公开(公告)号：US09890096B2

公开(公告)日：2018-02-13

申请号：US13313649

申请日：2011-12-07

申请人： Stephen A. Cottrell ,  Yuon Chiu ,  Haluk Kopkalli ,  Hsueh Sung Tung ,  Kevin D. Uhrich ,  Peter Scheidle

发明人： Stephen A. Cottrell ,  Yuon Chiu ,  Haluk Kopkalli ,  Hsueh Sung Tung ,  Kevin D. Uhrich ,  Peter Scheidle

IPC分类号： C07C17/25 ,  C07C17/38 ,  C07C17/383 ,  C07C17/21 ,  C07C17/20 ,  C07C17/087

CPC分类号： C07C17/21 ,  C07C17/087 ,  C07C17/206 ,  C07C17/25 ,  C07C17/38 ,  C07C17/383 ,  C07C19/10 ,  C07C21/18

摘要： Disclosed is a process for the manufacture of 1234yf from 1,1,2,3-tetrachloropropene, abbreviated herein as “TCP,” in three integrated steps: (a) the R-1 hydrofluorination of TCP to form 1233xf in the vapor phase; (b) the R-2 hydrofluorination of 1233xf to form 244bb in either the liquid phase or in the liquid phase followed by the vapor phase; and (c) the R-3 dehydrochlorination of the 244bb in either the liquid or the vapor phase to produce 1234yf; wherein the vapor phase hydrofluorination of TCP in step (a) is carried out at a higher pressure than the liquid phase hydrofluorination of 1233xf; andwherein the HC1 generated during these steps is scrubbed with water to form an acid solution and the organic components are scrubbed with a caustic solution and then dried before further processing.

公开(公告)号：US20120184785A1

公开(公告)日：2012-07-19

申请号：US13313649

申请日：2011-12-07

申请人： Stephen A. Cottrell ,  Yuon Chiu ,  Haluk Kopkalli ,  Hsueh Sung Tung ,  Kevin D. Uhrich ,  Peter Scheidle

发明人： Stephen A. Cottrell ,  Yuon Chiu ,  Haluk Kopkalli ,  Hsueh Sung Tung ,  Kevin D. Uhrich ,  Peter Scheidle

IPC分类号： C07C21/18

CPC分类号： C07C17/21 ,  C07C17/087 ,  C07C17/206 ,  C07C17/25 ,  C07C17/38 ,  C07C17/383 ,  C07C19/10 ,  C07C21/18

摘要： Disclosed is a process for the manufacture of 1234yf from 1,1,2,3-tetrachloropropene, abbreviated herein as “TCP,” in three integrated steps: (a) the R-1 hydrofluorination of TCP to form 1233xf in the vapor phase; (b) the R-2 hydrofluorination of 1233xf to form 244bb in either the liquid phase or in the liquid phase followed by the vapor phase; and (c) the R-3 dehydrochlorination of the 244bb in either the liquid or the vapor phase to produce 1234yf; wherein the vapor phase hydrofluorination of TCP in step (a) is carried out at a lower pressure than the liquid phase hydrofluorination of 123xf; and wherein the HCl generated during these steps is scrubbed with water to form an acid solution and the organic components are scrubbed with a caustic solution and then dried before further processing.

摘要翻译： 公开了一种在1,1,3,3-四氯丙烯中制备1234yf的方法，在本文中简称为“TCP”，在三个一体化步骤中：（a）TCP的R-1氢氟化在气相中形成1233xf; （b）1233xf的R-2氢氟化在液相或液相中形成244bb，随后是气相; 和（c）244bb在液相或气相中的R-3脱氯化氢以产生1234yf; 其中步骤（a）中TCP的气相氢氟化在比123xf的液相氢氟化更低的压力下进行; 并且其中在这些步骤期间产生的HCl用水洗涤以形成酸溶液，并且用苛性碱溶液洗涤有机组分，然后在进一步加工之前干燥。

公开(公告)号：US20090287026A1

公开(公告)日：2009-11-19

申请号：US12466271

申请日：2009-05-14

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Hsueh Sung Tung

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Hsueh Sung Tung

IPC分类号： C07C17/25

CPC分类号： C07C21/18 ,  C07C17/087 ,  C07C17/204 ,  C07C17/206 ,  C07C17/25 ,  C07C19/10

摘要： Disclosed is a process for producing tetrafluoropropene comprising: (a) catalytically fluorinating at least one tetrafluoropropene in a first reactor to produce HCFO-1233xf; (b) reacting said HCFO-1233xf with hydrogen fluoride in a second reactor to produce HCFC-244bb; (c) recycling at least a portion of said HCFC-244bb back to said first reactor as recycled HCFC-244bb; and (d) catalytically dehydrochlorinating said recycled HCFC-244bb in said first reactor to produce HFO-1234yf.

