公开(公告)号：US08247366B2

公开(公告)日：2012-08-21

申请号：US13198162

申请日：2011-08-04

Applicant: Hsueh S. Tung ,  Hang T. Pham ,  Rajiv R. Singh ,  Daniel C. Merkel ,  Robert Johnson

Inventor： Hsueh S. Tung ,  Hang T. Pham ,  Rajiv R. Singh ,  Daniel C. Merkel ,  Robert Johnson

IPC: C11D7/50

CPC classification number: C07C21/18 ,  C01B7/191 ,  C07C17/206 ,  C07C17/386 ,  C07C21/04 ,  C09K3/30 ,  C11D7/5059 ,  C23G1/00

Abstract: An azeotrope-like composition consisting essentially of 1,1,2,3-tetrachloropropene and hydrogen fluoride is provided, as well as methods that involve such an azeotrope-like composition.

Abstract translation: 提供了基本上由1,1,2,3-四氯丙烯和氟化氢组成的类共沸组合物，以及涉及这种类共沸组合物的方法。

公开(公告)号：US20120053371A1

公开(公告)日：2012-03-01

申请号：US13287199

申请日：2011-11-02

Applicant: ROBERT C. JOHNSON ,  HSUEH S. TUNG ,  DANIEL C. MERKEL

Inventor： ROBERT C. JOHNSON ,  HSUEH S. TUNG ,  DANIEL C. MERKEL

IPC: C07C17/25 ,  C07C21/18 ,  C07C19/10 ,  C07C17/20

CPC classification number: C07C17/25 ,  C07C17/04 ,  C07C17/087 ,  C07C17/204 ,  C07C17/206 ,  C07C17/21 ,  C07C17/23 ,  C07C21/18 ,  C07C19/01 ,  C07C19/10 ,  C07C19/08 ,  C07C21/073

Abstract: Disclosed are processes for the production of fluorinated olefins, preferably adapted to commercialization of CF3CF═CH2 (1234yf). In certain preferred embodiments the processes comprise first exposing a compound of Formula (IA) C(X)2═CClC(X)3  (IA) where each X is independently F, Cl or H, preferably CCl2═CClCH2Cl, to one or more sets of reaction conditions, but preferably a substantially single set of reaction conditions, effective to produce at least one chlorofluoropropane, preferably in accordance with Formula (IB): CF3CClX′C(X′)3  Formula (IB) where each X′ is independently F, Cl or H, and then exposing the compound of Formula (IB) to one or more sets of reaction conditions, but preferably a substantially single set of reaction conditions, effective to produce a compound of Formula (II) CF3CF═CHZ  (II) where Z is H, F, Cl, I or Br.

Abstract translation: 公开了用于生产氟化烯烃的方法，优选适于CF 3CF≡CH2（1234yf）的商业化。 在某些优选实施方案中，方法包括首先将式（IA）C（X）2 = CClC（X）3（IA）的化合物暴露于其中每个X独立地为F，Cl或H，优选CCl 2 = CClCH 2 Cl， 反应条件，但优选基本上单一组反应条件，有效产生至少一种氯氟丙烷，优选按照式（IB）：CF 3 CClX'C（X'）3式（IB）其中每个X'独立地为 F，Cl或H，然后将式（IB）化合物暴露于一组或多组反应条件，但优选基本上单组的反应条件，有效产生式（II）化合物CF 3 CF = CHZ（II ）其中Z是H，F，Cl，I或Br。

公开(公告)号：US08084653B2

公开(公告)日：2011-12-27

申请号：US11619592

申请日：2007-01-03

Applicant: Hsueh S. Tung ,  Sudip Mukhopadhyay ,  Michael Van Der Puy ,  Daniel C. Merkel ,  Jing Ji Ma ,  Cheryl L. Bortz ,  Barbara A. Light ,  Steven D. Phillips ,  Rajesh K. Dubey

Inventor： Hsueh S. Tung ,  Sudip Mukhopadhyay ,  Michael Van Der Puy ,  Daniel C. Merkel ,  Jing Ji Ma ,  Cheryl L. Bortz ,  Barbara A. Light ,  Steven D. Phillips ,  Rajesh K. Dubey

IPC: C07C17/00 ,  C07C19/08 ,  C07C21/18 ,  C07C23/00 ,  C07C25/13

CPC classification number: C07C17/25 ,  C07C17/00 ,  C07C17/04 ,  C07C17/087 ,  C07C17/10 ,  C07C17/20 ,  C07C17/204 ,  C07C17/206 ,  C07C17/21 ,  C07C17/26 ,  C07C17/269 ,  C07C17/272 ,  C07C17/278 ,  C07C21/18 ,  C07C19/01 ,  C07C19/10 ,  C07C19/08 ,  C07C21/073 ,  C07C21/04

