公开(公告)号：US5387753A

公开(公告)日：1995-02-07

申请号：US174319

申请日：1993-12-30

Applicant: John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

Inventor： John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

IPC: B01J23/72 ,  B01J23/889 ,  B01J23/90 ,  B01J38/10 ,  C07B61/00 ,  C07C27/02 ,  C07C29/10 ,  C07C29/149 ,  C07C31/00 ,  C07C31/20 ,  C07C31/27 ,  C07C35/14 ,  C07C27/04 ,  C07C31/135 ,  C07C31/18 ,  C07C33/14

CPC classification number: B01J23/8892 ,  C07C29/149 ,  C07C35/14 ,  Y02P20/584

Abstract: A process is described for reactivating an at least partially deactivated copper-containing ester hydrogenation catalyst which has undergone deactivation through use in hydrogenation of an unsaturated organic compound selected from esters of C.sub.8 to C.sub.22 monocarboxylic acids, diesters of dicarboxylic acids, and lactones, to yield a corresponding hydroxylic compound selected from alcohols and diols which comprises contacting the at least partially deactivated copper-containing catalyst at an effective reactivation temperature and for an effective period of time with a stream of hydrogen-containing gas which is substantially free from the unsaturated organic compound thereby to reactivate the at least partially deactivated copper-containing catalyst.

Abstract translation: 描述了一种方法，用于重新激活至少部分失活的含铜酯氢化催化剂，其通过用于氢化选自C8至C22单羧酸的酯，二羧酸和内酯的二酯的不饱和有机化合物而失活，以产生 选自醇和二醇的相应的羟基化合物，其包括使所述至少部分失活的含铜催化剂在有效的再活化温度下和有效的一段时间内与基本上不含不饱和有机化合物的含氢气体流接触 从而使至少部分失活的含铜催化剂再活化。

公开(公告)号：US5395991A

公开(公告)日：1995-03-07

申请号：US175545

申请日：1993-12-30

Applicant: John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

Inventor： John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

IPC: C07C29/136 ,  C07B61/00 ,  C07C29/149 ,  C07C31/02 ,  C07C31/20 ,  C07C31/27 ,  C07C29/147 ,  C07C27/04 ,  C07C29/143

CPC classification number: C07C29/149 ,  C07C31/276 ,  C07C2101/14 ,  Y02P20/584

Abstract: A hydrogenation process is described for the production of a hydroxylic compound selected from alcohols and diols by hydrogenation of a corresponding unsaturated organic compound selected from esters, diesters and lactones which involves use of two hydrogenation zones (11, 36), each containing a charge of a hydrogenation catalyst (12, 37). In a first phase of operation one of the hydrogenation zones (36 or 11) is in standby condition and a stream of hot hydrogen-containing gas is passed therethrough. Meanwhile a vaporous feed stream comprising a hydrogen-containing gas and the unsaturated organic compound to be hydrogenated, e.g. dimethyl 1,4-cyclohexanedicarboxylate, is fed to the active zone (11 or 36). This feed stream can include the gas stream from the first mentioned hydrogenation zone (36 or 11). In a second phase of operation the roles of the reactors (11, 36) are switched so that the zone (36 or 11) previously in reactivation condition becomes the active zone whilst the zone that was formerly active (11 or 36) goes into reactivation condition and its partially deactivated catalyst charge is reactivated by the hot hydrogen-containing gas stream.

Abstract translation: 描述了氢化方法，用于通过氢化选自酯，二酯和内酯的相应的不饱和有机化合物来制备选自醇和二醇的羟基化合物，其包括使用两个氢化区（11,36），每个含有 氢化催化剂（12,37）。 在第一阶段的操作中，一个氢化区（36或11）处于待机状态，热的含氢气体流通过。 同时，包含含氢气体和待氢化的不饱和有机化合物的气态进料流，例如。 1,4-环己烷二羧酸二甲酯进料到活性区（11或36）。 该进料流可以包括来自第一个所述氢化区（36或11）的气流。 在第二阶段操作中，反应器（11,36）的作用被切换，使得先前处于再活化状态的区域（36或11）变为活性区域，而先前有活性的区域（11或36）进入再活化 条件和其部分失活的催化剂装料通过含氢气的气流再活化。

