公开(公告)号：US08962895B2

公开(公告)日：2015-02-24

申请号：US14001120

申请日：2012-02-24

申请人： Juntao Liu ,  Weimin Yang ,  Lei Li ,  Wanmin Wang ,  Linna Zhang ,  Haifeng Song

发明人： Juntao Liu ,  Weimin Yang ,  Lei Li ,  Wanmin Wang ,  Linna Zhang ,  Haifeng Song

IPC分类号： C07C29/149 ,  B01J8/06

CPC分类号： C07C29/149 ,  B01J8/067 ,  B01J2208/0053 ,  Y02P20/52 ,  C07C31/202

摘要： The present invention relates to a method for the production of ethylene glycol using a feedstock comprising an oxalate and a catalyst containing copper and/or a copper oxide, comprising contacting the feedstock with the catalyst in a reactor under the conditions of a temperature in the range from about 170 to about 270° C., a weight hourly space velocity of the oxalate in the range from about 0.2 to about 5 h−1, a molar ratio of hydrogen to the oxalate in the range from about 40:1 to about 200:1 and a reaction pressure in the range from about 1.5 to about 10 MPa, to produce an effluent containing ethylene glycol, in which the reactor is a tube-array reactor using partitioned heat exchange and adopting outer and inner tubes configured in a double-tube structure to facilitate the heat exchange of the catalyst.

摘要翻译： 本发明涉及使用包含草酸盐和含有铜和/或氧化铜的催化剂的原料生产乙二醇的方法，包括在反应器中在等温范围内的温度条件下将反应器与催化剂接触 约170至约270℃，草酸盐的重时空速在约0.2至约5小时-1的范围内，氢与草酸的摩尔比在约40:1至约200的范围内 ：1，反应压力在约1.5至约10MPa的范围内，以产生含有乙二醇的流出物，其中反应器是使用分隔热交换的管阵列反应器，并采用配置在双组分中的外管和内管， 管结构以促进催化剂的热交换。

公开(公告)号：US08921592B2

公开(公告)日：2014-12-30

申请号：US13702280

申请日：2011-06-09

申请人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Lei Li

发明人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Lei Li

IPC分类号： C07C69/36 ,  C07C67/36 ,  B01J23/44

CPC分类号： C07C67/36 ,  B01J23/44 ,  C07C69/36

摘要： A process of producing oxalate by CO gas phase method includes the following steps: a) introducing nitrite salt, water and an inorganic acid first into a reactor I to produce a NO containing effluent I; and separating the resultant effluent to obtain the effluent II of NO; b) introducing the effluent II of NO, a C1-C4 alkanol and oxygen into a reactor II to be subjected to the reaction, and separating the resultant effluent to obtain the effluent IV of C1-C4 alkyl nitrites; c) introducing the effluent IV of C1-C4 alkyl nitrites and a CO gas stream into a coupling reactor where they are reacted to produce a NO containing effluent VI. The reactor I and/or the reactor II are preferably rotating supergravity reactors. Therefore, the process is applicable to the industrial production of oxalate by CO gas phase method.

摘要翻译： 通过CO气相法制备草酸盐的方法包括以下步骤：a）首先将亚硝酸盐，水和无机酸引入反应器I中以产生含NO的流出物I; 并分离出所得的流出物，得到NO的流出物II; b）将NO，C1-C4链烷醇和氧气的流出物II引入待反应的反应器II中，并分离得到的流出物，得到C1-C4烷基亚硝酸盐的流出物IV; c）将C1-C4烷基亚硝酸盐的流出物IV和CO气流引入偶联反应器中，在其中反应生成含NO的流出物VI。 反应器I和/或反应器II优选为旋转超重力反应器。 因此，该方法适用于CO气相法工业生产草酸盐。

公开(公告)号：US20130338406A1

公开(公告)日：2013-12-19

申请号：US14001120

申请日：2012-02-24

申请人： Juntao Liu ,  Weimin Yang ,  Lei Li ,  Wanmin Wang ,  Linna Zhang ,  Haifeng Song

发明人： Juntao Liu ,  Weimin Yang ,  Lei Li ,  Wanmin Wang ,  Linna Zhang ,  Haifeng Song

IPC分类号： C07C29/149

CPC分类号： C07C29/149 ,  B01J8/067 ,  B01J2208/0053 ,  Y02P20/52 ,  C07C31/202

摘要： The present invention relates to a method for the production of ethylene glycol using a feedstock comprising an oxalate and a catalyst containing copper and/or a copper oxide, comprising contacting the feedstock with the catalyst in a reactor under the conditions of a temperature in the range from about 170 to about 270° C., a weight hourly space velocity of the oxalate in the range from about 0.2 to about 5 h−1, a molar ratio of hydrogen to the oxalate in the range from about 40:1 to about 200:1 and a reaction pressure in the range from about 1.5 to about 10 MPa, to produce an effluent containing ethylene glycol, in which the reactor is a tube-array reactor using partitioned heat exchange and adopting outer and inner tubes configured in a double-tube structure to facilitate the heat exchange of the catalyst.

