公开(公告)号：US09938212B2

公开(公告)日：2018-04-10

申请号：US13432300

申请日：2012-03-28

Applicant: Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Haiyou Wang ,  Hsueh Sung Tung

Inventor： Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Haiyou Wang ,  Hsueh Sung Tung

IPC: C07C17/25 ,  C07C17/20 ,  C07C17/38 ,  C07C17/383 ,  C07C17/395 ,  C07C17/21

CPC classification number: C07C17/25 ,  C07C17/206 ,  C07C17/208 ,  C07C17/21 ,  C07C17/38 ,  C07C17/383 ,  C07C17/395 ,  Y02P20/125 ,  Y02P20/582 ,  C07C21/18 ,  C07C19/08

Abstract: Disclosed is an integrated manufacturing process to co-produce (E) 1-chloro-3,3,3-trifluoropropene, (E) 1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoro-propane starting from a single starting feed material or a mixture of unsaturated hydrochlorocarbon feed materials comprising 1,1,1,3-tetrachloropropene and/or 1,1,3,3-tetrachloropropene. The process includes a combined liquid or vapor phase reaction/purification operation which directly produces (E) 1-chloro-3,3,3-trifluoro-propene (1233zd (E)) from these feed materials, which may also include 240fa. In the second liquid phase fluorination reactor 1233zd (E) is contacted with HF in the presence of catalyst to produce 1,1,1,3,3-pentafluoropropane (245fa) with high conversion and selectivity. A third reactor is used for dehydrofluorination of 245fa to produce (E) 1,3,3,3-tetrafluoropropene (1234ze (E)) by contacting in the liquid phase with a caustic solution or in the vapor phase using a dehydrofluorination catalyst. This operation may be followed by one or more purification processes to recover the 1234ze (E) product.

公开(公告)号：US20150225316A1

公开(公告)日：2015-08-13

申请号：US14618500

申请日：2015-02-10

Applicant: Daniel C. MERKEL ,  Barry Asher MAHLER ,  Hsueh Sung TUNG ,  Mario Joseph NAPPA

Inventor： Daniel C. MERKEL ,  Barry Asher MAHLER ,  Hsueh Sung TUNG ,  Mario Joseph NAPPA

IPC: C07C17/087 ,  C07C17/25

CPC classification number: C07C17/087 ,  B01J19/18 ,  B01J19/1868 ,  C07C17/20 ,  C07C17/206 ,  C07C17/25 ,  C07C19/10

Abstract: The present invention relates to a hydrofluorinating process which comprises reacting a fluoroolefin with hydrogen fluoride in the liquid phase in the presence of a hydrofluorination catalyst in the reaction zone of a reactor, said reactor comprised of a reactor body having a length to diameter ratio of about 2:1 or greater; a stirred reaction zone containing said hydrofluorination catalyst, which may be prepared in situ, at least one inlet for supplying said hydrogen fluoride and fluoroolefin to the reaction zone and at least one outlet for recovering said fluoroalkane, said stirrer disposed in the reaction zone and comprising a plurality of blades fixedly attached to shaft drivable by a motor, said blades extending from about the bottom of the reaction zone to about the top of the reaction zone and said shaft extending on a longitudinal axis from the bottom of the reactor to the top of the reactor, said stirrer being rotated at a speed sufficient to promote a swirling of the liquid to effect the occurrence of hydrofluorination reaction and minimize overfluorination. The present invention also relates to said hydrofluorination reactor.

Abstract translation: 本发明涉及一种氢氟化方法，其包括在反应器的反应区中在氟化氢催化剂存在下，在液相中使氟烯烃与氟化氢反应，所述反应器包括长径比为约 2：1或更大; 包含可以原位制备的所述氢氟化催化剂的搅拌反应区，至少一个用于将所述氟化氢和氟代烯烃供应到反应区的入口和用于回收所述氟烷烃的至少一个出口，所述搅拌器设置在反应区中并且包含 多个叶片固定地附接到由马达驱动的轴上，所述叶片从反应区域的底部延伸到反应区域的顶部，并且所述轴线在纵向轴线上从反应器底部延伸到顶部 反应器，所述搅拌器以足以促进液体旋转的速度旋转以实现氢氟化反应的发生并使过度氟化最小化。 本发明还涉及所述氢氟化反应器。

