公开(公告)号：US06730800B2

公开(公告)日：2004-05-04

申请号：US10433425

申请日：2003-06-04

申请人： Rolf-Hartmuth Fischer ,  Frank Stein ,  Rolf Pinkos ,  Michael Hesse ,  Michael Jolyon Sprague ,  Markus Rösch ,  Holger Borchert ,  Stephan Schlitter ,  Ralf-Thomas Rahn ,  Alexander Weck

发明人： Rolf-Hartmuth Fischer ,  Frank Stein ,  Rolf Pinkos ,  Michael Hesse ,  Michael Jolyon Sprague ,  Markus Rösch ,  Holger Borchert ,  Stephan Schlitter ,  Ralf-Thomas Rahn ,  Alexander Weck

IPC分类号： C07D33102

CPC分类号： B01J23/72 ,  B01J23/80 ,  C07D307/08

摘要： Unsubstituted or alkyl-substituted THF is obtained by catalytic hydrogenation in the gas phase of C4-dicarboxylic acids and/or their derivatives using a catalyst comprising 20% by weight, preferably >30% by weight, in particular from 35 to 90% by weight, of an oxidic support having acid centers, at a hot spot temperature of from 240 to 310° C., preferably from 240 to 280° C., and a WHSV over the catalyst of from 0.01 to 1.0, preferably from 0.02 to 1, in particular from 0.05 to 0.5, kg of starting material/l of catalyst x hour.

摘要翻译： 未取代或烷基取代的THF通过使用包含<80重量％，优选<70重量％，特别是10至65重量％的催化剂在C4-二羧酸和/或其衍生物的气相中通过催化氢化获得， 重量的CuO和> 20重量％，优选> 30重量％，特别是35至90重量％的具有酸中心的氧化载体，在热点温度为240-310℃， 优选为240〜280℃，催化剂上的WHSV为0.01〜1.0，优选为0.02〜1，特别优选为0.05〜0.5kg的原料/ l催化剂x小时。

公开(公告)号：US07217679B2

公开(公告)日：2007-05-15

申请号：US10433008

申请日：2001-12-07

申请人： Holger Borchert ,  Stephan Schlitter ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Frank Stein ,  Ralf-Thomas Rahn ,  Alexander Weck

发明人： Holger Borchert ,  Stephan Schlitter ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Frank Stein ,  Ralf-Thomas Rahn ,  Alexander Weck

IPC分类号： B01J37/02

CPC分类号： C07D307/33 ,  B01J23/72 ,  B01J23/76 ,  B01J23/80 ,  B01J23/8926 ,  B01J37/0215 ,  B01J37/0223 ,  C07D307/08 ,  C07D315/00

摘要： A catalyst for the hydrogenation of C4-dicarboxylic acids and/or their derivatives, preferably maleic anhydride, in the gas phase comprises from 5 to 100% by weight, preferably from 40 to 90% by weight, of copper oxide and from 0 to 95% by weight, preferably from 10 to 60% by weight, of one or more metals or compounds thereof selected from the group consisting of Al, Si, Zn, Pd, La, Ce, the elements of groups III A to VIII A and groups I A and II A as active composition applied in the form of a thin layer to an inert support material.

摘要翻译： 在气相中用于氢化C 4 - 二羧酸和/或其衍生物，优选马来酸酐的催化剂包含5至100重量％，优选40至90重量％ 的氧化铜和0至95重量％，优选10至60重量％的一种或多种选自Al，Si，Zn，Pd，La，Ce的金属或其化合物，其元素为 作为活性组合物，将IIIA至VIIIA族和IAA和IIA族作为以薄层形式施用于惰性载体材料的活性组合物。

公开(公告)号：US06831182B2

公开(公告)日：2004-12-14

申请号：US10433424

申请日：2003-06-04

申请人： Holger Borchert ,  Stephan Schlitter ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Frank Stein ,  Ralf-Thomas Rahn ,  Alexander Weck ,  Gerd Kaibel

发明人： Holger Borchert ,  Stephan Schlitter ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Frank Stein ,  Ralf-Thomas Rahn ,  Alexander Weck ,  Gerd Kaibel

