Dehydrogenation reforming

Dehydrogenation (Reforming)17-20—to increase octane number of gasoline, to produce alkenes from alkanes [Eq. (1.2)], as well as aromatics, such as benzene, toluene, and xylenes [Eq. (1.3)] ... 

Dehydrogenation / reforming Pt/Al203 alkanes alkenes polymers, bulk chemicals... 

Oil refinery processes [catalytic cracking, isomerization, hydrogenation (dearomatization), dehydrogenation, reforming, steam reforming, desulfurization, metal removal, hydro-oxygenation, methane activation, etherification, benzene-toluene xylene (BTX) process]... 

Styrene is manufactured by alkylating benzene with ethene followed by dehydrogenation, or from petroleum reformate coproduction with propylene oxide. Styrene is used almost exclusively for the manufacture of polymers, of which the most important are polystyrene, ABS plastics and styrene-butadiene rubber. U.S. production 1980 3 megatonnes. 

It is produced from petroleum fractions rich in naphthenes by catalytic reforming in the presence of hydrogen (hydroforming) in this process dehydrogenation .nd dealkylation... 

The composition of a reforming catalyst is dictated by the composition of the feedstock and the desired reformate. The catalysts used are principally platinum or platinum—rhenium on an alumina base. The purpose of platinum on the catalyst is to promote dehydrogenation and hydrogenation reactions. Nonplatinum catalysts are used in regenerative processes for feedstocks containing sulfur, although pretreatment (hydrodesulfurization) may permit platinum catalysts to be employed. 

Catalytic Reforming. Worldwide, approximately 30% of commercial benzene is produced by catalytic reforming, a process ia which aromatic molecules are produced from the dehydrogenation of cycloparaffins, dehydroisomerization of alkyl cyclopentanes, and the cycHzation and subsequent dehydrogenation of paraffins (36). The feed to the catalytic reformer may be a straight-mn, hydrocracked, or thermally cracked naphtha fraction ia the... 

In the alkylcyclohexane (ACH) to aromatic equihbrium, ACH Ar, aromatics are favored by high temperatures and low pressures. Normal reforming conditions promote rapid ACH dehydrogenation and a high conversion to aromatics. 

The mechanistic steps are as follows paraffins dehydrogenate to olefins the olefins oligomerize and cyclize and the cycHcs aromatize. Because the first step is rate controlling, very Httie olefin is actually present. The BTX product is relatively free of nonaromatics and therefore is very desirable as a chemical feed. As in reforming, some C —C2 fuel gas is produced along with a valuable hydrogen stream. Prom a C —feed the BTX product is roughly 35 45 20, respectively. 

Catalysts in this service can deactivate by several different mechanisms, but deactivation is ordinarily and primarily the result of deposition of carbonaceous materials onto the catalyst surface during hydrocarbon charge-stock processing at elevated temperature. This deposit of highly dehydrogenated polymers or polynuclear-condensed ring aromatics is called coke. The deposition of coke on the catalyst results in substantial deterioration in catalyst performance. The catalyst activity, or its abiUty to convert reactants, is adversely affected by this coke deposition, and the catalyst is referred to as spent. The coke deposits on spent reforming catalyst may exceed 20 wt %. 

Reforming is the conversion primarily of naphthenes and alkanes to aromatics, but other reactions also occur under commercial conditions. Platinum or platinum/rhenium are the hydrogenation/ dehydrogenation component of the catalyst and alumina is the acid component responsible for skeletal rearrangements. 

Selecting the naphtha type can be an important processing procedure. For example, a paraffinic-base naphtha is a better feedstock for steam cracking units because paraffins are cracked at relatively lower temperatures than cycloparaffins. Alternately, a naphtha rich in cycloparaffins would be a better feedstock to catalytic reforming units because cyclo-paraffins are easily dehydrogenated to aromatic compounds. Table 2-5 is a typical analysis of naphtha from two crude oil types. 

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. 

The catalysts generally used in catalytic reforming are dual functional to provide two types of catalytic sites, hydrogenation-dehydrogenation sites and acid sites. The former sites are provided by platinum, which is the best known hydrogenation-dehydrogenation catalyst and the latter (acid sites) promote carbonium ion formation and are provided by an alumina carrier. The two types of sites are necessary for aromatization and isomerization reactions. 

This is also an endothermic reaction, and the equilibrium production of aromatics is favored at higher temperatures and lower pressures. However, the relative rate of this reaction is much lower than the dehydrogenation of cyclohexanes. Table 3-6 shows the effect of temperature on the selectivity to benzene when reforming n-hexane using a platinum catalyst. 

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. 

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