Dehydrocyclization

Mesitylene can be synthesized from acetone by catalytic dehydrocyclization (17). Similarly, cyclotrimerization of acetylenes has produced PMBs such as hexamethylbenzene (18). Durene has been recovered from Methanex s methanol-to-gasoline (MTG) plant in New Zealand (19). 

Of the main reactions, aromatization takes place most readily and proceeds ca 7 times as fast as the dehydroisomerization reaction and ca 20 times as fast as the dehydrocyclization. Hence, feeds richest in cycloparaftins are most easily reformed. Hydrocracking to yield paraffins having a lower boiling point than feedstock proceeds at about the same rate as dehydrocyclization. 

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. 

Attempted dehydrocyclization of the 6-acylhydrazinopyrimidine 65 by heating with polyphosphoric acid led, instead, to pyrimidine ring rupture, yielding the l,l-diamino-2-nitro-2-(3-phenyl-l,2,4-triazol-5-yl)ethene 66. Cyclocondensation of the latter with triethyl orthoformate gave the fully aromatic triazolopyrimidine 67 (94JHC1171) (Scheme 23). 

Increasing the octane number of a low-octane naphtha fraction is achieved by changing the molecular structure of the low octane number components. Many reactions are responsible for this change, such as the dehydrogenation of naphthenes and the dehydrocyclization of paraffins to aromatics. Catalytic reforming is considered the key process for obtaining benzene, toluene, and xylenes (BTX). These aromatics are important intermediates for the production of many chemicals. 

Aromatization. The two reactions directly responsible for enriching naphtha with aromatics are the dehydrogenation of naphthenes and the dehydrocyclization of paraffins. The first reaction can he represented hy the dehydrogenation of cyclohexane to benzene. 

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. 

It should be noted that both reactions leading to aromatics (dehydrogenation of naphthenes and dehydrocyclization of paraffins) produce hydrogen and are favored at lower hydrogen partial pressure. 

For more aromatics yield, the end point of the feed may be raised to include higher molecular weight hydrocarbons in favor of hydrocracking and dehydrocyclization. However, excessive hydrocracking is not desirable because it lowers liquid yields. 

Catalytic reformers are normally designed to have a series of catalyst beds (typically three beds). The first bed usually contains less catalyst than the other beds. This arrangement is important because the dehydrogenation of naphthenes to aromatics can reach equilibrium faster than the other reforming reactions. Dehydrocyclization is a slower reaction and may only reach equilibrium at the exit of the third reactor. Isomerization and hydrocracking reactions are slow. They have low equilibrium constants and may not reach equilibrium before exiting the reactor. 

The second and third reactors contain more catalyst than the first one to enhance the slow reactions and allow more time in favor of a higher yield of aromatics and branched paraffins. Because the dehydrogenation of naphthenes and the dehydrocyclization of paraffins are highly endothermic, the reactor outlet temperature is lower than the inlet temperature. The effluent from the first and second reactors are reheated to compensate for the heat loss. 

Aromatization of paraffins can occur through a dehydrocyclization reaction. Olefinic compounds formed by the beta scission can form a carbocation intermediate with the configuration conducive to cyclization. For example, if a carbocation such as that shown below is formed (by any of the methods mentioned earlier), cyclization is likely to occur. 

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... 

Pt-Re-alumina catalysts were prepared, using alumina containing potassium to eliminate the support acidity, in order to carry out alkane dehydrocyclization studies that paralleled earlier work with nonacidic Pt-alumina catalysts. The potassium containing Pt-Re catalyst was much less active than a similar Pt catalyst. It was speculated that the alkali metal formed salts of rhenic acid to produce a catalyst that was more difficult to reduce. However, the present ESCA results indicate that the poisoning effect of alkali in Pt-Re catalysts is not primarily due to an alteration in the rhenium reduction characteristics. 

The purpose of this article is to focus on a single series of reactions and to illustrate some of these uses of isotopic tracers. The set of reactions involves the dehydrocyclization of n-paraffins into aromatics over non-acidic Te NaX zeolite (4-7). 

According to this scheme, the catalyst serves primarily to promote dehydrogenation. Cyclization of the hexatriene was shown years ago (JJ.) to occur thermally in the gas phase at temperatures well below these dehydrocyclization conditions. Thus, the overall reaction is projected to be the combination of several catalytic dehydrogenation steps and a non-catalytic cyclization step. This projection implies that the design of the catalytic reactor may be important in order to optimize the ratio of void space for cyclization and catalyst space for dehydrogenation. 

We have explored rare earth oxide-modified amorphous silica-aluminas as "permanent" intermediate strength acids used as supports for bifunctional catalysts. The addition of well dispersed weakly basic rare earth oxides "titrates" the stronger acid sites of amorphous silica-alumina and lowers the acid strength to the level shown by halided aluminas. Physical and chemical probes, as well as model olefin and paraffin isomerization reactions show that acid strength can be adjusted close to that of chlorided and fluorided aluminas. Metal activity is inhibited relative to halided alumina catalysts, which limits the direct metal-catalyzed dehydrocyclization reactions during paraffin reforming but does not interfere with hydroisomerization reactions. 

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