KR940018341A - 1,1,1,2-테트라플루오로-2-클로로에탄 및 펜타플루오로에탄의 제조방법 - Google Patents
1,1,1,2-테트라플루오로-2-클로로에탄 및 펜타플루오로에탄의 제조방법 Download PDFInfo
- Publication number
- KR940018341A KR940018341A KR1019940001484A KR19940001484A KR940018341A KR 940018341 A KR940018341 A KR 940018341A KR 1019940001484 A KR1019940001484 A KR 1019940001484A KR 19940001484 A KR19940001484 A KR 19940001484A KR 940018341 A KR940018341 A KR 940018341A
- Authority
- KR
- South Korea
- Prior art keywords
- chloroethane
- tetrafluoro
- pentahaloethane
- nickel
- seconds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract 9
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 title claims abstract 3
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract 4
- 239000011651 chromium Substances 0.000 claims abstract 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052794 bromium Chemical group 0.000 claims abstract 2
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- 229910052801 chlorine Inorganic materials 0.000 claims abstract 2
- 239000000460 chlorine Substances 0.000 claims abstract 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract 2
- 238000003682 fluorination reaction Methods 0.000 claims abstract 2
- 150000004820 halides Chemical class 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims abstract 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical group FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 229960003750 ethyl chloride Drugs 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- -1 oxy halides Chemical class 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
- C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/86—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/132—Compounds comprising a halogen and chromium, molybdenum, tungsten or polonium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
Claims (8)
- 불화 알루미늄 또는 불화 알루미늄과 알루미나의 혼합물로 구성된 지지체상에 침착된 니켈 및 크롬의 산화물, 할로겐화물 및/또는 옥시할로겐화물로 이루어진 혼합 촉매를 사용함을 특징으로 하는, 식 C2HX2-nF3+n(식중, X는 염소 또는 브롬원자이고, n은 0 또는 1이다)의 펜타할로에탄 하나 이상을 불화 수소산을 사용하여 기상 촉매 불화함으로써 1,1,1,2-테트라플루오로-2-클로로에탄 및/또는 펜타플루오르에탄을 제조하는 방법.
- 제1항에 있어서, 촉매중의 니켈 및 크롬의 함량이 중량 기준으로 각 금속에 대해 0.5∼20%이고, 니켈/크롬 원자비가 0.5∼5, 바람직하게는 1인 방법.
- 제2항에 있어서, 함량이 각 금속에 대해 2∼10%인 방법.
- 제1항 내지 제3항중 어느 한 항에 있어서, 불화수소산 및 펜타할로에탄을 HF/펜타할로에탄 몰비 1/1∼20/1로 3-100초간 250∼470℃에서 접촉시키는 방법.
- 제4항에 있어서, 몰비가 2/1∼9/1이고, 접촉시간이 5∼30초, 바람직하게는 7∼15초이며, 온도가 280∼410℃인 방법.
- 제1항 내지 제5항중 어느 한 항에 있어서, 출발 펜타할로에탄이 1,1,1-트리플루오로-2,2-디클로로에탄 및/또는 1,1,1,2-테트라플루오로-2-클로로에탄인 방법.
- 제1항 내지 제6항중 어느 한 항에 있어서, 압력 0-25바(상대), 바람직하게는 대기압에서 수행되는 방법.
