公开(公告)号：US08710282B2

公开(公告)日：2014-04-29

申请号：US13229016

申请日：2011-09-09

申请人： Selma Bektesevic ,  Hsueh Sung Tung ,  Haluk Kopkalli

发明人： Selma Bektesevic ,  Hsueh Sung Tung ,  Haluk Kopkalli

IPC分类号： C07C17/25 ,  C07C19/08 ,  C07C21/18

CPC分类号： C07C17/25 ,  C07C17/354 ,  C07C17/38 ,  Y02P20/125 ,  Y02P20/582 ,  C07C21/18 ,  C07C19/08

摘要： The instant invention relates, at least in part, to a method increasing the cost efficiency for dehydrohalogenation production of a fluorinated olefin by recovering and recycling spent dehydrohalogenation agent. In one aspect, the present invention relates to dehydrohalogenating a fluorinated alkane (e.g. pentafluoropropane and/or hexafluoropropane) in the presence of a dehydrohalogenating agent to produce a fluorinated olefin (e.g. tetrafluoropropenes and/or pentafluoropropenes). Removal of spent dehydrohalogenating agent from the reactor allows for facile separation of organic and dehydrohalogenating agent, the latter of which is recycled.

摘要翻译： 本发明至少部分地涉及通过回收和再循环使用的脱卤化氢剂来提高氟化烯烃的脱卤化氢生产的成本效率的方法。 一方面，本发明涉及在脱卤化氢剂的存在下氟化烷烃（例如五氟丙烷和/或六氟丙烷）脱卤化氢以制备氟化烯烃（例如四氟丙烯和/或五氟丙烯）。 从反应器中除去用过的脱卤化氢剂允许容易地分离有机和脱卤化氢剂，其中后者被再循环。

公开(公告)号：US08058486B2

公开(公告)日：2011-11-15

申请号：US12404130

申请日：2009-03-13

申请人： Daniel C. Merkel ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski ,  Selma Bektesevic ,  Robert C. Johnson ,  Haiyou Wang

发明人： Daniel C. Merkel ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski ,  Selma Bektesevic ,  Robert C. Johnson ,  Haiyou Wang

IPC分类号： C07C17/25

CPC分类号： C07C21/18 ,  C01B7/035 ,  C01B7/0706 ,  C01B7/195 ,  C07C17/087 ,  C07C17/10 ,  C07C17/206 ,  C07C17/25 ,  C07C17/383 ,  Y02P20/125 ,  Y02P20/582 ,  C07C19/10

摘要： A method for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising (a) providing a starting composition comprising at least one compound having a structure selected from Formulae I, II and III: CX2═CCl—CH2X  (Formula I) CX3—CCl═CH2  (Formula II) CX3—CHCl—CH2X  (Formula III) wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine; (b) contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct; (c) contacting said first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane and a second chlorine-containing byproduct; and (d) catalytically dehydrochlorinating at least a portion of said 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.

摘要翻译： 一种制备2,3,3,3-四氟丙-1-烯的方法，包括（a）提供起始组合物，其包含至少一种具有选自式I，II和III的结构的化合物：CX2 = CCl-CH2X（式I ）CX3-CCl = CH2（式II）CX3-CHCl-CH2X（式III）其中X独立地选自F，Cl，Br和I，条件是至少一个X不是氟; （b）使所述起始组合物与第一氟化剂接触以产生包含2-氯-3,3,3-三氟丙烯和第一含氯副产物的第一中间体组合物; （c）使所述第一中间体组合物与第二氟化剂接触以产生包含2-氯-1,1,1,2-四氟丙烷和第二含氯副产物的第二中间体组合物; 和（d）将至少一部分所述2-氯-1,1,1,2-四氟丙烷催化脱氯化氢以产生包含2,3,3,3-四氟丙-1-烯的反应产物。

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：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：US20140316170A1

公开(公告)日：2014-10-23

申请号：US14351732

申请日：2012-10-11

申请人： Selma BEKTESEVIC ,  Daniel C. MERKEL ,  Mario Joseph NAPPA ,  Xuehui SUN ,  Hsueh Sung TUNG ,  Haiyou WANG

发明人： Selma Bektesevic ,  Daniel C. Merkel ,  Mario Joseph Nappa ,  Xuehui Sun ,  Hsueh Sung Tung ,  Haiyou Wang

IPC分类号： C07C17/20 ,  C07C17/25 ,  C07C21/04

CPC分类号： C07C17/20 ,  C07C17/087 ,  C07C17/25 ,  C07C21/04 ,  C07C21/18 ,  C07C19/10

摘要： The present invention relates, in part, to the discovery that the presence of impurities in 1,1,2,3-tetrachloropropene (1230xa) results in catalyst instability during the fluorination of 1230xa to 2-chloro-3,3,3-trifluoropropene. By substantially removing the impurities, it is shown that the catalyst life is extended and results in improved operation efficiency of the fluorination reaction. Such steps similarly result in an overall improvement in the production of certain hydrofluoroolefins, particularly 2,3,3,3-tetrafluoropropene (1234yf).

