Platinum dehydrocyclization

The nature of the metal Dehydrogenating properties are important for Cg dehydrocyclization. Platinum, palladium, iridium, and rhodium... 

Dehydrocyclization refers to the conversion of feed paraffins into alkylcyclohexane and alkylcyclopentane naphthenes. These, in turn, are subsequently converted by isomerization and dehydrogenation into aromatics. Dehydrocyclization is controlled by both acid and platinum functions and is the most sensitive indicator of catalyst selectivity. 

Powerforming is one tecnique used for aromatics chemical production. Powerforming uses a platinum catalyst to reform virgin naphthas. The principal reaction is the conversion of naphthenes in virgin naphthas to aromatics e.g., isomerization and dehydrocyclization reactions also occur in catalytic reforming. 

The second aromatization reaction is the dehydrocyclization of paraffins to aromatics. For example, if n-hexane represents this reaction, the first step would be to dehydrogenate the hexane molecule over the platinum surface, giving 1-hexene (2- or 3-hexenes are also possible isomers, but cyclization to a cyclohexane ring may occur through a different mechanism). Cyclohexane then dehydrogenates to benzene. 

Supported bimetallic Re—Pt catalysts are important in selective reforming of petroleum. It is believed that sulhding the catalyst before use gives ReS units which act as inert diluents to reduce the size of a local ensemble of platinum atoms. Selectivity for desirable dehydrocyclization and isomerization reactions... 

Fig. 12. Variation with average platinum particle diameter of the initial rate of reaction (isomerization plus dehydrocyclization) of n-hexane (- -) and 2-methylpentane (-O-) over ultrathin film catalysts at 275°C. Hydrogen/reactant hydrocarbon, 10/1 total reactant pressure 100 Torr.

Muller (ISO) has recently shown that the dehydrocyclization of 2,2,4,4-tetramethylpentane to 1,1,3,3-tetramethylcyclopentane occurs on thick polycrystalline platinum film catalysts with a rate that is comparable to the formation of 1,1,3-trimethylcyclopentane from 1,2,2-trimethyl-pentane. As Muller points out, reactions (10)—(12) cannot occur from 2,2,4,4-tetramethypentane, and it is clear that either these mechanisms are inadequate, or at least there must be an alternative mechanism available. Muller suggests mechanism (14) which requires two adjacent platinum sites. 

In hydrocarbon reforming processes the vapour of an alkane is passed over a supported metal catalyst such as platinum on silica or alumina. Dehydrocyclization, isomerization and cracking reactions all take place to... 

As previously mentioned, Davis (8) has shown that in model dehydrocyclization reactions with a dual function catalyst and an n-octane feedstock, isomerization of the hydrocarbon to 2-and 3-methylheptane is faster than the dehydrocyclization reaction. Although competitive isomerization of an alkane feedstock is commonly observed in model studies using monofunctional (Pt) catalysts, some of the alkanes produced can be rationalized as products of the hydrogenolysis of substituted cyclopentanes, which in turn can be formed on platinum surfaces via free radical-like mechanisms. However, the 2- and 3-methylheptane isomers (out of a total of 18 possible C8Hi8 isomers) observed with dual function catalysts are those expected from the rearrangement of n-octane via carbocation intermediates. Such acid-catalyzed isomerizations are widely acknowledged to occur via a protonated cyclopropane structure (25, 28), in this case one derived from the 2-octyl cation, which can then be the precursor... 

While a majority of laboratory-scale dehydrocyclization studies involve carefully chosen feedstocks, often a single alkane, commercial operators use a naphtha fraction consisting of a complex mixture of hydrocarbons. At least some of these will be incapable of easily undergoing direct dehydrocyclization and need to be isomerized into reactive structures if aromatics are to be formed. The work of Davis suggests that the acidity of dual function catalysts is an important added factor in these isomerizations, one which likely complements the different set of isomerizations that may be catalyzed by the platinum function. 

Dehydrocyclization, 30 35-43, 31 23 see also Cyclization acyclic alkanes, 30 3 7C-adsorbed olefins, 30 35-36, 38-39 of alkylaromatics, see specific compounds alkyl-substituted benzenes, 30 65 carbene-alkyl insertion mechanism, 30 37 carbon complexes, 32 179-182 catalytic, 26 384 C—C bond formation, 30 210 Q mechanism, 29 279-283 comparison of rates, 28 300-306 dehydrogenation, 30 35-36 of hexanes over platintim films, 23 43-46 hydrogenolysis and, 23 103 -hydrogenolysis mechanism, 25 150-158 iridium supported catalyst, 30 42 mechanisms, 30 38-39, 42-43 metal-catalyzed, 28 293-319 n-hexane, 29 284, 286 palladium, 30 36 pathways, 30 40 platinum, 30 40 rate, 30 36-37, 39... 

