Reaction mechanisms catalytic cracking

We conclude, therefore, that the mechanisms of catalytic cracking reactions on nickel metal and nickel carbide are closely comparable, but that the latter process is subject to an additional constraint, since a mechanism is required for the removal of deposited carbon from the active surfaces of the catalyst. Two phases are present during reactions on the carbide, the relative proportions of which may be influenced by the composition of the gaseous reactant present, but it is not known whether the contribution from reactions on the carbide phase is appreciable. Since reactions involving nickel carbide yielded products other than methane, surface processes involved intermediates other than those mentioned in Scheme I, although there is also the possibility that if cracking reactions were confined to the metal present, entirely different chemical changes may proceed on the surface of nickel carbide. 

The hydrocarbon catalytic cracking is also a chain reaction. It involves adsorbed carbonium and carbenium ions as active intermediates. Three elementary steps can describe the mechanism initiation, propagation and termination [6]. The catalytic cracking under supercritical conditions is relatively unknown. Nevertheless, Dardas et al. [7] studied the n-heptane cracking with a commercial acid catalyst. They observed a diminution of the catalyst deactivation (by coking) compared to the one obtained under sub-critical conditions. This result is explained by the extraction of the coke precursors by the supercritical hydrocarbon. 

Several reaction pathways for the cracking reaction are discussed in the literature. The commonly accepted mechanisms involve carbocations as intermediates. Reactions probably occur in catalytic cracking are visualized in Figure 4.14 [17,18], In a first step, carbocations are formed by interaction with acid sites in the zeolite. Carbenium ions may form by interaction of a paraffin molecule with a Lewis acid site abstracting a hydride ion from the alkane molecule (1), while carbo-nium ions form by direct protonation of paraffin molecules on Bronsted acid sites (2). A carbonium ion then either may eliminate a H2 molecule (3) or it cracks, releases a short-chain alkane and remains as a carbenium ion (4). The carbenium ion then gets either deprotonated and released as an olefin (5,9) or it isomerizes via a hydride (6) or methyl shift (7) to form more stable isomers. A hydride transfer from a second alkane molecule may then result in a branched alkane chain (8). The... 

Also shown in Tables III through V is the effect of hydrotreating on hydrogen transfer during catalytic cracking. This effect is shown by the ratio of saturated to olefinic C. In catalytic cracking, there are two mechanisms for the formation of saturates. These are the primary cracking reaction, such as... 

The catalytic cracking of four major classes of hydrocarbons is surveyed in terms of gas composition to provide a basic pattern of mode of decomposition. This pattern is correlated with the acid-catalyzed low temperature reverse reactions of olefin polymerization and aromatic alkylation. The Whitmore carbonium ion mechanism is introduced and supported by thermochemical data, and is then applied to provide a common basis for the primary and secondary reactions encountered in catalytic cracking and for acid-catalyzed polymerization and alkylation reactions. Experimental work on the acidity of the cracking catalyst and the nature of carbonium ions is cited. The formation of liquid products in catalytic cracking is reviewed briefly and the properties of the gasoline are correlated with the over-all reaction mechanics. 

The acid-catalyzed reactions of olefin polymerization and aromatic alkylation by olefins have been very well explained by the carbonium ion mechanism developed by Whitmore (21). This mechanism provides the basis of the ensuing discussion, which is devoted to the application of such concepts (7,17) to catalytic cracking systems and to the provision of much added support in terms of recently developed structural energy relationships among hydrocarbons and new experimental evidence. 

Fundamental studies of catalytic cracking have led to the conclusion that the chief characteristics of the products may be traced to the primary cracking of the hydrocarbons in the feed stock and to the secondary reactions of the olefins produced both correspond to the ionic reaction mechanisms of hydrocarbons in the presence of acidic catalysts. The chemistry of both the hydrocarbons and catalysts dealt with here has advanced rapidly in the last decade. Nevertheless, much further exploration is required with respect to the nature of the catalyst and the properties of the hydrocarbons undergoing reaction. A promising field lies ahead for future research. 

A central feature of the mechanism that accounts for the catalytic cracking of hydrocarbons by appropriately cation exchanged zeolites is the formation of carbonium ions (also designated carbocations and alkylcarbenium ions) as intermediates. Many other reactions for which aluminosilicates, be they clay-or zeolite-based, also predicate (320) the existence of carbonium ion intermediates, formed usually by proton donation from Bronsted acid sites, have been discussed earlier (Section III,K). 

Zeolites are crystalline aluminosilicates that have exhibited catalytic activities ranging from one to four orders of magnitude greater than amorphous aluminosilicates for reactions involving carbonium ion mechanisms such as catalytic cracking (144). As a result extensive efforts have been undertaken to understand the nature of the catalytic sites that are responsible for the observed high activity. The crystalline nature of zeolites permits more definite characterization of the catalyst than is possible for amorphous acidic supports such as alumina and silica-alumina. Spectral techniques, in conjunction with structural information derived from X-ray diffraction studies, have led to at least a partial understanding of the nature of the acidic sites in the zeolite framework. 

Wojdechowski, B.W. (1998) The reaction mechanism of catalytic cracking quantifying activity, selectivity, and catalyst decay. Catal. Rev. — Sci. Eng., 40, 209. 

For quite some time, it was not clear whether the catalytic cracking process of these aluminosilicates involves the concerted action of both Lewis and Bronstedt acid sides, or only Lewis sites, or even the dissociation of the adsorbed hydrocarbons by surface metal ions (impurities).16,17,18 19 The need for oxide systems that allow evidence concerning the above catalytic theories was one of the driving forces for the efforts that have been done to coat a silica surface with aluminium compounds. One of the earlier studies, concerning both the reaction mechanisms of the aluminium... 

From a series of experiments in this reactor, the deactivation effect of coke on a complex reaction mechanism may be obtained. This is illustrated for the catalytic cracking of n-hcxane on a US-Y zeolite catalyst. On a faujasite, the coke formation deactivates the main reactions, but not the coking reaction. Moreover, the coke formation induces selectivity changes, which can be explained by the distribution of acid site strength in Y-zeolites and the acid strength requirements of the various reactions. 

One method of overcoming this problem is to increase the space time during the experiment by adapting the feed rate, so as to keep the conversion at a constant level. This, however, necessitates an instantaneous effluent analysis, coupled with a control circuit adjusting the inlet flow rates. For the study of the deactivation of a complex reaction mechanism subject to rapid deactivation, such as catalytic cracking on a Y-zcolite catalyst, this would be a... 

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