摘要翻译： 本发明涉及使用包含草酸盐和含有铜和/或氧化铜的催化剂的原料生产乙二醇的方法，包括在反应器中在等温范围内的温度条件下将反应器与催化剂接触 约170至约270℃，草酸盐的重时空速在约0.2至约5小时-1的范围内，氢与草酸的摩尔比在约40:1至约200的范围内 ：1，反应压力在约1.5至约10MPa的范围内，以产生含有乙二醇的流出物，其中反应器是使用分隔热交换的管阵列反应器，并采用配置在双组分中的外管和内管， 管结构以促进催化剂的热交换。

公开(公告)号：US20130079549A1

公开(公告)日：2013-03-28

申请号：US13702280

申请日：2011-06-09

申请人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Lei Li

发明人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Lei Li

IPC分类号： C07C67/36

CPC分类号： C07C67/36 ,  B01J23/44 ,  C07C69/36

摘要： A process of producing oxalate by CO gas phase method includes the following steps: a) introducing nitrite salt, water and an inorganic acid first into a reactor I to produce a NO containing effluent I; and separating the resultant effluent to obtain the effluent II of NO; b) introducing the effluent II of NO, a C1-C4 alkanol and oxygen into a reactor II to be subjected to the reaction, and separating the resultant effluent to obtain the effluent IV of C1-C4 alkyl nitrites; c) introducing the effluent IV of C1-C4 alkyl nitrites and a CO gas stream into a coupling reactor where they are reacted to produce a NO containing effluent VI. The reactor I and/or the reactor II are preferably rotating supergravity reactors. Therefore, the process is applicable to the industrial production of oxalate by CO gas phase method.

摘要翻译： 通过CO气相法制备草酸盐的方法包括以下步骤：a）首先将亚硝酸盐，水和无机酸引入反应器I中以产生含NO的流出物I; 并分离出所得的流出物，得到NO的流出物II; b）将NO，C1-C4链烷醇和氧气的流出物II引入待反应的反应器II中，并分离得到的流出物，得到C1-C4烷基亚硝酸盐的流出物IV; c）将C1-C4烷基亚硝酸盐的流出物IV和CO气流引入偶联反应器中，在其中反应生成含NO的流出物VI。 反应器I和/或反应器II优选为旋转超重力反应器。 因此，该方法适用于CO气相法工业生产草酸盐。

公开(公告)号：US09102583B2

公开(公告)日：2015-08-11

申请号：US14000876

申请日：2012-02-24

申请人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Jun Kuai

发明人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Jun Kuai

IPC分类号： C07C27/04 ,  C07C29/149 ,  B01J23/83 ,  B01J23/84 ,  B01J23/843 ,  B01J23/888 ,  B01J29/48

CPC分类号： C07C29/149 ,  B01J23/83 ,  B01J23/84 ,  B01J23/8437 ,  B01J23/888 ,  B01J29/48 ,  Y02P20/52 ,  C07C31/202

摘要： A process for producing ethylene glycol includes contacting an oxalate with a fluidized bed catalyst under the following conditions: a reaction temperature of from about 170 to about 270° C., a weight space velocity of oxalate of from about 0.2 to about 7 hours−1, a hydrogen/ester molar ratio of about 20˜200:1, a reaction pressure of from about 1.5 to about 10 MPa, and a reaction temperature difference T of from about 1 to about 15° C. The fluidized bed catalyst includes: a) from about 5 to about 80 parts by weight of copper and the oxide thereof, b) from about 10 to about 90 parts by weight of at least one carrier selected from silica, molecular sieve or alumina, c) from about 0.01 to about 30 parts by weight of bismuth and tungsten metallic elements or the oxides thereof, or cerium and niobium metallic elements or the oxides thereof.