公开(公告)号：US06204395B1

公开(公告)日：2001-03-20

申请号：US09554239

申请日：2000-06-29

Applicant: Michael W. M. Tuck ,  Michael A. Wood ,  Andrew G. Hiles

Inventor： Michael W. M. Tuck ,  Michael A. Wood ,  Andrew G. Hiles

IPC: C07D30708

CPC classification number: C07D315/00 ,  C07C29/149 ,  C07C31/207

Abstract: A process is described for the production of butane-1,4-diol, &ggr;-butyrolactone and/or tetrahydrofuran. A vaporous stream containing maleic anhydride, water, and carbon oxides is contact in an absorption zone with a high boiling ester as solvent to form a solution of maleic anhydride in the high boiling ester which has a boiling point at the atmospheric pressure at least about 30° C. higher than that of maleic anhydride and is selected from di-(C1 to C4 alkyl) esters of alkyl dicarboxylic acids containing up to 3 carbon atoms, mono- and di-(C10 to C18 alkyl) esters of maleic acid, fumaric acid, succinic acid, and mixtures thereof, (C1 to C4 alkyl) esters of naphthalene-monocarboxylic acids, tri-(C1 to C4 alkyl) esters of aromatic tricarboxylic acids, and di-(C1 to C4 alkyl) esters of isophthalic acid. The maleic anhydride in the solution is stripped with a gaseous stream containing hydrogen thereby forming a vaporous stream comprising hydrogen and maleic anhydride, which is contacted in a hydrogenation zone with a heterogeneous hydrogenation catalyst to convert maleic anhydride to at least one C4 compound selected from butane-1,4-diol, &ggr;-butyrolactone and tetrahydrofuran.

Abstract translation: 描述了制备丁烷-1,4-二醇，γ-丁内酯和/或四氢呋喃的方法。 含有马来酸酐，水和碳氧化物的气流在吸收区与高沸点酯作为溶剂接触，形成马来酸酐在高沸点酯中的溶液，其沸点在大气压至少约30℃ ℃，高于马来酸酐，并且选自含有至多3个碳原子的烷基二羧酸的二（C1-C4烷基）酯，马来酸的单 - 和二 - （C 10 -C 18烷基）酯，富马酸 酸，琥珀酸及其混合物，萘 - 一元羧酸的（C1-C4烷基）酯，芳族三羧酸的三（C1-C4烷基）酯和间苯二甲酸的二（C1-C4烷基）酯。 溶液中的马来酸酐用含有氢气的气流汽提，从而形成包含氢气和马来酸酐的蒸气流，其在氢化区与非均相氢化催化剂接触以将马来酸酐转化成至少一种选自丁烷的C 4化合物 -1,4-二醇，γ-丁内酯和四氢呋喃。

公开(公告)号：US5395987A

公开(公告)日：1995-03-07

申请号：US175502

申请日：1993-12-30

Applicant: Colin Rathmell ,  Richard C. Spratt ,  Michael W. M. Tuck

Inventor： Colin Rathmell ,  Richard C. Spratt ,  Michael W. M. Tuck

IPC: B01J23/889 ,  C07B61/00 ,  C07C27/02 ,  C07C29/149 ,  C07C31/27 ,  C07C31/13 ,  C07C27/04

CPC classification number: C07C31/276 ,  C07C29/149 ,  C07C2101/14

Abstract: A continuous process is described for the production of 1,4-cyclohexanedimethanol (CHDM) having a desired or predetermined trans-:cis- isomer ratio by catalytic hydrogenation of a dialkyl 1,4-cyclohexanedicarboxylate in the presence of an ester hydrogenation catalyst. The process is capable of being operated for an extended period of time during which the hydrogenation catalyst declines in catalytic activity and comprises feeding a vaporous mixture of the dialkyl 1,4-cyclohexanedicarboxylate and hydrogen to a hydrogenation zone containing the hydrogenation catalyst and recovering CHDM product. The degree of conversion of the dialkyl 1,4-cyclohexanedicarboxylate at a particular combination of temperature and pressure is related to the trans-:cis- isomer ratio of the CHDM product and may be varied by adjusting at least one feed condition selected from (i) the dialkyl 1,4-cyclohexanedicarboxylate feed rate and (ii) the hydrogen-containing gas:dialkyl 1,4-cyclohexanedicarboxylate molar ratio. As catalyst activity declines during operation of the process over an extended period of time at a particular combination of temperature and pressure, the degree of conversion of the dialkyl 1,4-cyclohexanedicarboxylate and/or the trans-:cis- isomer ratio of the CHDM product may be maintained at a constant value by adjusting at least one of the feed conditions referred to above. The determination of the Actual Activity and Reference Activity of the catalyst and the Actual and Effective Residence Times are included in the hydrogenation process.