公开(公告)号：US09040759B2

公开(公告)日：2015-05-26

申请号：US12167159

申请日：2008-07-02

Applicant: Haiyou Wang ,  Hsueh Sung Tung ,  Sudip Mukhopadhyay

Inventor： Haiyou Wang ,  Hsueh Sung Tung ,  Sudip Mukhopadhyay

IPC: C07C21/18 ,  B01J35/00 ,  B01J27/10 ,  B01J27/12 ,  B01J27/138 ,  C07B35/06 ,  C07C17/25

CPC classification number: C07C17/25 ,  B01J27/10 ,  B01J27/12 ,  B01J27/138 ,  B01J35/0006 ,  C07B35/06 ,  C07C21/18

Abstract: A process for making a fluorinated olefin having the step of dehydrochlorinating a hydrochlorofluorocarbon having at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms, preferably carried out in the presence of a catalyst selected from the group consisting of (i) one or more metal halides, (ii) one or more halogenated metal oxides, (iii) one or more zero-valent metals/metal alloys, (iv) a combination of two or more of the foregoing.

Abstract translation: 一种制备氟化烯烃的方法，该方法具有以下步骤：在相邻碳原子上具有至少一个氢原子和至少一个氯原子的氢氯氟烃脱氯化氢，优选在选自以下的催化剂的存在下进行：（i）一种 或更多的金属卤化物，（ii）一种或多种卤化金属氧化物，（iii）一种或多种零价金属/金属合金，（iv）上述两种或更多种的组合。

公开(公告)号：US09000240B2

公开(公告)日：2015-04-07

申请号：US13471565

申请日：2012-05-15

Applicant: Stephen A. Cottrell ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski

Inventor： Stephen A. Cottrell ,  Hsueh Sung Tung ,  Konstantin A. Pokrovski

IPC: C07C17/25 ,  C07C17/20 ,  C07C21/18 ,  C07C17/38 ,  C07C17/383

CPC classification number: C07C17/383 ,  C07C17/206 ,  C07C17/25 ,  C07C17/38 ,  C07C21/18 ,  Y02P20/125

Abstract: The present invention is directed to processes for the production of 1233zd from 240fa and HF, with or without a catalyst, at a commercial scale. The 240fa and HF are fed to a reactor operating at high pressure. The resulting product stream comprising 1233zd, HCl, HF, and other byproducts is treated to one or more purification techniques including phase separation and one or more distillations to provide purified 1233zd, which meets commercial product specifications, i.e., having a GC purity of 99.5% or greater.

Abstract translation: 本发明涉及以商业规模从240fa和HF生产1233zd（有或没有催化剂）的方法。 将240fa和HF进料到在高压下操作的反应器。 将包含1233zd，HCl，HF和其他副产物的所得产物流处理成一种或多种纯化技术，包括相分离和一种或多种蒸馏以提供满足商业产品规格的纯化的1233zd，即GC纯度为99.5％ 或更大。

公开(公告)号：US08796493B2

公开(公告)日：2014-08-05

申请号：US13249342

申请日：2011-09-30

Applicant: Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsueh Sung Tung

Inventor： Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsueh Sung Tung

IPC: C07C17/38

CPC classification number: C07C17/389 ,  B01D15/00 ,  C07C21/18

Abstract: The present invention provides a method for separating halocarbons. In particular, the invention provides a method for separating halogenated olefin impurities from 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) using a solid adsorbent, particularly activated carbon. More particularly the invention pertains to a method for separating 2-chloro-3,3,3-trifluoro-propene (HCFO-1233xf) from HCFC-244bb, which are useful as intermediates in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

Abstract translation: 本发明提供一种分离卤代烃的方法。 特别地，本发明提供了使用固体吸附剂，特别是活性炭从2-氯-1,1,1,2-四氟丙烷（HCFC-244bb）分离卤代烯烃杂质的方法。 更具体地说，本发明涉及从HCFC-244bb中分离出2-氯-3,3,3-三氟丙烯（HCFO-1233xf）的方法，它们可用作制备2,3,3,3-三氟丙烯 四氟丙烯（HFO-1234yf）。

公开(公告)号：US08704017B2

公开(公告)日：2014-04-22

申请号：US13220212

申请日：2011-08-29

Applicant: Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Hsueh Sung Tung

Inventor： Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Hsueh Sung Tung

IPC: C07C17/20

CPC classification number: C07C17/20 ,  B01D3/009 ,  C01B7/0706 ,  C01B7/0712 ,  C07C17/206 ,  C07C17/25 ,  C07C17/358 ,  C07C17/383 ,  C07C21/18 ,  Y02P20/582