摘要翻译： 制备乙二醇的方法包括在以下条件下使草酸盐与流化床催化剂接触：反应温度为约170至约270℃，草酸的重量空间速度为约0.2至约7小时-1 氢/酯摩尔比为约20〜200:1，反应压力为约1.5〜约10MPa，反应温度差T为约1〜约15℃。流化床催化剂包括： ）约5至约80重量份的铜及其氧化物，b）约10至约90重量份的至少一种选自二氧化硅，分子筛或氧化铝的载体，c）约0.01至约30 铋和钨金属元素或其氧化物或铈和铌金属元素或其氧化物的重量份。

公开(公告)号：US20130331617A1

公开(公告)日：2013-12-12

申请号：US14000876

申请日：2012-02-24

申请人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Jun Kuai

发明人： Weimin Yang ,  Juntao Liu ,  Wanmin Wang ,  Jun Kuai

IPC分类号： C07C29/149

CPC分类号： C07C29/149 ,  B01J23/83 ,  B01J23/84 ,  B01J23/8437 ,  B01J23/888 ,  B01J29/48 ,  Y02P20/52 ,  C07C31/202

摘要： A process for producing ethylene glycol includes contacting an oxalate with a fluidized bed catalyst under the following conditions: a reaction temperature of from about 170 to about 270° C., a weight space velocity of oxalate of from about 0.2 to about 7 hours−1, a hydrogen/ester molar ratio of about 20˜200:1, a reaction pressure of from about 1.5 to about 10 MPa, and a reaction temperature difference T of from about 1 to about 15° C. The fluidized bed catalyst includes: a) from about 5 to about 80 parts by weight of copper and the oxide thereof, b) from about 10 to about 90 parts by weight of at least one carrier selected from silica, molecular sieve or alumina, c) from about 0.01 to about 30 parts by weight of bismuth and tungsten metallic elements or the oxides thereof, or cerium and niobium metallic elements or the oxides thereof.

摘要翻译： 制备乙二醇的方法包括在以下条件下使草酸盐与流化床催化剂接触：反应温度为约170至约270℃，草酸的重量空间速度为约0.2至约7小时-1 氢/酯摩尔比为约20〜200:1，反应压力为约1.5〜10MPa，反应温度差T为约1〜约15℃。流化床催化剂包括： ）约5至约80重量份的铜及其氧化物，b）约10至约90重量份的至少一种选自二氧化硅，分子筛或氧化铝的载体，c）约0.01至约30 铋和钨金属元素或其氧化物或铈和铌金属元素或其氧化物的重量份。

公开(公告)号：US08476469B2

公开(公告)日：2013-07-02

申请号：US13087285

申请日：2011-04-14

申请人： Juntao Liu ,  Weimin Yang ,  Wanmin Wang ,  Linna Zhang

发明人： Juntao Liu ,  Weimin Yang ,  Wanmin Wang ,  Linna Zhang

IPC分类号： C07C203/00

CPC分类号： C07C201/04 ,  C07C203/00

摘要： A process of producing C1-C4 alkyl nitrite, comprising the following steps: a) firstly feeding nitrogen oxide and oxygen into Reactor I, contacting with an aluminosilicate catalyst, and reacting to produce an effluent I containing NO2 and unreacted NO; b) feeding the effluent I and C1-C4 alkanol into Reactor II, and reacting to produce an effluent II containing C1-C4 alkyl nitrite; and c) separating the effluent II containing C1-C4 alkyl nitrite to obtain C1-C4 alkyl nitrite; wherein reactor I is a fixed bed reactor, and Reactor II is a rotating high-gravity reactor; said nitrogen oxide in step a) is NO, or a mixed gas containing NO and one or more of N2O3 and NO2, wherein the molar number of NO is greater than that of NO2, if any; and the molar ratio of NO in nitrogen oxide to oxygen is 4-25:1.

摘要翻译： 一种生产C1-C4烷基亚硝酸盐的方法，包括以下步骤：a）首先将氮氧化物和氧气加入到反应器I中，与铝硅酸盐催化剂接触，并产生含有NO 2和未反应的NO的流出物I; b）将流出物I和C 1 -C 4烷醇加入到反应器II中，并产生含有亚硝酸C1-C4烷基酯的流出物II; 和c）分离含有C1-C4烷基亚硝酸盐的流出物II，得到亚硝酸C1-C4烷基酯; 其中反应器I是固定床反应器，反应器II是旋转的高重力反应器; 步骤a）中的氮氧化物为NO，或含有NO和一种或多种N 2 O 3和NO 2的混合气体，其中NO的摩尔数大于NO 2的摩尔数（如果有的话）。 氮氧化物中的NO与氧的摩尔比为4-25：1。