- 제1항 내지 제7항중 어느 한 항에 있어서, 반응이 산소 존재하에 수행되는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9300780 | 1993-01-27 | ||
FR9300780A FR2700770B1 (fr) | 1993-01-27 | 1993-01-27 | Procédé de fabrication du 1,1,1,2-tétrafluoro-2-chloroéthane et du pentafluoroéthane. |
Publications (2)
Publication Number | Publication Date |
---|---|
KR940018341A true KR940018341A (ko) | 1994-08-16 |
KR970000398B1 KR970000398B1 (en) | 1997-01-09 |
Family
ID=9443387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR94001484A Expired - Lifetime KR970000398B1 (en) | 1993-01-27 | 1994-01-27 | Process for the preparation of 1,1,1,2-tetrafluoro-2-chloroethan and pentafluorethane |
Country Status (13)
Country | Link |
---|---|
US (1) | US5616820A (ko) |
EP (1) | EP0609124B1 (ko) |
JP (1) | JP2510126B2 (ko) |
KR (1) | KR970000398B1 (ko) |
CN (1) | CN1035323C (ko) |
AU (1) | AU663816B2 (ko) |
BR (1) | BR9400338A (ko) |
CA (1) | CA2113511C (ko) |
DE (1) | DE69400342T2 (ko) |
ES (1) | ES2091097T3 (ko) |
FR (1) | FR2700770B1 (ko) |
GR (1) | GR3021203T3 (ko) |
TW (1) | TW258727B (ko) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2700766B1 (fr) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Procédé de fluoration de perchloréthylène ou du pentachloréthane. |
IT1270959B (it) * | 1993-08-13 | 1997-05-26 | Ausimont Spa | Processo per la preparazione di pentafluoroetano |
US5919728A (en) * | 1996-04-17 | 1999-07-06 | Ausimont S.P.A. | Catalyst for the fluorination of halogenated hydrocarbons |
FR2771027B1 (fr) * | 1997-11-20 | 2000-01-14 | Atochem Elf Sa | Catalyseur mixte de fluoration |
US6187976B1 (en) * | 1998-04-09 | 2001-02-13 | Alliedsignal Inc. | Process for the preparation of fluorine containing hydrohalocarbons |
IT1303074B1 (it) * | 1998-05-07 | 2000-10-23 | Ausimont Spa | Catalizzatore per la fluorurazione di composti organici alogenati |
FR2805534B1 (fr) * | 2000-02-29 | 2002-05-17 | Atofina | Procede de preparation du 1,1,1-trifluoro-2,2-dichloroethane |
FR2828193B1 (fr) * | 2001-08-03 | 2004-04-02 | Atofina | Nouveau procede de preparation du 1,1,1,-trifluoro-2,2-dichloroethane |
EP1502906A1 (en) * | 2003-07-31 | 2005-02-02 | Solvay Solexis S.p.A. | Process for activation of AIF3 based catalysts and process for isomerising hydrochlorofluorocarbons |
CN100338001C (zh) * | 2004-11-17 | 2007-09-19 | 浙江莹光化工有限公司 | 一种同时制备1,1,1,2-四氟乙烷和五氟乙烷的方法 |
KR100680766B1 (ko) * | 2005-09-23 | 2007-02-09 | 울산화학주식회사 | 펜타플루오로에탄 제조용 촉매의 제조방법 |
CN115624981A (zh) * | 2022-11-30 | 2023-01-20 | 北京宇极科技发展有限公司 | 金属氟化物、制备方法及其应用 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2435551A (en) * | 1944-04-20 | 1948-02-03 | Standard Oil Dev Co | Production of hydrocarbons from carbon monoxide and hydrogen |
US2900423A (en) * | 1957-12-13 | 1959-08-18 | Allied Chem | Manufacture of perfluoropropene |
DK126161B (da) * | 1968-07-25 | 1973-06-18 | Montedison Spa | Katalysator til fremstilling af chlorflourerede ethaner, der har høj symmetrigrad med hensyn til fordelingen af flouratomerne. |
DK138673B (da) * | 1968-10-10 | 1978-10-16 | Montedison Spa | Katalysator til fremstilling af chlorfluorerede ethaner. |
US3661805A (en) * | 1969-11-21 | 1972-05-09 | Universal Oil Prod Co | Method of manufacturing an extruded catalyst composition |
