Patent DE-102008007081-A1 (DE)
Title: Producing n-butene-oligomers and 1-butene from mixture-I made of hydrocarbons having four carbon atoms, comprises e.g. optionally washing the mixture to produce a mixture-II and removing 1,3-butadiene from mixture-I to produce a mixture-III
Inventor: PETERS UDO
IPC: C07C5/05
Filed: 2008-01-31
Abstract: Production of n-butene-oligomers and 1-butene from a technical mixture-I made of 4 carbon hydrocarbons, comprises: e.g. (a) optionally washing the technical mixture-I to produce a technical mixture-II; (b) removing 1,3-butadiene from technical mixture-I or -II to produce a technical mixture-III; and (c) separating the isobutene containing in the technical mixture-IIIa, by reacting with an excess of methanol in a two-stage methyl-tert-butylether-synthesis and separating the obtained methyl-tert-butylethers and the non-converted methanol under the production of a technical mixture-IV. Production of n-butene-oligomers and 1-butene from technical mixtures-I made of 4C-hydrocarbons, which contain at least 1-butene, isobutene, butane, 2-butene and many unsaturated 4C-hydrocarbons, comprises: (a) optionally washing the technical mixture-I under the production of a technical mixture-II; (b) removing of 1,3-butadiene from the technical mixture-I or -II under the production of a technical mixture-III; (c) separating the isobutene containing in the technical mixture-IIIa, which is identical with the technical mixture-III or is obtained by mixing the mixture-III with a 4C-hydrocarbon mixture, by reacting with an excess of methanol in a two-stage methyl-tert-butylether-synthesis and separating the obtained methyl-tert-butylethers and the non-converted methanol under the production of a technical mixture-IV, where the first step of the methyl-tert-butylether-synthesis is carried out in three solid bed reactors and the second step of the methyl-tert-butylether-synthesis is carried out on a solid acid ion-exchange resin, which exhibits sulfonic acid groups, in a reactive distillation column, which is operated in a pressure range of 0.5-1.5 MPa and at a temperature in the reaction zone of 50-90[deg] C at a reflux ratio of 0.5-1.5, (d) removing of many unsaturated 4C-hydrocarbons from the technical mixture-IV under the production of a technical mixture-V, by selective hydrogenation of many unsaturated 4C-hydrocarbon containing in the technical mixture, with hydrogen in liquid phase on a solid bed catalyst, which exhibits 0.1-2 mass-% of palladium on a carrier, in the presence of 0.05-10 mass-ppm of carbon monoxide, relative to the mass of the technical mixture-IV, at a temperature of 0-7500; (e) distillative separation of the technical mixture-V into a low boiling fraction L1, which contains 1-butene and isobutane and is largely free of n-butane and 2-butene, and into a high boiling fraction S1, which contains 2-butene and n-butane; (f) distillative separation of low boiling fraction L1 in 1-butene and isobutane; (g) optionally treating the high boiling fraction S1 with a molecular sieve with an average pore diameter of greater than 0.4-1.5 nm at a pressure of 0.1-5 MPa and a temperature of 20-160[deg] C under the production of technical mixture-VI; and (h) oligomerizing the n-butene containing in the high boiling fraction S1 or in the technical mixture-VI, under the production of oligomers at 0-200[deg] C and pressure of 0.1-7 MPa on a solid catalyst containing nickel, silicon and aluminum.