IPC分类号： C07D30708

CPC分类号： C07D307/08

摘要： The present invention relates to a process for the gas-phase hydrogenation of C4-dicarboxylic acids and/or their derivatives over a catalyst based on copper oxide to give substituted or unsubstituted &ggr;-butyrolactone and/or tetrahydrofuran, which comprises, which a first reaction zone in which the C4-dicarboxylic acid and/or its derivatives is/are reacted to give a mixture comprising a substituted or unsubstituted &ggr;-butyrolactone as main product and a subsequent second reaction zone in which the substituted or unsubstituted &ggr;-butyrolactone present in the mixture from the first hydrogenation step is reacted at a temperature lower than the temperature in the first hydrogenation step to give substituted or unsubstituted tetrahydrofuran.

公开(公告)号：US06958404B2

公开(公告)日：2005-10-25

申请号：US10450114

申请日：2001-12-07

申请人： Holger Borchert ,  Stephan Schlitter ,  Michael Hesse ,  Frank Stein ,  Rolf-Hartmuth Fischer ,  Ralf-Thomas Rahn ,  Alexander Weck ,  Markus Rösch

发明人： Holger Borchert ,  Stephan Schlitter ,  Michael Hesse ,  Frank Stein ,  Rolf-Hartmuth Fischer ,  Ralf-Thomas Rahn ,  Alexander Weck ,  Markus Rösch

IPC分类号： C07B61/00 ,  C07C51/36 ,  C07C55/10 ,  C07D307/08 ,  C07D307/33 ,  C07D307/58 ,  C07D307/60

CPC分类号： C07D307/33 ,  C07D307/08

摘要： C4-dicarboxylic acids or derivatives thereof are hydrogenated in the gas phase in a fluidized-bed reactor. It is possible to use catalyst compositions known per se.

摘要翻译： C 4 N 4 - 二羧酸或其衍生物在气相中在流化床反应器中氢化。 可以使用本身已知的催化剂组合物。

公开(公告)号：US06888011B2

公开(公告)日：2005-05-03

申请号：US10433012

申请日：2001-12-07

申请人： Holger Borchert ,  Stephan Schlitter ,  Markus Rösch ,  Rolf-Hartmuth Fischer ,  Ralf-Thomas Rahn ,  Alexander Weck

发明人： Holger Borchert ,  Stephan Schlitter ,  Markus Rösch ,  Rolf-Hartmuth Fischer ,  Ralf-Thomas Rahn ,  Alexander Weck

IPC分类号： B01J23/72 ,  B01J23/76 ,  B01J23/80 ,  B01J35/10 ,  B01J37/00 ,  B01J37/03 ,  C07B61/00 ,  C07D307/08 ,  C07D307/33 ,  C07D315/00

CPC分类号： C07D307/33 ,  B01J23/72 ,  B01J23/76 ,  B01J23/80 ,  B01J35/1061 ,  B01J35/1066 ,  B01J35/108 ,  B01J37/0018 ,  B01J37/03 ,  C07D307/08 ,  C07D315/00

摘要： A hydrogenation catalyst which is suitable, in particular, for the hydrogenation of maleic anhydride and its derivatives to THF or its derivatives comprises copper oxide and at least one further metal or compound thereof, preferably an oxide, selected from the group consisting of Al, Si, Zn, La, Ce, the elements of groups IIIA to VIIIA and the elements of groups IA and IIA and having a pore volume of ≧0.01 ml/g for pore diameters of >50 nm and a ratio of the pore volume of macropores having a diameter of >50 nm to the total pore volume for pores having a diameter of >4 nm of >10%.