摘要翻译： 公开了一种生产四氟丙烯的方法，包括：（a）在第一反应器中催化氟化至少一种四氟丙烯以产生HCFO-1233xf; （b）在第二反应器中使所述HCFO-1233xf与氟化氢反应以产生HCFC-244bb; （c）将所述HCFC-244bb的至少一部分再循环回所述第一反应器作为再循环HCFC-244bb; 和（d）在所述第一反应器中对所述再循环HCFC-244bb进行催化脱氯化氢以产生HFO-1234yf。

公开(公告)号：US08618340B2

公开(公告)日：2013-12-31

申请号：US12611288

申请日：2009-11-03

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Kevin Uhrich

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Kevin Uhrich

IPC分类号： C07C23/18

CPC分类号： C07C21/18 ,  C01B7/0718 ,  C01B7/0737 ,  C01B7/195 ,  C07C17/087 ,  C07C17/10 ,  C07C17/206 ,  C07C17/25 ,  Y02P20/125 ,  C07C19/10

摘要： Disclosed is a process for the manufacture of HFO-1234yf from TCP in three integrated steps that include hydrofluorination of TCP (tetrachloropropene) to HCFC-1233xf in the vapor phase followed by hydrofluorination of HCFC-1233xf to HCFC-244bb in the liquid phase which is then followed by dehydrochlorination in liquid or vapor phase to produce HFO-1234yf. The vapor phase hydrofluorination is carried out at a higher pressure than the liquid phase hydrofluorination, thereby eliminating the need for compression and/or intermediate recovery. Also, any HCl generated from this reaction is fed to the liquid phase hydrofluorination section to promote agitation and mixing. This results in a more economical process from an initial capital and operating cost versus conducting the 3-steps sequentially.

摘要翻译： 公开了一种从TCP制造HFO-1234yf的方法，其包括在气相中将TCP（四氯丙烯）氢氟化为HCFC-1233xf，然后在液相中HCFC-1233xf氢氟化为HCFC-244bb的三个整合步骤 然后在液相或汽相中进行脱氯化氢以产生HFO-1234yf。 气相氢氟化在比液相氢氟化更高的压力下进行，从而不需要压缩和/或中间回收。 此外，将由该反应生成的任何HCl进料至液相氢氟化部分以促进搅拌和混合。 这导致了从初始资本和运营成本的更经济的过程，而不是依次执行3个步骤。

公开(公告)号：US08242316B2

公开(公告)日：2012-08-14

申请号：US13195429

申请日：2011-08-01

申请人： Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Haluk Kopkalli ,  Gustavo Cerri

发明人： Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Haluk Kopkalli ,  Gustavo Cerri

IPC分类号： C07C17/00

CPC分类号： C07C17/25 ,  B01J7/00 ,  B01J19/0046 ,  B01J19/14 ,  B01J2219/00452 ,  B01J2219/0059 ,  B01J2219/00594 ,  B01J2219/0072 ,  B01J2219/00759 ,  C07C17/23 ,  C07C17/354 ,  C07C17/38 ,  C07C21/18 ,  C07C19/08

摘要： A method for producing 1,1,1,2-tetrafluoropropene and/or 1,1,1,2,3-pentafluoropropene using a single set of four unit operations, the unit operations being (1) hydrogenation of a starting material comprising hexafluoropropene and optionally recycled 1,1,1,2,3-pentafluoropropene; (2) separation of the desired intermediate hydrofluoroalkane, such as 1,1,1,2,3,3-hexafluoropropane and/or 1,1,1,2,3-pentafluoropropane; (3) dehydrofluorination of the intermediate hydrofluoroalkane to produce the desired 1,1,1,2-tetrafluoropropene and/or 1,1,1,2,3-pentafluoropropene, followed by another separation to isolate the desired product and, optionally, recycle of the 1,1,1,2,3-pentafluoropropene.

摘要翻译： 使用单组四个单元操作制备1,1,1,2-四氟丙烯和/或1,1,1,2,3-五氟丙烯的方法，单元操作是（1）将包含六氟丙烯的原料氢化 和任选的再循环的1,1,1,2,3-五氟丙烯; （2）所需中间体氢氟烷烃如1,1,1,2,3,3-六氟丙烷和/或1,1,1,2,3-五氟丙烷的分离; （3）中间体氢氟烷烃的脱氟化氢以产生所需的1,1,1,2-四氟丙烯和/或1,1,1,2,3-五氟丙烯，然后进行另一次分离以分离所需产物，并且任选地再循环 的1,1,1,2,3-五氟丙烯。

公开(公告)号：US09302963B2

公开(公告)日：2016-04-05

申请号：US13570668

申请日：2012-08-09

申请人： Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Haluk Kopkalli ,  Gustavo Cerri