Abstract: Disclosed is process for the production of (E) 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) by conducting a continuous reaction without the use of a catalyst. Also disclosed is an integrated system for producing hydrofluoro olefins, particularly 1233zd(E). The manufacturing process includes six major unit operations: (1) a fluorination reaction of HCC-240fa (in continuous or semi-batch mode) using HF with simultaneous removal of by-product HCl and the product 1233zd(E); (2) recycle of unreacted HCC-240fa and HF together with under-fluorinated by-products back to (1); (3) separation and purification of by-product HCl; (4) separation of excess HF back to (1); (5) purification of final product, 1233zd(E); and (6) isomerization of by-product 1233zd(Z) to 1233zd(E) to maximize the process yield.

Abstract translation: 公开了通过在不使用催化剂的情况下进行连续反应来制备（E）1-氯-3,3,3-三氟丙烯（HCFO-1233zd（E））的方法。 还公开了用于制备氢氟烯烃的综合系统，特别是1233zd（E）。 制造过程包括六个主要单元操作：（1）使用HF同时除去副产物HCl和产物1233zd（E）的HCC-240fa（连续或半间歇模式）的氟化反应; （2）将未反应的HCC-240fa和HF与未氟化的副产物一起回收至（1）; （3）副产物HCl的分离纯化; （4）将过量的HF分离回（1）; （5）最终产物的纯化，1233zd（E）; 和（6）副产物1233zd（Z）异构化为1233zd（E）以使工艺产率最大化。

公开(公告)号：US20130261353A1

公开(公告)日：2013-10-03

申请号：US13432300

申请日：2012-03-28

Applicant: Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Haiyou Wang ,  Hsueh Sung Tung

Inventor： Konstantin A. Pokrovski ,  Daniel C. Merkel ,  Haiyou Wang ,  Hsueh Sung Tung

IPC: C07C17/25

CPC classification number: C07C17/25 ,  C07C17/206 ,  C07C17/208 ,  C07C17/21 ,  C07C17/38 ,  C07C17/383 ,  C07C17/395 ,  Y02P20/125 ,  Y02P20/582 ,  C07C21/18 ,  C07C19/08

Abstract: Disclosed is an integrated manufacturing process to co-produce (E) 1-chloro-3,3,3-trifluoropropene, (E) 1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoro-propane starting from a single starting feed material or a mixture of unsaturated hydrochloro-carbon feed materials comprising 1,1,1,3-tetrachloropropene and/or 1,1,3,3-tetrachloro-propene. The process includes a combined liquid or vapor phase reaction/purification operation which directly produces (E) 1-chloro-3,3,3-trifluoro-propene (1233zd (E)) from these feed materials, which may also include 240fa. In the second liquid phase fluorination reactor 1233zd (E) is contacted with HF in the presence of catalyst to produce 1,1,1,3,3-pentafluoropropane (245fa) with high conversion and selectivity. A third reactor is used for dehydrofluorination of 245fa to produce (E) 1,3,3,3-tetrafluoro-propene (1234ze (E)) by contacting in the liquid phase with a caustic solution or in the vapor phase using a dehydrofluorination catalyst. This operation may be followed by one or more purification processes to recover the 1234ze (E) product.

Abstract translation: 公开了共同生产（E）1-氯-3,3,3-三氟丙烯，（E）1,3,3,3-四氟丙烯和1,1,1,3,3-五氟 丙烷从单起始原料或包含1,1,1,3-四氯丙烯和/或1,1,3,3-四氯丙烯的不饱和氯碳 - 碳进料的混合物开始。 该方法包括从这些进料中直接生产（E）1-氯-3,3,3-三氟丙烯（1233zd（E））的液相或汽相反应/纯化操作，其也可以包括240fa。 在第二液相氟化反应器1233zd（E）中，在催化剂存在下与HF接触，得到具有高转化率和选择性的1,1,1,3,3-五氟丙烷（245fa）。 第三反应器用于245fa的脱氟化氢以通过使用脱氟化氢催化剂在液相中与苛性碱溶液或气相接触来制备（E）1,3,3,3-四氟丙烯（1234ze（E）） 。 该操作之后可以进行一个或多个纯化过程以恢复1234ze（E）产物。