摘要翻译： 本发明部分涉及发现在1,1,2,3-四氯丙烯（1230xa）中杂质的存在导致在1230xa氟化为2-氯-3,3,3-三氟丙烯期间的催化剂不稳定性 。 通过基本上除去杂质，显示催化剂寿命延长并且导致改善氟化反应的操作效率。 这些步骤类似地导致某些氢氟烯烃，特别是2,3,3,3-四氟丙烯（1234yf）的生产的总体改进。

公开(公告)号：US20140256996A1

公开(公告)日：2014-09-11

申请号：US14355894

申请日：2012-11-02

申请人： Haiyou Wang ,  Hsueh Sung Tung ,  Selma Bektesevic ,  Daniel C. Merkel

发明人： Haiyou Wang ,  Hsueh Sung Tung ,  Selma Bektesevic ,  Daniel C. Merkel

IPC分类号： C07C17/20

CPC分类号： C07C17/202 ,  B01J21/04 ,  B01J23/26 ,  B01J23/34 ,  B01J23/745 ,  B01J23/75 ,  B01J23/755 ,  B01J27/10 ,  B01J27/12 ,  B01J27/138 ,  C07C17/087 ,  C07C17/206 ,  C07C17/25 ,  C07C17/42 ,  C07C21/18 ,  C07C19/10

摘要： The present invention relates, in part, to the discovery that, during the fluorination of certain fluoroolefm starting reagents, oligomerization/polymerization of such reagents reduces the conversion process and leads to increased catalyst deactivation. The present invention also illustrates that vaporizing such starting reagents in the presence of one or more organic co-feed reduces such oligomerization/polymerization and improves catalytic stability.

摘要翻译： 本发明部分地涉及在某些氟代起始试剂的氟化期间，这种试剂的低聚/聚合降低了转化过程并导致催化剂失活增加的发现。 本发明还说明，在一种或多种有机共进料存在下蒸发这种起始试剂可以减少这种低聚/聚合反应并提高催化稳定性。

公开(公告)号：US20090240090A1

公开(公告)日：2009-09-24

申请号：US12404130

申请日：2009-03-13

申请人： Daniel C. Merkel ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski ,  Selma Bektesevic ,  Robert Johnson ,  Haiyou Wang

发明人： Daniel C. Merkel ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski ,  Selma Bektesevic ,  Robert Johnson ,  Haiyou Wang

IPC分类号： C07C17/20

CPC分类号： C07C21/18 ,  C01B7/035 ,  C01B7/0706 ,  C01B7/195 ,  C07C17/087 ,  C07C17/10 ,  C07C17/206 ,  C07C17/25 ,  C07C17/383 ,  Y02P20/125 ,  Y02P20/582 ,  C07C19/10

摘要： A method for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising (a) providing a starting composition comprising at least one compound having a structure selected from Formulae I, II and III: CX2═CCl—CH2X  (Formula I) CX3—CCl═CH2  (Formula II) CX3—CHCl—CH2X  (Formula III) wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine; (b) contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct; (c) contacting said first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane and a second chlorine-containing byproduct; and (d) catalytically dehydrochlorinating at least a portion of said 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.

摘要翻译： 一种制备2,3,3,3-四氟丙-1-烯的方法，包括（a）提供起始组合物，其包含至少一种具有选自式I，II和III的结构的化合物： =“直线公式”end =“lead”？> CX2-CCl-CH2X（式I）<？in-line-formula description =“In-line Formulas”end =“tail”？> <？in-line -formulae description =“In-line Formulas”end =“lead”？> CX3-CCl-CH2（式II）<？in-line-formula description =“In-line Formulas”end =“tail”？> in-line-formula description =“In-line Formulas”end =“lead”？> CX3-CHCl-CH2X（式III）<？in-line-formula description =“In-line Formulas”end =“tail”？ >其中X独立地选自F，Cl，Br和I，条件是至少一个X不是氟; （b）使所述起始组合物与第一氟化剂接触以产生包含2-氯-3,3,3-三氟丙烯和第一含氯副产物的第一中间体组合物; （c）使所述第一中间体组合物与第二氟化剂接触以产生包含2-氯-1,1,1,2-四氟丙烷和第二含氯副产物的第二中间体组合物; 和（d）将至少一部分所述2-氯-1,1,1,2-四氟丙烷催化脱氯化氢以产生包含2,3,3,3-四氟丙-1-烯的反应产物。