Abstract translation: 描述了在酯加氢催化剂存在下通过催化氢化1,4-环己烷二羧酸二烷基酯生产具有所需或预定的反式 - 顺式 - 异构体比例的1,4-环己烷二甲醇（CHDM）的连续方法。 该方法能够长时间运行，在此期间氢化催化剂催化活性下降，并且包括将1,4-环己烷二羧酸二烷基酯和氢气的蒸气混合物进料到含氢化催化剂的氢化区和回收CHDM产物 。 在特定的温度和压力组合下，1,4-环己烷二羧酸二烷基酯的转化度与CHDM产物的反式 - 顺式 - 异构体比例有关，并且可以通过调节至少一种进料条件来改变，所述进料条件选自（i ）1,4-环己烷二羧酸二烷基酯进料速率和（ii）含氢气体：1,4-环己烷二羧酸二烷基酯摩尔比。 随着催化剂活性在特定的温度和压力组合下长时间运行过程中催化剂活性下降，1,4-环己烷二羧酸二烷基酯的转化率和/或CHDM的反式 - 顺式异构体比例 可以通过调节至少一种上述进料条件将产物保持在恒定值。 催化剂的实际活性和参考活性的确定以及实际和有效的停留时间包括在加氢过程中。

公开(公告)号：US06274743B1

公开(公告)日：2001-08-14

申请号：US09555015

申请日：2000-06-29

Applicant: Michael W. M. Tuck ,  Philip H. D. Eastland ,  Andrew G. Hiles ,  Graham Reed

Inventor： Michael W. M. Tuck ,  Philip H. D. Eastland ,  Andrew G. Hiles ,  Graham Reed

IPC: C07D30702

CPC classification number: C07C29/172 ,  C07C29/149 ,  C07D307/08 ,  C07C31/207

Abstract: Butane-1,4-diol, gamma-butyrolactone or tetrahydrofuran are prepared by vapor phase hydrogenation of a C4-dicarboxylic acid derivative. A maleic anhydride containing vapor stream is contacted in an absorption zone with a first high boiling solvent. A waste gas stream is passed to a scrubbing zone containing a second, higher boiling solvent. The waste gas is purged and the first and second solvents are recovered and recycled. Maleic anhydride is obtained from the absorption zone and converted to a maleic acid diester, which is stripped from the first solvent with hydrogen. The desired products are obtained by hydrogenation.

Abstract translation: 通过C4-二羧酸衍生物的气相氢化制备丁烷-1,4-二醇，γ-丁内酯或四氢呋喃。 含有马来酸酐的蒸气流在吸收区与第一高沸点溶剂接触。 将废气流送至含有第二较高沸点溶剂的洗涤区。 净化废气，回收和回收第一和第二溶剂。 马来酸酐由吸收区获得并转化成马来酸二酯，其用氢气从第一溶剂中汽提。 所需产物通过氢化获得。

公开(公告)号：US5406004A

公开(公告)日：1995-04-11

申请号：US175546

申请日：1993-12-30

Applicant: Philip H. D. Eastland ,  John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

Inventor： Philip H. D. Eastland ,  John Scarlett ,  Michael W. M. Tuck ,  Michael A. Wood

IPC: B01J23/42 ,  B01J23/60 ,  B01J23/72 ,  B01J23/889 ,  B01J23/89 ,  C07B53/00 ,  C07B61/00 ,  C07C29/141 ,  C07C29/145 ,  C07C29/149 ,  C07C31/125 ,  C07C31/20 ,  C07C31/27 ,  C07C31/13

CPC classification number: C07C31/276 ,  C07C29/149 ,  C07B2200/09 ,  C07C2101/14

Abstract: A process is described for the production of a hydroxylic compound selected from alcohols and diols by hydrogenation of a corresponding hydrogenatable material selected from monoesters of carboxylic acids, monoesters of dicarboxylic acids, diesters of dicarboxylic acids, lactones, and mixtures of two or more thereof which comprises:(a) providing a hydrogenation zone containing a charge of a granular heterogeneous ester hydrogenation catalyst;(b) supplying to the hydrogenation zone a vaporous feed stream containing hydrogen and a hydrogenatable material selected from monoesters of carboxylic acids, monoesters of dicarboxylic acids, diesters of dicarboxylic acids, lactones, and mixtures of two or more thereof, at an inlet temperature which is above the dew point of the mixture;(c) maintaining the hydrogenation zone under temperature and pressure conditions which are conducive to effecting hydrogenation of esters;(d) recovering from the hydrogenation zone a two phase product stream containing a hydroxylic compound selected from alcohols and diols at an exit temperature which is below its dew point.In a preferred process the hydrogenatable material comprises dimethyl cyclohexanedicarboxylate.

