Olefinic hydrocarbons production

Fig. 6 Schematic drawing of ZSM5 catalyst bed deactivation. View of the fused silica reaction tube at about 40 % of catalyst life time. Black zone (I) of deactivated catalyst particles covered with coke ("methanol coke"). Small dark reaction zone (II) in which methanol conversion to 100 % occurs. Blue/grey zone (III) of active catalyst on which a small amount of "olefin coke" produced by the olefinic hydrocarbon product mixture has been deposited on the crystallite surfaces. The quartz particles before and behind the catalyst bed (zones 0) remain essentially white.

Alkylation combines lower-molecular-weight saturated and unsaturated hydrocarbons (alkanes and alkenes) to produce high-octane gasoline and other hydrocarbon products. Conventional paraffin-olefin (alkane-alkene) alkylation is an acid-catalyzed reaction, such as combining isobutylene and isobutane to isooctane. 

The feedstocks used ia the production of petroleum resias are obtaiaed mainly from the low pressure vapor-phase cracking (steam cracking) and subsequent fractionation of petroleum distillates ranging from light naphthas to gas oil fractions, which typically boil ia the 20—450°C range (16). Obtaiaed from this process are feedstreams composed of atiphatic, aromatic, and cycloatiphatic olefins and diolefins, which are subsequently polymerized to yield resias of various compositioas and physical properties. Typically, feedstocks are divided iato atiphatic, cycloatiphatic, and aromatic streams. Table 2 illustrates the predominant olefinic hydrocarbons obtained from steam cracking processes for petroleum resia synthesis (18). 

Coal tar is the condensation product obtained by cooling to approximately ambient temperature, the gas evolved in the destmctive distillation of coal. It is a black viscous Hquid denser than water and composed primarily of a complex mixture of condensed ring aromatic hydrocarbons. It may contain phenoHc compounds, aromatic nitrogen bases and their alkyl derivatives, and paraffinic and olefinic hydrocarbons. Coal-tar pitch is the residue from the distillation of coal tar. It is a black soHd having a softening point of 30—180°C (86—359°F). 

Volume of olefin/(volume of ionic liquid.hour). i-C = 2,2- and 2,3-dimethylbutanes, i-Cg = isooctanes, TMP trimethylpentanes, = hydrocarbon products with more than eight carbon atoms, Light ends = hydrocarbon products with fewer than eight carbon atoms, RON = research octane number, MON = motor octane number... 

Products from hydrocracking processes lack olefinic hydrocarbons. The product slate ranges from light hydrocarbon gases to gasolines to residues. Depending on the operation variables, the process could... 

Traditionally, iron-based catalysts have been used for FT synthesis when the syngas is coal derived, because of their activity in both FTS and WGS reactions. Complex mixtures of straight-chain paraffins, olefins, and oxygenate (in substantial proportions) compounds are known to be formed during iron-based FTS. Olefin selectivity of iron catalysts is typically greater than 50% of the hydrocarbon products at low carbon numbers, and more than 60% of the produced olefins are a-olefins.13 For iron-based catalysts, the olefin selectivity decreases asymptotically with increasing carbon number. 

The first commercial Fischer-Tropsch facility was commissioned in 1935, and by the end of the Second World War a total of fourteen plants had been constructed. Of these, nine were in Germany, one in France, three in Japan, and one in China. Both German normal-pressure and medium-pressure processes (Table 18.1) were employed. The cobalt-based low-temperature Fischer-Tropsch (Co-LTFT) syncrude produced in these two processes differed slightly (Table 18.2), with the product from the medium-pressure process being heavier and less olefinic.11 In addition to the hydrocarbon product, the syncrude also contained oxygenates, mostly alcohols and carboxylic acids. 

In a recent publication, Chang and Silvestri have discussed this reaction in detail (109). They reported that under conditions of low (ca. 10%) conversion substantial amounts of dimethyl ether, formed by the reversible dehydration of methanol, are present and 78% of the primary hydrocarbon product consists of C2-C4 olefins. Also, if dimethyl ether, in the absence of water, is used instead of methanol, essentially the same hydrocarbon product distribution is obtained. On the basis of these observations, Chang and Silvestri suggest the reaction path shown below ... 

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. 

Steady-state operation was quickly achieved under SCF conditions and the SCF-FT process has a marked effect on the hydrocarbon product distribution with a shift to higher carbon number products owing to enhanced heat and mass transfer from the catalyst surface. In addition, an obvious difference in the olefin content was observed where the 1-olefin content in the SCF phase was always higher than in the gas phase. Based on the experimental observations, a mechanistic explanation is provided for the difference of the reaction behavior under supercritical and gas-phase environments. 

A feature of the FT process is that the primary hydrocarbon products are linear alpha olefins. Since chain branching is a temperature sensitive secondary reaction, a higher yield of linear olefins is obtained when the FT process is operated at lower temperatures (eg see the data in Table III comparing the low temperature Arge with the high temperature Synthol process). 

The plausible deoxygenation routes for production of diesel like hydrocarbons from fatty acids and their derivates are decarboxylation, decarbonylation, hydrogenation and decarbonylation/hydrogenation. The main focus in this study is put on liquid phase decarboxylation and decarbonylation reactions, as depicted in Figure 1. Decarboxylation is carried out via direct removal of the carboxyl group yielding carbon dioxide and a linear paraffinic hydrocarbon, while the decarbonylation reaction yields carbon monoxide, water and a linear olefinic hydrocarbon. 

Water, carbon dioxide, olefin hydrocarbons, and alcohols are shown as products. It is obvious that other equations could be written showing the formation of hydrocarbons of other types—that is CH4, C2H6—and of the other oxygenates produced in this synthesis. Although Equations 8, 9, and 10 do not represent the reaction mechanism but simply express the stoichiometry of the system, they do indicate certain fundamental actions that... 

A new commercial use for butadiene is its employment in the nylon synthesis joining furfural, benzene, and cyclohexane as raw materials for nylon salt components. Amother olefinic hydrocarbon, which has found large scale application in recent years, is propylene tetramer, widely employed in reaction with aromatic nuclei to yield an alkylated aromatic base used in synthetic detergent production. 

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