摘要翻译： 特别适用于马来酸酐及其衍生物氢化成THF或其衍生物的氢化催化剂包含氧化铜和至少一种其它金属或其化合物，优选选自Al，Si ，Zn，La，Ce，IIIA至VIIIA族的元素和IA和IIA族的元素，孔径> 50nm的细孔容积> 0.01ml / g，孔的孔体积比 具有> 50nm的直径> 50nm的直径> 10nm的孔的总孔体积。

公开(公告)号：US07307040B2

公开(公告)日：2007-12-11

申请号：US10482645

申请日：2002-07-03

申请人： Stephan Schlitter ,  Holger Borchert ,  Michael Hesse ,  Markus Schubert ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Gunnar Heydrich ,  Alexander Weck

发明人： Stephan Schlitter ,  Holger Borchert ,  Michael Hesse ,  Markus Schubert ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Gunnar Heydrich ,  Alexander Weck

IPC分类号： B01J23/56 ,  B01J23/00

CPC分类号： B01J23/8926 ,  B01J37/0201 ,  B01J37/0223 ,  B01J37/03 ,  C07D307/08

摘要： A catalyst for the hydrogenation of C4-dicarboxylic acids and/or derivatives thereof, preferably maleic anhydride, in the gas phase comprises a) 20-94% by weight of copper oxide (CuO), preferably 40-92% by weight of CuO, in particular 60-90% by weight of CuO, and b) 0.005-5% by weight, preferably 0.01-3% by weight, in particular 0.05-2% by weight, palladium and/or a palladium compound (calculated as metallic palladium) and c) 2-79.995% by weight, preferably 5-59.99% by weight, in particular 8-39.95% by weight, of an oxidic support selected from the group consisting of the oxides of Al, Si, Zn, La, Ce, the elements of groups IIIA to VIIIA and of groups IA and IIA of the Periodic Table of the Elements.

摘要翻译： 在气相中用于氢化C 4-14 - 二羧酸和/或其衍生物，优选马来酸酐的催化剂包括a）20-94重量％的氧化铜（CuO），优选40 -92重量％的CuO，特别是60-90重量％的CuO，和b）0.005-5重量％，优选0.01-3重量％，特别是0.05-2重量％的钯和/或 钯化合物（以金属钯计算）和c）2-79.995重量％，优选5-59.99重量％，特别是8-39.95重量％的选自Al的氧化物的氧化物载体 ，Si，Zn，La，Ce，元素周期表IIIA至VIIIA族和IA和IIA族的元素。

公开(公告)号：US07351311B2

公开(公告)日：2008-04-01

申请号：US10505774

申请日：2003-02-28

申请人： Gunther Windecker ,  Alexander Weck ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Nils Bottke ,  Michael Hesse ,  Stephan Schlitter ,  Holger Borchert

发明人： Gunther Windecker ,  Alexander Weck ,  Rolf-Hartmuth Fischer ,  Markus Rösch ,  Nils Bottke ,  Michael Hesse ,  Stephan Schlitter ,  Holger Borchert

IPC分类号： B01D3/14 ,  C07D307/08

CPC分类号： B01D3/146 ,  C07D307/08 ,  Y10S203/20

摘要： Crude water-containing tetrahydrofuran is purified by passing the crude tetrahydrofuran through three distillation columns, withdrawing water from the bottom of the first column, recycling water-containing tetrahydrofuran from the top of the second column into the first column, passing a sidestream of the first column into the second column, recycling the bottom product of the third column into the first column, and withdrawing a distillate at the top of the first column. Additionally, a sidestream of the second column is passed into the third column and the purified tetrahydrofuran is recovered as the top product of the third column.

摘要翻译： 通过将粗四氢呋喃通过三个蒸馏塔，从第一塔的底部排出水，将含水四氢呋喃从第二塔的顶部再循环到第一塔中，将第一个塔 塔进入第二列，将第三塔的底部产物回收到第一塔中，并且抽出第一塔顶部的馏出物。 此外，将第二塔的侧流送入第三塔，回收纯化的四氢呋喃作为第三塔的顶部产物。

公开(公告)号：US07271299B2

公开(公告)日：2007-09-18

申请号：US10516922

申请日：2003-06-11

申请人： Michael Hesse ,  Stephan Schlitter ,  Holger Borchert ,  Markus Schubert ,  Markus Rösch ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Alexander Weck ,  Gunther Windecker ,  Gunnar Heydrich