发明人： Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Haluk Kopkalli ,  Gustavo Cerri

IPC分类号： B01J19/00 ,  B01J19/24 ,  C07C17/23 ,  C07C17/25 ,  C07C17/354 ,  C07C17/38 ,  C07C21/18 ,  C07C17/35 ,  C07C21/00 ,  C07C21/02

CPC分类号： C07C17/25 ,  B01J7/00 ,  B01J19/0046 ,  B01J19/14 ,  B01J2219/00452 ,  B01J2219/0059 ,  B01J2219/00594 ,  B01J2219/0072 ,  B01J2219/00759 ,  C07C17/23 ,  C07C17/354 ,  C07C17/38 ,  C07C21/18 ,  C07C19/08

摘要： A method for producing 1,1,1,2-tetrafluoropropene and/or 1,1,1,2,3-pentafluoropropene using a single set of four unit operations, the unit operations being (1) hydrogenation of a starting material comprising hexafluoropropene and optionally recycled 1,1,1,2,3-pentafluoropropene; (2) separation of the desired intermediate hydrofluoroalkane, such as 1,1,1,2,3,3-hexafluoropropane and/or 1,1,1,2,3-pentafluoropropane; (3) dehydrofluorination of the intermediate hydrofluoroalkane to produce the desired 1,1,1,2-tetrafluoropropene and/or 1,1,1,2,3-pentafluoropropene, followed by another separation to isolate the desired product and, optionally, recycle of the 1,1,1,2,3-pentafluoropropene.

摘要翻译： 使用单组四个单元操作制备1,1,1,2-四氟丙烯和/或1,1,1,2,3-五氟丙烯的方法，单元操作是（1）将包含六氟丙烯的原料氢化 和任选的再循环的1,1,1,2,3-五氟丙烯; （2）所需中间体氢氟烷烃如1,1,1,2,3,3-六氟丙烷和/或1,1,1,2,3-五氟丙烷的分离; （3）中间体氢氟烷烃的脱氟化氢以产生所需的1,1,1,2-四氟丙烯和/或1,1,1,2,3-五氟丙烯，然后进行另一次分离以分离所需产物，并且任选地再循环 的1,1,1,2,3-五氟丙烯。

公开(公告)号：US08496892B2

公开(公告)日：2013-07-30

申请号：US13362031

申请日：2012-01-31

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Orlando George Rodrigues ,  Gus Cerri ,  Hsueh Sung Tung ,  Stephen A. Cottrell

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Orlando George Rodrigues ,  Gus Cerri ,  Hsueh Sung Tung ,  Stephen A. Cottrell

IPC分类号： B01J8/00 ,  B01J8/44

CPC分类号： B01J8/067 ,  B01J2208/00849 ,  B01J2208/00884 ,  C07C17/354 ,  C07C19/08

摘要： Disclosed is a process and apparatus for the catalytic hydrogenation of fluoro-olefins to fluorocarbons where the reaction is carried out in a multi-tube shell and tube reactor. Reactions involving hydrogenation of fluoro-olefins are typically exothermic. In commercial processes where a fluoro-olefin CnH2n−xFx to CnH2n−x2Fx is hydrogenated (e.g., hexafluoropropylene to 236ea, 1225ye to 245eb, and the like), inadequate management or control of heat removal may induce excess hydrogenation, decomposition and hot spots resulting in reduced yields and potential safety issues. In the hydrogenation of fluoro-olefins, it is therefore necessary to control the reaction temperature as precisely as practical to overcome challenges associated with heat management and safety.

摘要翻译： 公开了将氟代烯烃催化氢化成碳氟化合物的方法和装置，其中反应在多管壳管式反应器中进行。 涉及氟代烯烃氢化的反应通常是放热的。 在氟化烯烃CnH2n-xFx至CnH2n-x2Fx被氢化（例如六氟丙烯至236ea，1225ye至245eb等）的商业过程中，不充分的除热控制或控制可能引起过量氢化，分解和热点，导致 降低产量和潜在的安全问题。 在氟代烯烃的氢化中，因此需要精确地控制反应温度以克服与热管理和安全相关的挑战。

公开(公告)号：US08129574B2

公开(公告)日：2012-03-06

申请号：US12550909

申请日：2009-08-31

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Orlando George Rodrigues ,  Gus Cerri ,  Hsueh Sung Tung ,  Stephen A. Cottrell

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Orlando George Rodrigues ,  Gus Cerri ,  Hsueh Sung Tung ,  Stephen A. Cottrell

IPC分类号： C07C17/00

CPC分类号： B01J8/067 ,  B01J2208/00849 ,  B01J2208/00884 ,  C07C17/354 ,  C07C19/08

摘要： Disclosed is a process and apparatus for the catalytic hydrogenation of fluoroolefins to fluorocarbons where the reaction is carried out in a multi-tube shell and tube reactor. Reactions involving hydrogenation of fluoro-olefins are typically exothermic. In commercial processes where a fluoro-olefin C(n)H(2n−x)F(x) to C(n)H(2n−x+2)F(x) is hydrogenated (e.g. hexafluoropropylene to 236ea, 1225ye to 245eb, and the like), inadequate management or control of heat removal may induce excess hydrogenation, decomposition and hot spots resulting in reduced yields and potential safety issues. In the hydrogenation of fluoro-olefins, it is therefore necessary to control the reaction temperature as precisely as practical to overcome challenges associated with heat management and safety.

