.
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

REFERENCES
Avidan, A.A. Origin, development and scope of FCC. in Fluid Catalytic Cracking Science & Technology, Magee,J.S.; Mitchell, M.M (Eds.), Stud. Surf. Sci. Catal., 1993, Vol. 76. The Fluid Bed Reactor, A National Historic Chemical Landmark, published by American Chemical Society to commemorate the designation of the Fluid Reactor as a National Historic Chemical Ladmark, 1998. Schlosser, C.R.; Pinho, A.; OConnor, P.; Baptista, R.D.; Sandes, E.F.; Torem, M.A. Residue Catalytic Cracking Technology: State of the Art and future developments, Akzo Nobel Catalysts Symposium, June 2001. Corma, A.; Orchilles, A.V. Current views on the mechanism of catalytic cracking. In Microporous and Mesoporous Materials, 2000, 35-36, 21-30. Wojciechowski, B.V.; Corma, A. Catalytic Cracking: Catalysis, Chemistry, Kinetics, Marcel Dekker Inc: New York, 1986. OConnor, P.; Imhof, P.; Yanik, S.J. Catalyst Assembly Technology in FCC in Fluid Catalytic Cracking V. Materials and Technology Innovations, Studies in Surface Science and Catalysis, Occelli, M.L.; OConnor, P. (Eds.), 2001, Vol. 134. Boyle, J.; Pickert, J.; Rabo, J.; Stamires, D. in 2nd International Congress in Catalysis, July 1960, Paris. Plank, C.J. The invention of zeolite cracking catalysts, Chem. Tech., 1984, 243. Biswas, J.; Maxwell, I.E. Recent process and catalyst related developments in FCC, Appl. Catal., 1990, 63, 197-258. Cheng, W.C.; Kim, G.; Peters, A.W.; Zhao, X.; Rajagopalan, K. Environmental FCC technology, Catal. Rev Sci. Eng., 1998, 40 (1&2), 39-79. OConnor, P.; Pouwels, A.C. FCC Catalyst deactivation in Catalyst Deactivation, Stud. Surf. Sci. Catal., 1994, Vol. 88.. Hodgson, M.C.J.; Looi, C.K.; Yanik, S.J. Avoid excessive catalyst deactivation, Akzo Nobel Catalysts Symposium, June 1998. Yaluris, G.; Cheng, W.; Hunt, J.L.; Boock, L.T. The effects of Fe poisoning on FCC catalysts, NPRA Annual meeting 2001, AM-01-59.