Abstract translation: 描述了通过氢化可选择的可羧化材料的羧酸，二羧酸的单酯，二羧酸的二酯，内酯以及它们的两种或更多种的混合物来制备选自醇和二醇的羟基化合物的方法。 包括：（a）提供含有粒状非均相酯加氢催化剂装料的氢化区; （b）向加氢区供应含有氢气和可氢化材料的气态进料流，所述氢气和可氢化材料选自羧酸的单酯，二羧酸的单酯，二羧酸的二酯，内酯，以及它们的两种或多种的混合物， 高于混合物的露点; （c）在有利于酯化氢化的温度和压力条件下保持氢化区; （d）从氢化区回收含有选自醇和二醇的羟基化合物的出口温度低于其露点的两相产物流。 在优选的方法中，可氢化材料包括环己烷二羧酸二甲酯。

公开(公告)号：US5254758A

公开(公告)日：1993-10-19

申请号：US820655

申请日：1992-02-12

Applicant: Andrew G. Hiles ,  Michael W. M. Tuck

Inventor： Andrew G. Hiles ,  Michael W. M. Tuck

IPC: B01J23/86 ,  C07B61/00 ,  C07C5/02 ,  C07C29/141 ,  C07C29/149 ,  C07C29/17 ,  C07C29/20 ,  C07C31/20 ,  C07C209/48 ,  C07C5/10 ,  C07C29/145

CPC classification number: C07C29/177 ,  C07C29/141 ,  C07C29/149 ,  C07C29/175

Abstract: In a hydrogenation process, an organic feedstock, such as an unsaturated organic compound containing at least one unsaturated linkage selected from >C.dbd.C C.dbd.O, --C.tbd.C--, and --C.tbd.N, is contacted with hydrogen in a hydrogenation zone under vapor phase hydrogenation conditions in the presence of a heterogeneous hydrogenation catalyst characterized in that the hydrogenation zone includes first and second hydrogenation reactors connected in parallel, each containing a respective charge of the hydrogenation catalyst, that in a first phase of operations a vaporous mixture containing the organic feedstock and hydrogen is supplied to the first hydrogenation reactor only, that in a second phase of operation subsequent to the first phase the vaporous mixture is supplied to the second hydrogenation reactor only, and that in a third phase of operation subsequent to the second phase the vaporous mixture is supplied simultaneously both to the first hydrogenation reactor and to the second hydrogenation reactor.

Abstract translation: PCT No.PCT / GB90 / 01167 Sec。 371日期：1992年2月12日 102（e）日期1992年2月12日PCT提交1990年7月27日PCT公布。 公开号WO91 / 01961 日本1991年2月21日。在氢化方法中，有机原料，例如含有至少一个选自C = C，C = O，-C 3 -C（C）和-C 在非均相氢化催化剂的存在下，在气相氢化条件下，氢化区在氢化区中与氢接触，其特征在于氢化区包括平行连接的第一和第二氢化反应器，每个氢化反应器各自含有氢化催化剂， 在第一阶段操作中，含有有机原料和氢气的混合气体仅供应给第一氢化反应器，在第一阶段之后的第二阶段中，将蒸气混合物仅供应至第二氢化反应器， 在第二阶段之后的第三阶段中，将蒸汽混合物同时供应至第一氢化反应器a d到第二加氢反应器。

公开(公告)号：US5310954A

公开(公告)日：1994-05-10

申请号：US828903

申请日：1992-01-31

Applicant: Andrew G. Hiles ,  Michael W. M. Tuck

Inventor： Andrew G. Hiles ,  Michael W. M. Tuck

IPC: C07D307/08

CPC classification number: C07D307/08

Abstract: Separation of tetrahydrofuran (THF) from a mixture containing water, THF and a lower alkanol such as ethanol or methanol, is achieved by distillation in two zones, the vaporous mixture from the first zone being condensed and redistilled at a higher pressure in the second zone. Substantially pure THF is recovered from a lower part of the second zone, while the vapor from the top of the second zone is combined with the vapor from the first zone prior to condensation and the resulting condensate forms the liquid feed to the second zone. The process is suitable for recovering THF from complex reaction mixtures, containing also butane-1,4-diol and gamma-butyrolactone, obtained by hydrogenation of a dialkyl maleate.

Abstract translation: PCT No.PCT / GB90 / 01166 Sec。 371日期：1992年1月31日 102（e）日期1992年1月31日PCT提交1990年7月27日PCT公布。 出版物WO91 / 01981 日期：1991年2月21日。通过蒸馏在两个区域中，从含有水，THF和低级链烷醇如乙醇或甲醇的混合物中分离四氢呋喃（THF），将来自第一区的蒸气混合物冷凝并重新蒸馏 第二区域的压力较高。 基本上纯的THF从第二区的下部回收，而来自第二区的顶部的蒸气在冷凝之前与来自第一区的蒸气组合，并且所得的冷凝物形成液体进料至第二区。 该方法适用于通过马来酸二烷基酯氢化得到的复合反应混合物中还含有丁烷-1,4-二醇和γ-丁内酯来回收THF。