The first metallic catalyst used for dehydrocyclization of alkanes (/) was platinum on carbon (10-40 w/w% metal). It is typically used around atmospheric pressure and temperatures not exceeding 300°C. Such catalysts are inadequate for praetical purposes. This is the reason for commercial dual-function catalysts—typically platinum on silica-alumina—having been developed 32). 

Cg Dehydrocyclization. Arguments have been put forward that primary ring closure produces six-membered rings over three important catalyst types oxides, supported platinum, and bimetallic catalysts (107). The postulation of metal catalyzed Cg ring closure does not involve any definite suggestion whether its mechanism is direct or stepwise. ... 

Stepped surfaces withstand cyclic oxidation-reduction treatments (146) like [111] and some other low-index planes. Steps have either [311] or [110] structures. They are claimed to be the only places where orbital hybridization does not take place (136). No wonder that such platinum (138) and iridium (147) surfaces have enhanced activity in Cg dehydrocyclization of n-heptane. 

Hydroprocessing and special absorption techniques are utilized to remove sulfur and nitrogen from the reformer. If not removed through hydroprocessing, feedstock sulfur will be converted to H2S in the reformer. The H2S will then serve as a poison to the platinum reformer catalyst and diminish the dehydrogenation and dehydrocyclization reactions. When present, H2S can neutralize the acid sites on the catalyst diminishing the ability of the catalyst to promote isomerization, dehydrocyclization, and hydrocracking reactions. 

The platforming catalyst was the first example of a reforming catalyst having two functions.43 44 93 100-103 The functions of this bifunctional catalyst consist of platinum-catalyzed reactions (dehydrogenation of cycloalkanes to aromatics, hydrogenation of olefins, and dehydrocyclization) and acid-catalyzed reactions (isomerization of alkanes and cycloalkanes). Hyrocracking is usually an undesirable reaction since it produces gaseous products. However, it may contribute to octane enhancement. n-Decane, for example, can hydrocrack to C3 and C7 hydrocarbons the latter is further transformed to aromatics. 

McHenry and co-workers (Ml) have suggested that platinum on alumina catalysts, which are active for the dehydrocyclization of paraffins,... 

The formation of aromatics by the catalytic dehydrocyclization of paraffins with chains of six or more carbon atoms has been known for some time. Certain oxides of the 5th and 6th subgroups of the periodic table, such as chromia and molybdena, were shown early to be particularly effective catalysts for the reaction. Consequently, most of the reported studies of the kinetics and mechanism of the reaction have been carried out using these catalysts (P6, H4, H5). Since the available data on the kinetics of dehydrocyclization over oxide catalysts have been reviewed by Steiner (S9) in 1956, only a brief summary of the work will be made here, primarily for the purpose of orientation. The relatively few kinetic data which have been reported for dehydrocyclization over the bifunctional platinum on acidic oxide catalysts will be discussed subsequent to this. 

As a result of the studies discussed above, a reasonably consistent picture of the kinetics and mechanism of the dehydrocyclization reaction over oxide catalysts has evolved. However, as pointed out earlier in this section, relatively few kinetic data have been reported for dehydrocyclization over platinum-alumina reforming-type catalysts. The data which have been reported include those of Hettinger and co-workers (H7), who studied the dehydrocyclization of re-heptane over platinum catalysts. These investigators found that the rate of dehydrocyclization decreased with increasing total pressure at a constant hydrogen-to-hydrocarbon ratio (Fig. 9). They also reported that the extent of dehydrocyclization was substantially greater for re-nonane than for re-heptane, which is consistent with the results obtained on oxide catalysts. In a later study of the kinetics... 

Fig. 9. Effect of total pressure on dehydrocyclization of n-heptane over platinum-alumina catalyst (H7). Conditions 496°C., H2/HC = 5/1.

The dehydrocyclization of alkylaromatics was first described more than four decades ago. In 1936 Moldavskii and Kamusher reported the formation of naphthalene from u-butylbenzene on chromia at 475°C (7, 2). In 1945 Herington and Rideal reported the formation of indene from w-propyl-benzene over chromia-alumina (3). Platinum-containing catalysts were first used for these reactions in 1956 by Kazanskii and co-workers 4-6). 

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