Abstract: Disclosed are processes for the production of fluorinated olefins, preferably adapted to commercialization of CF3CF═CH2 (1234yf). Three steps may be used in preferred embodiments in which a feedstock such as CCl2═CClCH2Cl (which may be purchased or synthesized from 1,2,3-trichloropropane) is fluorinated (preferably with HF in gas-phase in the presence of a catalyst) to synthesize a compound such as CF3CCl═CH2, preferably in a 80-96% selectivity. The CF3CCl═CH2 is preferably converted to CF3CFClCH3 (244-isomer) using a SbCl5 as the catalyst which is then transformed selectively to 1234yf, preferably in a gas-phase catalytic reaction using activated carbon as the catalyst. For the first step, a mixture of Cr2O3 and FeCl3/C is preferably used as the catalyst to achieve high selectivity to CF3CCl═CH2 (96%). In the second step, SbCl5/C is preferably used as the selective catalyst for transforming 1233xf to 244-isomer, CF3CFClCH3. The intermediates are preferably isolated and purified by distillation and used in the next step without further purification, preferably to a purity level of greater than about 95%.

Abstract translation: 公开了用于生产氟化烯烃的方法，优选适于CF 3CF≡CH2（1234yf）的商业化。 在优选实施方案中可以使用三个步骤，其中诸如CCl 2 = CClCH 2 Cl（其可以从1,2,3-三氯丙烷购买或合成）的原料被氟化（优选在气相存在下在HF的情况下为催化剂） 合成化合物如CF 3 CCl = CH 2，优选选择性为80-96％。 CF 3 CCl = CH 2优选使用SbCl 5作为催化剂转化为CF 3 CFClCH 3（244-异构体），然后将其选择性地转化为1234yf，优选在使用活性炭作为催化剂的气相催化反应中。 对于第一步，优选使用Cr 2 O 3和FeCl 3 / C的混合物作为催化剂以实现对CF 3 CCl = CH 2（96％）的高选择性。 在第二步中，SbCl 5 / C优选用作用于将1233xf转化为244-异构体CF 3 CFClCH 3的选择性催化剂。 中间体优选通过蒸馏分离和纯化，并用于下一步骤而不进一步纯化，优选纯度高于约95％。

公开(公告)号：US08070975B2

公开(公告)日：2011-12-06

申请号：US12368395

申请日：2009-02-10

Applicant: Hang T. Pham ,  Rajiv R. Singh ,  HsuehSung Tung ,  Konstantin A. Pokrovski ,  Daniel C. Merkel

Inventor： Hang T. Pham ,  Rajiv R. Singh ,  HsuehSung Tung ,  Konstantin A. Pokrovski ,  Daniel C. Merkel

IPC: C09K5/00 ,  C09K5/04 ,  C11D17/00 ,  C03C15/00 ,  C03C25/68 ,  H01L21/302 ,  H01L21/461

CPC classification number: C07C19/10 ,  C07C17/38 ,  C07C17/383

Abstract: Provided are azeotropic and azeotrope-like compositions of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and hydrogen fluoride (HF). Such azeotropic and azeotrope-like compositions are useful as intermediates in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

Abstract translation: 提供了2-氯-1,1,1,2-四氟丙烷（HCFC-244bb）和氟化氢（HF）的共沸和类共沸组合物。 这种共沸和类共沸组合物可用作生产2,3,3,3-四氟丙烯（HFO-1234yf）的中间体。

公开(公告)号：US08058486B2

公开(公告)日：2011-11-15

申请号：US12404130

申请日：2009-03-13

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

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

IPC: C07C17/25

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

Abstract: 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.

Abstract translation: 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：US08034984B2

公开(公告)日：2011-10-11

申请号：US12887739

申请日：2010-09-22

Applicant: Daniel C. Merkel ,  Rajiv R. Singh ,  Hsueh S. Tung

Inventor： Daniel C. Merkel ,  Rajiv R. Singh ,  Hsueh S. Tung

IPC: C07C17/00

CPC classification number: C07C21/18 ,  C07C17/206 ,  C07C17/25 ,  C07C19/10 ,  C07C19/08

Abstract: Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF3CY═CXNHP, wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.

Abstract translation: 用于从相应的卤代丙烷制备氟丙烯的脱卤化氢方法，其中氟丙烯具有式CF 3C≡≡CXNHP，其中X和Y独立地是氢或选自氟，氯，溴和碘的卤素; 并且N和P独立地为等于0,1或2的整数，条件是（N + P）= 2。

公开(公告)号：US08034251B2

公开(公告)日：2011-10-11

申请号：US12406653

申请日：2009-03-18

Applicant: Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsuehsung Tung ,  Hang T. Pham ,  Rajiv R. Singh

Inventor： Daniel C. Merkel ,  Konstantin A. Pokrovski ,  Hsuehsung Tung ,  Hang T. Pham ,  Rajiv R. Singh

