Method for the production of defined mixtures of thf, bdo and gbl by gas phase hydrogenation

摘要

The present invention provides a process for variably preparing mixtures of optionally alkyl-substituted BDO, GBL and THF by two-stage hydrogenation in the gas phase of C₄ dicarboxylic acids and/or derivatives thereof, which comprises a) in a first step in the gas phase, hydrogenating a gas stream of C₄ dicarboxylic acids and/or derivatives thereof over a catalyst at a pressure of from 2 to 100 bar and a temperature of from 200° C. to 300° C. in a first reactor in the presence of a catalyst in the form of shaped catalyst bodies having a volume of less than 20 mm³, said catalyst from 5 to 95% by weight of oxide of copper and from 5 to 95% by weight of an oxide having acidic sites, to give a stream mainly containing of optionally alkyl-substituted GBL and THF, b) removing any succinic anhydride formed by partial condensation, c) converting the products remaining predominantly in the gas phase in the partial condensation, THF, water and GBL, under the same pressure or under a pressure reduced by the pressure drops in the hydrogenation circuit and at a temperature of from 150 to 240° C., in a second reactor over a catalyst which <=95% by weight of CuO and from 5 to 95% by weight of one or more oxides selected from the group of ZnO, Al₂O₃, SiO₂, TiO₂, ZrO₂, CeO₂, MgO, CaO, SrO, BaO, La₂O₃ and Mn₂O₃ to give a stream comprising a mixture of BDO, GBL and THF, d) removing the hydrogen from the products and recycling it into the hydrogenation, e) distillatively separating the products, THF, BDO, GBL and water, if appropriate recycling a GBL-rich stream into the second reactor or if appropriate discharging it, and working up BDO, THF and GBL distillatively, and setting the ratio of the products, THF, GBL and BDO, relative to one another within the range from 10 to 100% by weight of THF, from 0 to 90% by weight of GBL and from 0 to 90% by weight of BDO only by varying the temperatures in the two hydrogenation zones and also if appropriate the GBL recycle stream.