发明人： Michael Hesse ,  Stephan Schlitter ,  Holger Borchert ,  Markus Schubert ,  Markus Rösch ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Alexander Weck ,  Gunther Windecker ,  Gunnar Heydrich

IPC分类号： C07C31/18

CPC分类号： C07C29/149 ,  C07C31/207

摘要： Optionally alkyl-substituted 1,4-butanediol is prepared from C4-dicarboxylic acids and/or of derivatives thereof by: a) a gas stream of the C4-dicarboxylic acid or the derivative thereof in a first reactor in the gas phase to obtain a product which contains mainly optionally alkyl-substituted γ-butyro-lactone; b) removing succinic anhydride from the product of step a); c) catalytically hydrogenating the product of step b) in a second reactor in the gas phase to obtain optionally alkyl-substituted 1,4-butanediol; d) removing the desired product from intermediates, by-products and any unconverted reactants; and e) optionally recycling unconverted intermediates into one or both hydrogenation stages. The catalysts employed in each of the hydrogenation stages comprise ≦95% by weight of CuO, and ≦5% by weight of an oxidic support, and the second reactor has a higher pressure than the first reactor.

摘要翻译： 任选地，烷基取代的1,4-丁二醇由C 4-14二羧酸和/或其衍生物通过以下方法制备：a）引入C 4 - 二羧酸或其衍生物在气相中的第一反应器中，以获得主要含有烷基取代的γ-丁内酯的产物; b）从步骤a）的产物中除去琥珀酸酐; c）在气相中的第二反应器中催化氢化步骤b）的产物以获得任选的烷基取代的1,4-丁二醇; d）从中间体，副产物和任何未转化的反应物中除去所需的产物; 和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。 在每个氢化阶段中使用的催化剂包含<95重量％的CuO和<= 5重量％的氧化载体，并且第二反应器具有比第一反应器更高的压力。

公开(公告)号：US07169958B2

公开(公告)日：2007-01-30

申请号：US10516923

申请日：2003-06-10

申请人： Michael Hesse ,  Stephan Schlitter ,  Holger Borchert ,  Markus Schubert ,  Markus Rösch ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Alexander Weck ,  Gunther Windecker ,  Gunnar Heydrich

发明人： Michael Hesse ,  Stephan Schlitter ,  Holger Borchert ,  Markus Schubert ,  Markus Rösch ,  Nils Bottke ,  Rolf-Hartmuth Fischer ,  Alexander Weck ,  Gunther Windecker ,  Gunnar Heydrich

IPC分类号： C07C29/132 ,  C07C29/149 ,  C07C29/136 ,  C07C29/147

CPC分类号： C07C29/149 ,  C07C31/207

摘要： 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 γ-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.

摘要翻译： 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 主要含烷基取代的γ-丁内酯的产品; 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。

公开(公告)号：US07193091B2

公开(公告)日：2007-03-20

申请号：US10505706

申请日：2003-02-28

申请人： Rolf-Hartmuth Fischer ,  Markus Rösch ,  Nils Bottke ,  Alexander Weck ,  Gunther Windecker ,  Michael Hesse ,  Holger Borchert ,  Stephan Schlitter

发明人： Rolf-Hartmuth Fischer ,  Markus Rösch ,  Nils Bottke ,  Alexander Weck ,  Gunther Windecker ,  Michael Hesse ,  Holger Borchert ,  Stephan Schlitter

IPC分类号： C07D207/267 ,  C07D307/02

CPC分类号： C07D207/267 ,  C07D307/08

摘要： A process for coproducing alkyl-substituted or unsubstituted THF and pyrrolidones by catalytically hydrogenating C4-dicarboxylic acids and/or derivatives thereof in the gas phase in the presence of copper catalysts and reacting GBL with ammonia or primary amines to give pyrrolidones.

摘要翻译： 在铜催化剂存在下，在气相中催化氢化C4-二羧酸和/或其衍生物，共同生产烷基取代或未取代的THF和吡咯烷酮的方法，并使GBL与氨或伯胺反应得到吡咯烷酮。