IPC: C09K5/04 ,  C11D7/50 ,  C07C17/383

CPC classification number: C07C21/18 ,  C07C19/10

Abstract: Provided are ternary azeotropic and azeotrope-like compositions of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and hydrogen fluoride (HF). Such azeotropic and azeotrope-like compositions are useful as intermediates in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

Abstract translation: 提供了2-氯-3,3,3-三氟丙烯（HCFO-1233xf），2-氯-1,1,1,2-四氟丙烷（HCFC-244bb）和氟化氢（的三元共沸和类共沸组合物） HF）。 这种共沸和类共沸组合物可用作生产2,3,3,3-四氟丙烯（HFO-1234yf）的中间体。

公开(公告)号：US20110224465A1

公开(公告)日：2011-09-15

申请号：US12720763

申请日：2010-03-10

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

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

IPC: C07C17/25

CPC classification number: C07C17/25 ,  B01J27/128 ,  B01J27/132 ,  B01J38/12 ,  Y02P20/584 ,  C07C21/18

Abstract: This invention achieves a catalyst life improvement for the catalyzed vapor phase reaction of 1,1,1,3,3-pentachloropropane with hydrogen fluoride to form 1-chloro-3,3,3-trifluoropropene by introducing an oxygen co-feed into the fluorination reactor. By introduction of an oxygen co-feed to the reactor feed, the catalyst life was extended a minimum of two-fold (2×).

Abstract translation: 本发明为1,1,1,3,3-五氯丙烷与氟化氢的催化气相反应实现了催化剂寿命的改善，形成1-氯-3,3,3-三氟丙烯，通过将氧共进料引入 氟化反应器。 通过向反应器进料中引入氧共同进料，催化剂寿命延长至少两倍（2×）。

公开(公告)号：US07951982B2

公开(公告)日：2011-05-31

申请号：US11592842

申请日：2006-11-03

Applicant: Sudip Mukhopadhyay ,  Haridasan K. Nair ,  Hsueh S. Tung ,  Michael Van Der Puy ,  Robert C. Johnson ,  Daniel C. Merkel

Inventor： Sudip Mukhopadhyay ,  Haridasan K. Nair ,  Hsueh S. Tung ,  Michael Van Der Puy ,  Robert C. Johnson ,  Daniel C. Merkel

IPC: C07C21/18

CPC classification number: C07C17/25 ,  B01J23/02 ,  B01J23/44 ,  B01J23/755 ,  B01J23/78 ,  B01J23/83 ,  B01J35/06 ,  C07C17/00 ,  C07C17/269 ,  C07C21/18 ,  C07C19/08

Abstract: Disclosed is a process for the preparation of fluorinated olefins. In preferred embodiments C3 olefins are produced by methods comprising contacting a compound of the Formula (I) C(R1aR2bR3c)  (I) with a compound of Formula (II) C(R1aR2bR3c)Cn(R1aR2bR3c)  II wherein R1a, R2b, and R3c are independently a hydrogen atom or a halogen selected from the group consisting of fluorine; chlorine, bromine and iodine, provided that the compound of formula I has at least three halogen substituents and that said at three halogen substituents comprise at least one fluorine; a, b and c are independently=0, 1, 2 or 3 and (a+b+c)=2 or 3; and n is 0 or 1, under conditions effective to produce at least one C3 fluoroolefin.

Abstract translation: 公开了一种制备氟化烯烃的方法。 在优选实施方案中，C3烯烃通过以下方法制备：包括使式（I）C（R 1a R 2b b C 3）（I）的化合物与式（II）的化合物C（R1aR2bR3c）Cn（R1aR2bR3c）II的化合物接触，其中R1a，R2b和R3c 独立地为氢原子或选自氟的卤素; 氯，溴和碘，条件是式I化合物具有至少三个卤素取代基，并且在三个卤素取代基上含有至少一个氟; a，b和c独立地为= 0,1,2或3，（a + b + c）= 2或3; 在有效产生至少一种C3氟代烯烃的条件下，n为0或1。

公开(公告)号：US20110028770A1

公开(公告)日：2011-02-03

申请号：US12534323

申请日：2009-08-03

Applicant: HAIYOU WANG ,  HSUEH SUNG TUNG ,  DANIEL C. MERKEL

Inventor： HAIYOU WANG ,  HSUEH SUNG TUNG ,  DANIEL C. MERKEL

IPC: B01J21/04 ,  C07C19/08

CPC classification number: B01J32/00 ,  B01J21/04 ,  B01J23/36 ,  B01J23/40 ,  B01J23/44 ,  B01J23/48 ,  B01J23/70 ,  B01J35/1014 ,  B01J37/18 ,  C07C17/354 ,  C07C19/08

Abstract: An alpha-alumina support for a hydrogenation catalyst useful in hydrogenating fluoroolefins is provided.

Abstract translation: 提供了用于氢化氟烯烃的氢化催化剂的α-氧化铝载体。