摘要翻译： 公开了将氟烯烃催化氢化成碳氟化合物的方法和装置，其中反应在多管壳管式反应器中进行。 涉及氟代烯烃氢化的反应通常是放热的。 在氟化烯烃C（n）H（2n-x）F（x）至C（n）H（2n-x + 2）F（x）被氢化（例如六氟丙烯至236ea，1225ye至245eb） ，等等），不充分的除热控制或控制可能引起过度的氢化，分解和热点，导致产量降低和潜在的安全问题。 在氟代烯烃的氢化中，因此需要精确地控制反应温度以克服与热管理和安全相关的挑战。

公开(公告)号：US20110105807A1

公开(公告)日：2011-05-05

申请号：US12611288

申请日：2009-11-03

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Kevin D. Uhrich

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Stephen A. Cottrell ,  Hsueh Sung Tung ,  Kevin D. Uhrich

IPC分类号： C07C17/25

CPC分类号： C07C21/18 ,  C01B7/0718 ,  C01B7/0737 ,  C01B7/195 ,  C07C17/087 ,  C07C17/10 ,  C07C17/206 ,  C07C17/25 ,  Y02P20/125 ,  C07C19/10

摘要： Disclosed is a process for the manufacture of HFO-1234yf from TCP in three integrated steps that include hydrofluorination of TCP (tetrachloropropene) to HCFC-1233xf in the vapor phase followed by hydrofluorination of HCFC-1233xf to HCFC-244bb in the liquid phase which is then followed by dehydrochlorination in liquid or vapor phase to produce HFO-1234yf. The vapor phase hydrofluorination is carried out at a higher pressure than the liquid phase hydrofluorination, thereby eliminating the need for compression and/or intermediate recovery. Also, any HCl generated from this reaction is fed to the liquid phase hydrofluorination section to promote agitation and mixing. This results in a more economical process from an initial capital and operating cost versus conducting the 3-steps sequentially.

摘要翻译： 公开了一种从TCP制造HFO-1234yf的方法，其包括在气相中将TCP（四氯丙烯）氢氟化为HCFC-1233xf，然后在液相中HCFC-1233xf氢氟化为HCFC-244bb的三个整合步骤 然后在液相或汽相中进行脱氯化氢以产生HFO-1234yf。 气相氢氟化在比液相氢氟化更高的压力下进行，从而不需要压缩和/或中间回收。 此外，将由该反应生成的任何HCl进料至液相氢氟化部分以促进搅拌和混合。 这导致了从初始资本和运营成本的更经济的过程，而不是依次执行3个步骤。

公开(公告)号：US20110207974A9

公开(公告)日：2011-08-25

申请号：US12466271

申请日：2009-05-14

申请人： Haluk Kopkalli ,  Yuon Chiu ,  Hsueh Sung Tung

发明人： Haluk Kopkalli ,  Yuon Chiu ,  Hsueh Sung Tung

IPC分类号： C07C17/25

CPC分类号： C07C21/18 ,  C07C17/087 ,  C07C17/204 ,  C07C17/206 ,  C07C17/25 ,  C07C19/10

摘要： Disclosed is a process for producing tetrafluoropropene comprising: (a) catalytically fluorinating at least one tetrafluoropropene in a first reactor to produce HCFO-1233xf; (b) reacting said HCFO-1233xf with hydrogen fluoride in a second reactor to produce HCFC-244bb; (c) recycling at least a portion of said HCFC-244bb back to said first reactor as recycled HCFC-244bb; and (d) catalytically dehydrochlorinating said recycled HCFC-244bb in said first reactor to produce HFO-1234yf.

摘要翻译： 公开了一种生产四氟丙烯的方法，包括：（a）在第一反应器中催化氟化至少一种四氟丙烯以产生HCFO-1233xf; （b）在第二反应器中使所述HCFO-1233xf与氟化氢反应以产生HCFC-244bb; （c）将所述HCFC-244bb的至少一部分再循环回所述第一反应器作为再循环HCFC-244bb; 和（d）在所述第一反应器中对所述再循环HCFC-244bb进行催化脱氯化氢以产生HFO-1234yf。