公开(公告)号：US08513474B2

公开(公告)日：2013-08-20

申请号：US12822365

申请日：2010-06-24

Applicant: Haiyou Wang ,  Hsueh Sung Tung

Inventor： Haiyou Wang ,  Hsueh Sung Tung

IPC: C07C17/00 ,  C07C17/10

CPC classification number: C07C17/04 ,  C07C17/354 ,  C07C17/357 ,  C07C21/18 ,  C07C19/08

Abstract: Provided are methods for producing fluorinated organic compounds, which preferably comprises converting at least one compound of formula (I) CH2XCHZCF3 to at least one compound of formula (II) CHX═CZCF3 where X and Z are independently H or F, with the proviso that X and Z are not the same. The converting step comprises catalytically reacting at least one compound of formula (I), preferably via dehydrogenation or oxidative dehydrogenation. In another aspect, the inventive method of preparing fluorinated organic compounds comprises converting a reaction stream comprising at least one pentafluoropropene to a product stream comprising at least one pentafluoropropane and at least one compound of formula (I), separating out the compound of formula (I) from the product stream, and converting the compound of formula (I) separated from the product stream to at least one compound of formula (II), wherein the conversion the compound of formula (I) to 3,3,3-trifluoropropyne is substantially limited.

Abstract translation: 提供了用于生产氟化有机化合物的方法，其优选包括将至少一种式（I）CH 2 XCHZCF 3化合物转化为至少一种式（II）的化合物，其中X和Z独立地为H或F，式（II）化合物为CHX = CZCF3，条件是 X和Z不一样。 转化步骤包括使至少一种式（I）化合物催化反应，优选通过脱氢或氧化脱氢。 在另一方面，制备含氟有机化合物的本发明方法包括将包含至少一种五氟丙烯的反应物流转化为包含至少一种五氟丙烷和至少一种式（I）化合物的产物流，将式（I）化合物 ），并将从产物流分离的式（I）化合物转化为至少一种式（II）化合物，其中式（I）化合物与3,3,3-三氟丙炔的转化率为 基本上有限。

公开(公告)号：US08373010B2

公开(公告)日：2013-02-12

申请号：US12875170

申请日：2010-09-03

Applicant: Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsueh Sung Tung ,  Selma Bektesevic

Inventor： Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsueh Sung Tung ,  Selma Bektesevic

IPC: C07C17/25

CPC classification number: C07C17/25 ,  C07C17/206 ,  C07C17/354 ,  C07C21/18 ,  C07C19/08

Abstract: Disclosed is a process for the preparation of 3,3,3-trifluoropropene comprising the steps of; (1) fluorination of 240fa to form 245fa; (2) conversion of 245fa to a cis/trans mixture of 1234ze; (3) hydrogenation of the cis/trans mixture of 1234ze to form 254fb ; and (4) dehydrofluorination of 254fb to produce 3,3,3-trifluoropropene. Alternatively or additionally, a second process for the preparation of the desired compound comprises the following steps; (1) fluorination of HCC-240fa to form HCFC-244fa; (2) conversion of 244fa to a cis/trans mixture of HFO-1234ze; (3) hydrogenation of the cis/trans mixture of 1234ze to form HFC-254fb; and (4) dehydrofluorination of 254fb to produce 3,3,3-trifluoropropene.

Abstract translation: 公开了制备3,3,3-三氟丙烯的方法，包括以下步骤： （1）240fa的氟化以形成245fa; （2）将245fa转化为1234ze的顺式/反式混合物; （3）将1234ze的顺式/反式混合物氢化成254fb; 和（4）254fb的脱氟化氢，得到3,3,3-三氟丙烯。 或者或另外，制备所需化合物的第二种方法包括以下步骤： （1）HCC-240fa氟化形成HCFC-244fa; （2）将244fa转化为HFO-1234ze的顺式/反式混合物; （3）将1234ze的顺式/反式混合物氢化形成HFC-254fb; 和（4）254fb的脱氟化氢，得到3,3,3-三氟丙烯。

公开(公告)号：US20120301373A1

公开(公告)日：2012-11-29

申请号：US13570668

申请日：2012-08-09

Applicant: YUON CHIU ,  STEPHEN A. COTTRELL ,  HSUEH SUNG TUNG ,  HALUK KOPKALLI ,  GUSTAVO CERRI

Inventor： YUON CHIU ,  STEPHEN A. COTTRELL ,  HSUEH SUNG TUNG ,  HALUK KOPKALLI ,  GUSTAVO CERRI

IPC: C07C17/25

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。