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    • 4. 发明申请
    • Method for the production of defined mixtures of thf, bdo and gbl by gas phase hydrogenation
    • US20070135650A1
    • 2007-06-14
    • US10581074
    • 2004-12-04
    • Markus RoschRolf PinkosMichael HesseStephan SchlitterHenrik JunickeOlga SchubertAlexander WeckGunther Windecker
    • Markus RoschRolf PinkosMichael HesseStephan SchlitterHenrik JunickeOlga SchubertAlexander WeckGunther Windecker
    • C07D307/02
    • C07D307/33C07D307/08
    • 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.
    • 5. 发明授权
    • Method for the production of defined mixtures of THF, BDO and GBL by gas phase hydrogenation
    • 通过气相氢化制备THF,BDO和GBL的限定混合物的方法
    • US07442810B2
    • 2008-10-28
    • US10581074
    • 2004-12-04
    • Markus RoeschRolf PinkosMichael HesseStephan SchlitterHenrik JunickeOlga SchubertAlexander WeckGunther Windecker
    • Markus RoeschRolf PinkosMichael HesseStephan SchlitterHenrik JunickeOlga SchubertAlexander WeckGunther Windecker
    • C07D307/00C07D307/02
    • C07D307/33C07D307/08
    • 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) hydrogenating in a gas phase a gas stream of C4 dicarboxylic acids and/or derivatives thereof over a particular catalyst at a particular pressure and temperature to give a stream mainly containing of optionally alkyl-substituted GBL and THF, b) removing any succinct anhydride, c) converting the products remaining predominantly in the gas phase in the partial condensation, THF, water and GBL 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 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.
    • 一种在可能地制备任选烷基取代的BDO,GBL和THF的混合物的方法,其通过在C 4 C 4羧酸和/或其衍生物的气相中进行两步氢化,其包括a)在 在特定的压力和温度下,将特定催化剂上的C 4 O 2羧酸和/或其衍生物的气流气相,得到主要含有烷基取代的GBL和THF的物流,b)除去 任何简单的酸酐,c)将部分冷凝,THF,水和GBL中主要保留在气相中的产物进行转化,得到包含BDO,GBL和THF的混合物的流,d)从产物中除去氢并将其再循环 进入氢化,e)蒸馏分离产物,THF,BDO,GBL和水,如果适当回收富含GBL的物流或适当排放,并蒸馏处理BDO,THF和GBL,并设定产物的比例 ,TH F,GBL和BDO相对于10重量%至100重量%的THF,0至90重量%的GBL​​和0至90重量%的BDO,仅通过改变两者中的温度 加氢区,如果合适的话也可以使用GBL再循环流。
    • 10. 发明申请
    • Method for the production of 1,4- butane-diol by combined gas-phase and liquid-phase hydrogenation
    • 通过组合气相和液相氢化生产1,4-丁二醇的方法
    • US20050267318A1
    • 2005-12-01
    • US10516923
    • 2003-06-10
    • Michael HesseStephan SchlitterHolger BorchertMarkus SchubertMarkus RoschNils BottkeRolf-Hartmuth FischerAlexander WeckGunther WindeckerGunnar Heydrich
    • Michael HesseStephan SchlitterHolger BorchertMarkus SchubertMarkus RoschNils BottkeRolf-Hartmuth FischerAlexander WeckGunther WindeckerGunnar Heydrich
    • B01J23/80C07B61/00C07C29/149C07C31/20C07C31/18
    • C07C29/149C07C31/207
    • The present invention relates to a process for preparing optionally alkyl-substituted 1,4-butanediol by two-stage catalytic hydrogenation in the gas phase of C4-dicarboxylic acids and/or of derivatives thereof having the following steps: a) introducing a gas stream of a C4-dicarboxylic acid or of a derivative thereof at from 200 to 300° C. and from 2 to 60 bar into a first reactor and catalytically hydrogenating it to a product which contains mainly optionally alkyl-substituted 7-butyrolactone; b) converting the product stream into the liquid phase; c) introducing the product stream obtained in this way into a second reactor at a temperature of from 100° C. to 240° C. and a pressure of from 20 to 250 bar and catalytically hydrogenating it in the liquid phase to optionally alkyl-substituted 1,4-butanediol; d) removing the desired product from by-products and any unconverted reactants; e) optionally recycling unconverted intermediates into one or both hydrogenation stages, said hydrogenation stages both using a catalyst which comprises ≦95% by weight, preferably from 5 to 95% by weight, in particular from 10 to 80% by weight, of CuO, and ≧5% by weight, preferably from 5 to 95% by weight, in particular from 20 to 90% by weight, of a support, said second reactor having a higher pressure than said first reactor, and the product mixture removed from said first reactor being introduced without further purification into said second reactor.
    • 本发明涉及通过在具有下列物质的C 4 - 二羧酸和/或其衍生物的气相中通过两阶段催化氢化制备任选的烷基取代的1,4-丁二醇的方法 步骤:a)将200-300℃和2-60巴的C 4-14二羧酸或其衍生物的气流引入第一反应器,并将其催化氢化至 主要含有烷基取代的7-丁内酯的产物; b)将产物流转化成液相; c)将以这种方式获得的产物流在100℃至240℃的温度和20至250巴的压力下引入第二反应器,并将其在液相中催化氢化为任选的烷基取代的 1,4-丁二醇 d)从副产物和任何未转化的反应物中除去所需的产物; e)任选地将未转化的中间体再循环到一个或两个氢化阶段中,所述氢化步骤均使用包含<= 95重量%,优选5至95重量%,特别是10至80重量%的CuO ,和> = 5重量%,优选5至95重量%,特别是20至90重量%的载体,所述第二反应器具有比所述第一反应器更高的压力,并将产物混合物从 所述第一反应器不经进一步纯化地引入所述第二反应器。