Kinetics catalytic cracking

Erosion. The abrasive is likely to be gas borne (as in catalytic cracking units), liquid borne (as in abrasive slurries), or gravity pulled (as in catalyst transfer lines). Because of the association of velocity and kinetic energy, the severity of erosion may increase as some power (usually up to the 3d) of the velocity. The angle of impingement also influences severity. At supersonic speeds, even water droplets can be seriously erosive. There is some evidence that the response of resisting metals is influenced by whether they are ductile or brittle. Probably most abrasion involved with hydrocarbon processing is of the erosive type. 

Catalytic Cracking Catalysts, Chemistry, and Kinetics, Bohdan W. 

An analogous situation occurs in the catalytic cracking of mixed feed gas oils, where certain components of the feed are more difficult to crack (less reactive or more refractory) than the others. The heterogeneity in reactivities (in the form of Equations 3 and 5) makes kinetic modelling difficult. However, Kemp and Wojclechowskl (11) describe a technique which lumps the rate constants and concentrations into overall quantities and then, because of the effects of heterogeneity, account for the changes of these quantities with time, or extent of reaction. First a fractional activity is defined as... 

T. H. Tsai, J. W. Lane, and C. S. Lin Temperature-Programmed Reduction for Solid Materials Characterization, Alan Jones and Brian McNichol Catalytic Cracking Catalysts, Chemistry, and Kinetics,... 

Wojciechowski, B.W., and Corma, A., Catalytic Cracking—Catalysts, Chemistry, and Kinetics. Marcel Dekker, New York, 1986, p. 5. 

Fluidised catalysts are also used in the synthesis of high-grade fuels from mixtures of carbon monoxide and hydrogen, obtained either by coal carbonisation or by partial oxidation of methane. An important application in the chemical industry is the oxidation of naphthalene to phthalic anhydride, as discussed by Riley(131). The kinetics of this reaction are much slower than those of catalytic cracking, and considerable difficulties have been experienced in correctly designing the system. 

A number of mechanistic modeling studies to explain the fluid catalytic cracking process and to predict the yields of valuable products of the FCC unit have been performed in the past. Weekman and Nace (1970) presented a reaction network model based on the assumption that the catalytic cracking kinetics are second order with respect to the feed concentration and on a three-lump scheme. The first lump corresponds to the entire charge stock above the gasoline boiling range, the second... 

Lee, L.S., Chen, T.W., Haunh, T.N., and Pan, W.Y. (1989) Four lump kinetic model for fluid catalytic cracking process. Canadian Journal of Chemical Engineering, 67, 615. 

A model for the riser reactor of commercial fluid catalytic cracking units (FCCU) and pilot plants is developed This model is for real reactors and feedstocks and for commercial FCC catalysts. It is based on hydrodynamic considerations and on the kinetics of cracking and deactivation. The microkinetic model used has five lumps with eight kinetic constants for cracking and two for the catalyst deactivation. These 10 kinetic constants have to be previously determined in laboratory tests for the feedstock-catalyst considered. The model predicts quite well the product distribution at the riser exit. It allows the study of the effect of several operational parameters and of riser revampings. 

All the previously cited models and works also consider, and some explicitly cite, this assumption—that the catalyst activity varies with time-on-stream (or with coke concentration [12]) in the same manner or with the same deactivation function (VO for all reactions in the network. That is, a nonselective deactivation model is always used. Corella et al. (16) have recently demonstrated that in the FCC process this assumption is not true and that it would be better to use a selective deactivation model. Another work (17) also shows how this consideration, when applied to catalytic cracking, influences the yield-conversion curves. Nevertheless, to avoid an additional complication, we will use in this chapter a nonselective deactivation model with the same a—t kinetic equation and deactivation function (VO for all the cracking reactions of the network. 

Weekman Jr., V.W. and D.M. Nace, Kinetics and Catalytic Cracking Selectivity in Fixed, Moving and Fluid-Bed Reactors., AIChE Joum., 16,397,1970. 

The possibility of obtaining high levels of conversion and the ability to separate the influence of coke formation and of conversion changes on the reaction kinetics, makes this reactor configuration attractive for the study of the deactivation of complex reactions, such as catalytic cracking. 

Wojciechowski B.W.and Corma A., Catalytic Cracking Catalysts, Chemistry and Kinetics, Chemical Industries/25, Marcel Dekker, Inc. (1986)... 

Studies of hydrogenation, including destructive hydrogenation (Nemtsov, Prokopets, Dyakova), reported in the 1930 s, may have been utilized by now for industrial processes. A. V. Frost has been conducting research on the kinetics of catalytic reactions and on catalytic cracking. Frost and M. D. Tilicheev are co-editors of a series of publications on physical constants of hydrocarbons which may be used as a source of information on the synthesis of individual hydrocarbons. Other Russian groups have contributed (N. D. Zelinskii, A. D. Petrov) to this field. Some of this work involves catalytic reactions however, in this review mere mention of it may suffice. 

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