Hydrocarbon reactions kinetics, isomerization

Shape selectivity is not confined to reactions of hydrocarbons in the absence of polar functional groups. MFI type materials have been reported to catalyze the isomerisation of cresols, chlorotoluenes, toluonitriles and toluidines [259]. In the isomerization of aniline derivatives the reaction temperatures have to be relatively mild as under severe reaction temperatures isomerization to methylpyridine would occur [260]. For dimethylanilines it could be shown that only the isomers with the smallest minimum kinetic diameter reacted (reactant selectivity), and that those with a larger kinetic diameter did not form (product selectivity). The isomerization is concluded to occur via a 1,2 methyl shift which is interpreted to indicate transition state selectivity [261]. 

The transformations reviewed in Section 5.5 are potential maturity indicators.The most useful reactions are those in which only one of the pair of components is present initially in immature sediments, so that the extent of the transformation can be attributed entirely to thermal maturation (the kinetics of the transformation are also simpler Box 5.4). Such reactions include isomerization of pristane at C-6 and C-10, of steranes at C-20 and of hopanes at C-22, and also the aromati-zation of C-ring monoaromatic steroidal hydrocarbons. A number of molecular maturity parameters are shown in Fig. 5.47, together with some bulk maturity measurements.The correlation of values is approximate and varies with the type of organic matter present, its potential for generating petroleum and its heating rate. 

Hydrogen transfer is another important mechanism in FCC catalytic reaction kinetics. Unlike beta scission and isomerization, which involve only a single molecule, hydrogen transfer is a bimolecular reaction. In order for hydrogen transfer to occur, two hydrocarbon molecules have to be adsorbed on two active sits on the catalyst, and the two active sites have to be close... 

A similar mechanism of chain oxidation of olefinic hydrocarbons was observed experimentally by Bolland and Gee [53] in 1946 after a detailed study of the kinetics of the oxidation of nonsaturated compounds. Miller and Mayo [54] studied the oxidation of styrene and found that this reaction is in essence the chain copolymerization of styrene and dioxygen with production of polymeric peroxide. Rust [55] observed dihydroperoxide formation in his study of the oxidation of branched aliphatic hydrocarbons and treated this fact as the result of intramolecular isomerization of peroxyl radicals. 

Hj Dj exchange on, 26 39-43 heteropolyanion-supported, 41 230-231 high MiUer index, 26 12-15,35,36 -H-USY zeoUte, 39 186-187 hydrocarbons adsorption, 38 229-230 reactions of cyclopropane, cyclohexane, and n-heptane, 26 51-53 structural effects, 30 25-26 hydrogen adsorption on, 23 15 hydrogenation, 30 281-282 olefins, in ethanol, 30 352-353 in hydrogenation reaction, 33 101 -iron alloys, 26 75 isomerization, 30 2-3 isotope, NMR properties, 33 213,274 kinetic oscillations, 37 220-228 ball models of densely packed surfaces, 37 221-222... 

A reaction of particular relevance with respect to applied catalysis is the oxidative dehydrogenation (ODH) of hydrocarbon by VmOn ions according to reaction 2, which involves a two-electron reduction of the cluster. By means of a systematic study of the reactions of various YmOn ions as well as the related oxo-vanadium hydroxides VmO H+ ions with a set of C4-hydrocarbons, it was demonstrated recently that the ODH activity of the cluster ions shows a clear correlation with the formal valence of vanadium in the cluster ions with a maximum reactivity for formal vanadium (V) (Fig. 3) [84]. In such a kind of reactivity screening, it is essential to include more than a single reagent as a probe for the reactivity of the different ions in order to reduce interferences by kinetic barriers of one particular combination of neutral and ionic reactants [85]. Accordingly, the sums of the relative rate constants for the ODH reactions of the four different butenes are considered and normalized to the most reactive ion studied, which turns out to be the formally pure vanadium (V) compoimd In addition to isomeric... 

Whereas step 1 is stoichiometric, steps 2 and 3 form a catalytic cycle involving the continuous generation of carbenium ions via hydride transfer from a new hydrocarbon molecule (step 3) and isomerization of the corresponding carbenium ion (step 2). This catalytic cycle is controlled by two kinetic and two thermodynamic parameters that can help orient the isomer distribution, depending on the reaction conditions. Step 2 is kinetically controlled by the relative rates of hydrogen shifts, alkyl shifts, and protonated cyclopropane formation, and it is thermodynamically controlled by the relative stabilities of the secondary and tertiary ions. (This area is thoroughly studied see Chapter 3.) Step 3, however, is kinetically controlled by the hydride transfer from excess of the starting hydrocarbon and by the relative thermodynamic stability of the various hydrocarbon isomers. 

