Naphtha Reforming Reactions

The principal reforming reactions are shown in Table 6.14. The isomerization of -paraffins proceeds via a dehydrogenation step on the platinum component of the catalyst to an -olefin intermediate. The -olefin then migrates to the acidic alumina site and isomerizes to the iso-olefin. Finally the iso-olefin is hydrogenated to the isoparaffin by the platinum. This mechanism requires good dispersion of platinum on the highly acidic, chloride-treated alumina support. 

Similar mechanisms apply to the isomerization and dehydrocyclization of n-hexane to methyl cyclopentane and then benzene, as shown in Table 6.15. 

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A stripper column in a naphtha hydrotreating process unit needs to remove H2S, which is corrosive and could poison the catalyst in a downstream naphtha reforming unit. Another objective is to remove as much C5 as possible from the stripper bottom, as C5 does not contribute to the naphtha reforming reaction. 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

The previous example was a rather unique application and not a typical case for fluidization. Although some fluidized bed reactions are executed at elevated pressure, like the naphtha reforming, most are used at atmospheric or at low pressures. The proceeding conceptual sketch. Figure 8.2.4, gives the most important features of a fluid-bed, cataljdic reactor. 

In Europe, synthesis gas is mainly produced by steam reforming naphtha. Because naphtha is a mixture of hydrocarbons ranging approximately from C5-C10, the steam reforming reaction may be represented using n-heptane ... 

In addition to natural gas, steam reformers can be used on light hydrocarbons such as butane and propane and on naphtha with a special catalyst. Steam reforming reactions are highly endothermic and need a significant heat source. Often the residual fuel exiting the fuel cell is burned to supply this requirement. Fuels are typically reformed at temperatures of 760 to 980°C (1,400 to 1,800°F). 

Catalytic Naphtha Reforming Science and Technology, edited by George J. Antos, Abdullah M. Aitani, and Jose M. Parera Catalysis of Organic Reactions, edited by Mike G. Scares and Michael L. Prunier... 

A similar study reports the results of adding 100 ppm thiophene to As in the Palm et al. study,the catalyst is not described rather, it is identified only as a commercial naphtha reforming catalyst, presumably Pt-based. In their reactor, the reformate from the ATR step passes through separate high and low temperature shift reactors before being analyzed. Thus, it was not possible to determine the effect of sulfur on the reforming step alone, nor was any post-reaction characterization of the catalyst reported, for example to determine coke or sulfur content. Figure 16 shows the observed deactivation, as measured by a decrease in H2 and CO concentrations. 

Start-of-cycle kinetic lumps in KINPTR are summarized in Table V. A C5-light gas lump is required for mass balance. Thirteen hydrocarbon lumps are defined. The reforming kinetic behavior can be modeled without splitting the lumps into their individual isomers (e.g., isohexane and n-hexane). Also, the component distribution within the C5- lump can be described by simple correlations, as discussed later. The start-of-cycle reaction network that defines the interconversions between the 13 kinetic lumps is shown in Fig. 9. This reaction network results from kinetic studies on pure components and narrow boiling fractions of naphthas. It includes the basic reforming reactions... 

As seen in Figure 2.2 and from the corresponding discussion, dehydrocyclization is a key reaction in forming aromatic compounds.307 A study comparing dehydrocyclization over mono- and bifiinctional catalysts at atmospheric pressure and high pressure representative of naphtha reforming conditions concludes that primary aromatic products at all pressures are formed by direct six-carbon ring formation.313 Over bifunctional catalysts the acid-catalyzed cyclization is more rapid... 

Adiabatic with Intermediate Heat Transfer. Many tubular reactor systems use a series of adiabatic reactors with heating or cooling between the reactor vessels. For example, naphtha reforming has endothermic reactions of removing hydrogen from saturated cyclical naphthene hydrocarbons to form aromatics. The process has multiple adiabatic reactors with fired furnaces between the reactors to heat the material back up to the required reactor inlet temperature. 

A separate problem arises when the surface of the support bears non-metallic active centres. Such bifunctional catalysts are widely used in naphtha reforming and it has been suggested that a bifunctional mechanism may also operate in syngas reactions [35]. 

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