公开(公告)号：US08178734B2

公开(公告)日：2012-05-15

申请号：US12642621

申请日：2009-12-18

申请人： Juntao Liu ,  Weimin Yang ,  Fengxia Sun ,  Siqing Zhong ,  Wanmin Wang

发明人： Juntao Liu ,  Weimin Yang ,  Fengxia Sun ,  Siqing Zhong ,  Wanmin Wang

IPC分类号： C07C27/04

CPC分类号： B01J35/0006 ,  B01J21/08 ,  B01J23/72 ,  B01J23/745 ,  B01J23/78 ,  B01J23/80 ,  B01J23/868 ,  B01J23/8892 ,  B01J37/0201 ,  C07C29/149 ,  Y02P20/52 ,  C07C31/202

摘要： Provided are processes for producing ethylene glycol from oxalate(s), wherein two or more reaction zones in series are used, and oxalate feedstock is fed stagewise, or hydrogen feedstock and optionally a solvent are fed stagewise. The present processes achieve higher selectivity for the product and improved stability of catalysts.

摘要翻译： 提供了从草酸生产乙二醇的方法，其中使用串联的两个或更多个反应区，并且草酸进料进料阶段，或者氢原料和任选的溶剂进料阶段进料。 本发明方法对产物获得更高的选择性并提高催化剂的稳定性。

公开(公告)号：US08269036B2

公开(公告)日：2012-09-18

申请号：US12642590

申请日：2009-12-18

申请人： Juntao Liu ,  Zhiyan Zhu ,  Wanmin Wang ,  Lei Li

发明人： Juntao Liu ,  Zhiyan Zhu ,  Wanmin Wang ,  Lei Li

IPC分类号： C07C67/36

CPC分类号： C07C67/36 ,  C07C69/36

摘要： Provided are processes for producing an oxalate by coupling of CO in the presence of a nitrite, wherein two or more reaction zones in series are used, and at least a portion of the oxalate as reaction product is separated between the reaction zones, and/or the nitrite is fed stagewise. The processes described herein can effectively enhance the selectivity to the oxalate and the single-pass conversion of the feedstock.

摘要翻译： 本发明提供了在亚硝酸盐存在下偶联CO的方法，其中使用两个或更多个串联的反应区，并且至少一部分草酸盐作为反应产物在反应区之间分离，和/或 亚硝酸盐逐步进料。 本文所述的方法可以有效地提高对草酸盐的选择性和原料的单程转化。

公开(公告)号：US20130331618A1

公开(公告)日：2013-12-12

申请号：US14000878

申请日：2012-02-24

申请人： Juntao Liu ,  Yuhong Zhang ,  Wanmin Wang

发明人： Juntao Liu ,  Yuhong Zhang ,  Wanmin Wang

IPC分类号： C07C29/149

CPC分类号： C07C29/149 ,  C07C29/90 ,  Y02P20/52 ,  C07C31/202

摘要： A method for improving the quality of ethylene glycol products, which mainly solves the technical problem of low UV-light transmittance of the ethylene glycol products present in the prior art. The method successfully solves the problem by use of the technical solution wherein the ethylene glycol raw material and hydrogen are passed through a rotating packed bed reactor loaded with solid oxide catalyst at a temperature of about 20 to about 280 ° C., a pressure of about 0.1 to about 4.0 MPa, a space velocity of about 0.2 to about 100.0 hr−1 and a molar ratio of hydrogen to ethylene glycol of from about 0.01 to 40:1, and ethylene glycol is obtained after the reaction. The solid oxide catalyst is at least one of copper-based, nickel-based and palladium-based catalysts, and the rotation rate of the rotating packed bed reactor is about 300 to about 5000 rpm.

摘要翻译： 一种改善乙二醇产品质量的方法，其主要解决了现有技术中存在的乙二醇产品的紫外光透射率低的技术问题。 该方法通过使用技术方案成功地解决了该问题，其中乙二醇原料和氢气通过装有固体氧化物催化剂的旋转填充床反应器在约20至约280℃的温度下进行，压力约为 0.1至约4.0MPa，空间速度为约0.2至约100.0小时-1，氢与乙二醇的摩尔比为约0.01至40:1，反应后获得乙二醇。 固体氧化物催化剂是铜基，镍基和钯基催化剂中的至少一种，并且旋转填充床反应器的旋转速率为约300至约5000rpm。