Paraffins dehydrocyclization

Paraffin dehydrogenation, isomerization, and dehydrocyclization Paraffin cracking and isomerization Alcohol -> olefin + H20 Paraffin hydrocracking Olefin polymerization,... 

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. 

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. 

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. 

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). 

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. 

The predominant reaction during reforming is dehydrogenation of naphthenes. Important secondary reactions are isomerization and dehydrocyclization of paraffins. All three reactions result in high-octane products. 

Other reactions may also occur. These include carbon formation, hydrocracking or thermal cracking, dehydrocyclization of paraffins to naphthenes, and dehydrogenation of naphthenes to aromatics. These have been discussed in the deactivation of reforming catalysts, in Section 2. 

The hydrocarbon-type analysis of the Platformate discussed above was based on the product having an octane number of 92.9 (F-l plus 3 ml. of tetraethyllead per gallon). The aromatic content (based on charge) increases continually with increased severity. At the two highest severities, the aromatic yield (based on the charge) is in excess of the total naphthenes and aromatics present in the charge. This indicates the participation of the dehydrocyclization reaction of paraffins to form aromatics. 

The product coming out of the reactor consists of excess hydrogen and a reformate rich in aromatics. Typically the dehydrogenation of naphthenes approaches 100%. From 0% to 70% of the paraffins are dehydrocyclized. The liquid product from the separator goes to a stabilizer where light hydrocarbons are removed and sent to a debutanizer. The debutanized platformate is then sent to a splitter where Cg and C9 aromatics are removed. The platformate splitter overhead, consisting of benzene, toluene, and nonaromatics, is then solvent extracted (46). 

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. 

Bragin and co-workers found that over platinum-on-carbon catalysts, both paraffins and alkylaromatics follow zero-order kinetics. Activation energy for C5-dehydrocyclization in which the new bond is formed between two sp3 hybridized atoms is substantially less than the activation energy of cyclization in which the new bond is formed between one sp3 hybridized atom and the sp2 hybridized carbon atom of the aromatic ring. Over one batch of platinum-on-carbon catalyst, Bragin and co-workers obtained 20 kcal/mol and 27.5 kcal/mol activation energies for the dehydrocyclization of paraffins and monoalkylbenzenes, respectively (6). Another batch of platinum on carbon (which differed only in some minor details of preparation from the first batch), gave 14 kcal/mol for the cyclization of l-methyl-2-ethylbenzene and isooctane, and 29 kcal/mol for the cyclization of secondary butylbenzene ( ) (Fig. 1). 

Platinum-catalyzed cyclization of alkylaromatics is faster than the cyclization of paraffins because the presence of the aromatic ring enhances the rate. The rate of dehydrocyclization further increases with the number of aromatic rings in the feed molecule. A comparative study of the de-... 

Platinum catalyzes at least two types of C6- dehydrocyclization, one of which involves olefinic intermediates (13, 28, 29). In the case of paraffins, this latter reaction involves the ring-closure of hexatrienes (30, 31). In the C6-dehydrocyclization of n-butylbenzene and n-pentylbenzene, phenyl-butadiene and phenylpentadiene could correspond to these triene intermediates (13, 14). The second C6-dehydrocyclization mechanism is similar to C5-dehydrocyclization, and may not involve olefinic intermediates. 

Paraffins with more than eight carbon atoms can dehydrocyclize to form bicyclic products. According to Shuikin and Bekauri, bicyclic products can be formed from paraffins by either successive dehydrocyclization or by simultaneous closure of several carbon-carbon bonds (35). The second possibility follows Balandin s sextet model (56). A large number of hydrocarbons follow the consecutive mechanism (27). Thus far there is no evidence for simultaneous closure. 

There are at least two C6-dehydrocyclization mechanisms one of these proceeds through arylalkene intermediates and corresponds to the hexatriene-type C6-dehydrocyclization of paraffins. The other pathway is direct ring closure. It is probably related to C5-dehydrocyclization. 2-Butylnaphthalene may differentiate between the two mechanisms phenanthrene is probably formed by the first reaction, anthracene by the second. 

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