The discussion to this point has emphasized kinetics of catalytic reactions on a uniform surface where only one type of active site participates in the reaction. Bifunctional catalysts operate by utilizing two different types of catalytic sites on the same solid. For example, hydrocarbon reforming reactions that are used to upgrade motor fuels are catalyzed by platinum particles supported on acidified alumina. Extensive research revealed that the metallic function of Pt/Al203 catalyzes hydrogenation/dehydrogenation of hydrocarbons, whereas the acidic function of the support facilitates skeletal isomerization of alkenes. The isomerization of n-pentane (N) to isopentane (I) is used to illustrate the kinetic sequence associated with a bifunctional Pt/Al203 catalyst ... 

Related to their similar pore diameter and pore structure, unsurprisingly the Henry adsorption constants for linear alkanes are very close to each other on zeolite ZSM-22 and ZSM-23 (Table I). Somewhat higher constants are obtained for 2- and 3-methylbranched alkanes on ZSM-23 compared to zeolite ZSM-22. The adsorption constants of linear alkanes are obviously hi er than branched alkanes on the two cases. The separation power of a zeolite between a linear and a branched hydrocarbon may be given by the separation factor (a), which is the ratio of Henry consteints of linear and branched molecules at a certain temperature, a values at 523 K are given for both zeolites in Table 1. For comparison, values for ZSM-5 are also included, which is one of the most popular shape selective catalyst used in isomerization reactions. From this table it can be seen that both ZSM-22 and ZSM-23 have higher separation constants compared to ZSM-5. The zeolites can be listed in the following order with respect to their separation capacity between linear and 2- and 3-methylbranched alkanes ZSM-22 > ZSM-23 > ZSM-5. In narrow pore structures such as zeolites ZSM-22 and ZSM-23 it is very probable that linear alkanes with smaller kinetic diameters have more access to the available adsorption sites compared to the more bulky branched molecules. This may be regarded as the first... 

The catalytic properties of H-, Li-, Na-, K-, Mg-, Ca-, Zn-, Cd-, and Al-forms of synthetic mordenite in the reactions of cyclohexane and n-pentane isomerization and benzene hydrogenation have been studied. The cation forms of mordenite that do not involve the metals of column VIII of the Mendeleyev Table show high activity in these reactions. To elucidate the mechanism of n-pentane isomerization, the kinetics of the reaction on H-mordenite have been studied. Carbonium ion is supposed to result from splitting off hydride ion from hydrocarbon molecule. Na-mordenite catalytic activity in benzene hydrogenation reaction decreases linearly with the increase of decationization. This indicates that cations are responsible for the catalytic activity of zeolite. The high activity of cations of nontransition metals in oxidation-reduction reactions seems to be quite unexpected and may provide evidence for some uncommon mechanism of benzene hydrogenation. 

Thus, study of the kinetics of n-pentane isomerization on H-mordenite leads to the conclusion that the mechanism of the reaction in question is different from that of isomerization on bifunctional and metal-zeolite catalysts. This difference lies in the manner of carbonium ion formation. With bifunctional catalysts, carbonium ion originates with the attachment of a proton to the olefin molecule, while with H-mordenite it originates as a result of splitting off hydride ion from the saturated molecule of the starting hydrocarbon by mordenite proton, as has been suggested by the above reaction scheme. 

The kinetic parameters (apparent activation energies, orders versus hydrogen and hydrocarbon) have been determined for all the isomerization and hydrocracking reactions of n-pentane and 2-methylbutane on a Pt/AljOj catalyst of low dispersion (10% Pt d = 90 A) 40). n-Pentane-2- C and 2-methylbutane-2- C were used to estimate the contributions of cyclic type and bond shift isomerization, respectively. As shown in Table II, the reactions... 

Another important difference between oxidation of Ci-C2 and C3+ hydrocarbons is the appearance in the latter case of degeneration of the primary alkyl radicals. Already in the case of propane, the existence of two isomeric forms of propyl species (not always taken into account) can lead to substantial kinetic consequences because of the distinct difference in their thermochemistry and reactivity. Even certain reaction channels may vary depending on the isomeric form of propyl radicals. This factor may cause a substantial uncertainty especially in the case of modeling of catalytic oxidation due to a poor knowledge about thermochemistry and reactivity of surface active sites and chemisorbed species. 

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