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FUELS FROM PETROLEUM AND HEAVY OIL
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(aluminum chloride, noble metals) processes Natural gasoline or light straight-run gasoline can provide feed by first fractionating as a preparatory step High volumetric yields (>95 percent) and 40 to 60 percent conversion per pass are characteristic of the isomerization reaction Aluminum chloride was the first catalyst used to isomerize butane, pentane, and hexane Since then, supported metal catalysts have been developed for use in high-temperature processes which operate in the range 370 to 480 C (698 896 F) and 300 to 750 psi (20 51 atm) (Fig 313), while aluminum chloride plus hydrogen chloride are universally used for the low-temperature processes Nonregenerable aluminum chloride catalyst is employed with various carriers in a fixed-bed or liquid contactor Platinum or other metal catalyst processes utilized fixed bed operation and can be regenerable or nonregenerable The reaction conditions vary widely depending on the particular process and feedstock, [40 480 C (104 896 F)] and 150 to 1000 psi (10 68 atm)
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Isomerization reactor To fuel gas Organic chloride make-up
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C5+ Make-up reject gas Isomerized butanes recycle
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FIGURE 313 A butane isomerization unit
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338 Alkylation Processes The combination of olefins with paraffins to form higher isoparaffins is termed alkylation Since olefins are reactive (unstable) and are responsible for exhaust pollutants, their conversion to high-octane isoparaffins is desirable when possible In refinery practice, only isobutane is alkylated, by reaction with isobutene or normal butene and isooctane is the product Although alkylation is possible without catalysts, commercial processes use aluminum chloride, sulfuric acid, or hydrogen fluoride as catalysts, when the reactions can take place at low temperatures, minimizing undesirable side reactions, such as polymerization of olefins Alkylate is composed of a mixture of isoparaffins which have octane numbers that vary with the olefins from which they were made Butylenes produce the highest octane numbers, propylene the lowest and pentylenes the intermediate values All alkylates, however, have high octane numbers (>87) which makes them particularly valuable The alkylation reaction as now practiced is the union, through the agency of a catalyst, of an olefin (ethylene, propylene, butylene, and amylene) with isobutane to yield high-octane branched-chain hydrocarbons in the gasoline boiling range Olefin feedstock
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CHAPTER THREE
is derived from the gas produced in a catalytic cracker, while isobutane is recovered by refinery gases or produced by catalytic butane isomerization To accomplish this, either ethylene or propylene is combined with isobutane at 50 to 280 C (122 536 F) and 300 to 1000 psi (20 68 atm) in the presence of metal halide catalysts such as aluminum chloride Conditions are less stringent in catalytic alkylation; olefins (propylene, butylene, or pentylene) are combined with isobutane in the presence of an acid catalyst (sulfuric acid or hydrofluoric acid) at low temperatures and pressures [1 40 C (34 104 F) and 148 150 psi (1 10 atm)] (Fig 314)
Recycle isobutane Feedstock
Reactor
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FIGURE 314 An alkylation unit (sulfuric acid catalyst)
Sulfuric acid, hydrogen fluoride, and aluminum chloride are the general catalysts used commercially Sulfuric acid is used with propylene and higher boiling feeds, but not with ethylene, because it reacts to form ethyl hydrogen sulfate The acid is pumped through the reactor and forms an air emulsion with reactants, and the emulsion is maintained at 50 percent acid The rate of deactivation varies with the feed and isobutane charge rate Butene feeds cause less acid consumption than the propylene feeds Aluminum chloride is not currently used as an alkylation catalyst but when employed, hydrogen chloride is used as a promoter and water is injected to activate the catalyst as an aluminum chloride/hydrocarbon complex Hydrogen fluoride is used for alkylation of higher boiling olefins and the advantage of hydrogen fluoride is that it is more readily separated and recovered from the resulting product
339 Polymerization Processes Polymerization is the process by which olefin gases are converted to liquid products which may be suitable for gasoline (polymer gasoline) or other liquid fuels The feedstock usually consists of propylene and butylenes from cracking processes or may even be selective olefins for dimer, trimer, or tetramer production Polymerization may be accomplished thermally or in the presence of a catalyst at lower temperatures Thermal polymerization is regarded as not being as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that cannot be induced to react by catalysts The process consists of vapor-phase cracking of, for example, propane and butane followed by prolonged periods at the high temperature [510 595 C (950 1103 F)] for the reactions to proceed to near completion
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