Olefin production, isobutane oxidation

C4 Alkenes. Several industrial processes have been developed for olefin production through catalytic dehydrogenation138 166 167 of C4 alkenes. All four butenes are valuable industrial intermediates used mostly for octane enhancement. Isobutylene, the most important isomer, and its dimer are used to alkylate isobutane to produce polymer and alkylate gasoline (see Section 5.5.1). Other important utilizations include oxidation to manufacture maleic anhydride (see Section 9.5.4) and hydroformylation (see Section 7.1.3). 

Isobutane oxidation is performed in the liquid phase at 130-160 °C and elevated pressures. Since this exceeds the critical temperature of isobutane (134 °C), products (TBA, t-butyl hydroperoxide (TBHP)) must be present to maintain a liquid phase. The epoxidation step is performed at 100-130 °C using 10-300 ppm of Mo. Since propene is a rather unreactive olefin, a high propene/TBHP molar ratio is used to suppress nonproductive decomposition of TBHP. The high propene concentration leads to very high operating pressures and high recycle costs. The PO and TBA products are purified by a combination of direct and extractive distillation. TBHP conversion and PO selectivity are in excess of 90 %. 

There are other commercial processes available for the production of butylenes. However, these are site or manufacturer specific, eg, the Oxirane process for the production of propylene oxide the disproportionation of higher olefins and the oligomerisation of ethylene. Any of these processes can become an important source in the future. More recentiy, the Coastal Isobutane process began commercialisation to produce isobutylene from butanes for meeting the expected demand for methyl-/ rZ-butyl ether (40). 

Some of the many uses of isobutane include the production of high-octane gasoline blending components by reacting it with various olefins in alkylation processes and the production of propylene oxide and tertiary butyl alcohol. 

Results obtained in an investigation of the pyrolyses of four alkanes (ethane, n-butane, isobutane and isopentane) in the presence of trace amounts of oxygen, at low extent of reaction and around 500 C, are reported. The organic products of the primary oxidation are mainly olefins. According to experimental conditions (particularly to wall conditions of the reaction vessel), oxygen accelerates or inhibits the alkane decomposition. Walls inhibit the oxygen consumption. These experimental facts are interpreted and compared with recent results in literature. 

MTBE is produced by reacting methanol with isobutene. Isobutene is contained in the C4 stream from steam crackers and from fluid catalytic cracking m the crude oil-refining process. However, isobutene has been in short supply in many locations. The use of raw materials other than isobutene for MTBE production has been actively sought. Figure 2 describes the reaction network for MTBE production. Isobutene can be made by dehydration of i-butyl alcohol, isomerization of -butenes [73], and isomerization and dehydrogenation of n-butane [74, 75]. t-Butanol can also react with methanol to form MTBE over acid alumina, silica, clay, or zeolite in one step [7678]. t-Butanol is readily available by oxidation of isobutane or, in the future, from syngas. The C4 fraction from the methanol-to-olefins process may be used for MTBE production, and the C5 fraction may be used to make TAME. It is also conceivable that these... 

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