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reforming produces reformate with octane numbers on the order of 90 to 95 Catalytic reforming is conducted in the presence of hydrogen over hydrogenation-dehydrogenation catalysts, which may be supported on alumina or silica-alumina Depending on the catalyst, a definite sequence of reactions takes place, involving structural changes in the feedstock This more modern concept actually rendered thermal reforming somewhat obsolescent The commercial processes available for use can be broadly classified as the moving bed, fluid bed, and fixed bed types The fluid bed and moving bed processes used mixed nonprecious metal oxide catalysts in units equipped with separate regeneration facilities Fixed bed processes use predominantly platinum-containing catalysts in units equipped for cycle, occasional, or no regeneration Catalytic reformer feeds are saturated (ie, not olefinic) materials; in the majority of cases that feed may be a straight-run naphtha but other by-product low-octane naphtha (eg, coker naphtha) can be processed after treatment to remove olefins and other contaminants Hydrocracker naphtha that contains substantial quantities of naphthenes is also a suitable feed Dehydrogenation is a main chemical reaction in catalytic reforming and hydrogen gas is consequently produced in large quantities The hydrogen is recycled though the reactors where the reforming takes place to provide the atmosphere necessary for the chemical reactions and also prevents the carbon from being deposited on the catalyst, thus extending its operating life An excess of hydrogen above whatever is consumed in the process is produced, and, as a result, catalytic reforming processes are unique in that they are the only petroleum refinery processes to produce hydrogen as a by-product Catalytic reforming usually is carried out by feeding a naphtha (after pretreating with hydrogen if necessary) and hydrogen mixture to a furnace where the mixture is heated to the desired temperature, 450 to 520 C (842 968 F), and then passed through fixed bed catalytic reactors at hydrogen pressures of 100 to 1000 psi (7 68 atm) (Fig 312) Normally several reactors are used in series with heaters located between adjoining reactors in order to compensate for the endothermic reactions taking place Sometimes as many as four or five reactors are kept on stream in series while one or more is being regenerated
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FIGURE 312 Catalytic reforming
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CHAPTER THREE
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The composition of a reforming catalyst is dictated by the composition of the feedstock and the desired reformate The catalysts used are principally molybdena-alumina, chromiaalumina, or platinum on a silica-alumina or alumina base The nonplatinum catalysts are widely used in regenerative process for feeds containing, for example, sulfur, which poisons platinum catalysts, although pretreatment processes (eg, hydrodesulfurization) may permit platinum catalysts to be employed The purpose of platinum on the catalyst is to promote dehydrogenation and hydrogenation reactions, that is, the production of aromatics, participation in hydrocracking, and rapid hydrogenation of carbon-forming precursors For the catalyst to have an activity for isomerization of both paraffins and naphthenes the initial cracking step of hydrocracking and to participate in paraffin dehydrocyclization, it must have an acid activity The balance between these two activities is most important in a reforming catalyst In fact, in the production of aromatics from cyclic saturated materials (naphthenes), it is important that hydrocracking be minimized to avoid loss of the desired product and, thus, the catalytic activity must be moderated relative to the case of gasoline production from a paraffinic feed, where dehydrocyclization and hydrocracking play an important part
337 Isomerization Processes Catalytic reforming processes provide high-octane constituents in the heavier gasoline fraction but the normal paraffin components of the lighter gasoline fraction, especially butanes, pentanes, and hexanes, have poor octane ratings The conversion of these normal paraffins to their isomers (isomerization) yields gasoline components of high octane rating in this lower boiling range Conversion is obtained in the presence of a catalyst (aluminum chloride activated with hydrochloric acid), and it is essential to inhibit side reactions such as cracking and olefin formation Isomerization processes are to provide additional feedstock for alkylation units or high-octane fractions for gasoline blending (Table 35) Straight-chain paraffins (n-butane, n-pentane, n-hexane) are converted to respective isocompounds by continuous catalytic
TABLE 35 Component Streams for Gasoline Boiling range Stream Paraffinic Butane Conversion Isopentane Producing process C 0 27 F 32 81
Distillation Distillation Conversion Isomerization Alkylation Isomerization Distillation Hydrocracking Catalytic cracking Steam cracking Polymerization Catalytic reforming
Alkylate Isomerate Naphtha Hydrocrackate Olefinic Catalytic naphtha Cracked naphtha Polymer Aromatic Catalytic reformate
40 150 40 70 30 100 40 200 40 200 40 200 60 200 40 200
104 302 104 158 86 212 104 392 104 392 104 392 140 392 104 392
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