NL171235C (nl) * | 1970-06-10 | 1983-03-01 | Montedison Spa | Werkwijze voor het bereiden van katalysatoren die in hoofdzaak uit aluminiumfluoride bestaan en werkwijze voor het bereiden van gefluoreerde of gechloorfluoreerde koolwaterstoffen met behulp van een dergelijke katalysator. |
FR2135473B1 (ko) * | 1971-05-06 | 1973-05-11 | Rhone Progil | |
US4131616A (en) * | 1974-06-24 | 1978-12-26 | E. I. Du Pont De Nemours And Company | Methanation catalyst |
FR2407021A1 (fr) * | 1977-10-26 | 1979-05-25 | Anvar | Nouveaux derives metalliques, leur preparation et leur application en tant que catalyseurs, en particulier pour la fabrication de nitriles par ammoxydation d'alcanes a l'aide de monoxyde d'azote |
FR2501062A1 (fr) * | 1980-12-29 | 1982-09-10 | Ugine Kuhlmann | Catalyseurs de fluoruration en phase gazeuse de derives chlores aliphatiques, a base de microbilles d'oxyde de chrome, et procedes de fluoruration utilisant ces catalyseurs |
EP0128510A3 (en) * | 1983-06-07 | 1985-05-15 | Showa Denko Kabushiki Kaisha | Process for producing difluoromethane |
US4912270A (en) * | 1987-03-13 | 1990-03-27 | Allied-Signal Inc. | Chromia aerogel, method of producing same and fluorination process utilizing same |
US4766260A (en) * | 1987-07-07 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Gas-phase fluorination process |
CA1310335C (en) * | 1988-02-12 | 1992-11-17 | Leo E. Manzer | Gas-phase fluorination process |
IN171977B (ko) * | 1988-06-29 | 1993-02-27 | Du Pont | |
JP2764980B2 (ja) * | 1988-12-28 | 1998-06-11 | 旭硝子株式会社 | パークロロエチレンのフッ素化方法 |
DE3930507A1 (de) * | 1989-09-13 | 1991-03-21 | Hoechst Ag | Verfahren zur herstellung von 1,1,1,2-tetrafluorethan |
FR2669022B1 (fr) * | 1990-11-13 | 1992-12-31 | Atochem | Procede de fabrication du tetrafluoro-1,1,1,2-ethane. |
US5300710A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
CA2068832C (en) * | 1991-05-17 | 2002-10-29 | Martin Hoeveler | Process for the preparation of pentafluoroethane (r 125) |
FR2700766B1 (fr) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Procédé de fluoration de perchloréthylène ou du pentachloréthane. |
-
1993
- 1993-01-27 FR FR9300780A patent/FR2700770B1/fr not_active Expired - Fee Related
-
1994
- 1994-01-14 CA CA002113511A patent/CA2113511C/fr not_active Expired - Fee Related
- 1994-01-21 AU AU53951/94A patent/AU663816B2/en not_active Ceased
- 1994-01-21 TW TW083100495A patent/TW258727B/zh not_active IP Right Cessation
- 1994-01-24 EP EP94400140A patent/EP0609124B1/fr not_active Expired - Lifetime
- 1994-01-24 ES ES94400140T patent/ES2091097T3/es not_active Expired - Lifetime
- 1994-01-24 DE DE69400342T patent/DE69400342T2/de not_active Expired - Lifetime
- 1994-01-26 JP JP6007031A patent/JP2510126B2/ja not_active Expired - Fee Related
- 1994-01-26 BR BR9400338A patent/BR9400338A/pt not_active IP Right Cessation
- 1994-01-27 KR KR94001484A patent/KR970000398B1/ko not_active Expired - Lifetime
- 1994-01-27 CN CN94101164A patent/CN1035323C/zh not_active Expired - Lifetime
-
1995
- 1995-06-28 US US08/496,052 patent/US5616820A/en not_active Expired - Lifetime
-
1996
- 1996-09-30 GR GR960402558T patent/GR3021203T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
AU5395194A (en) | 1994-08-18 |
KR970000398B1 (en) | 1997-01-09 |
EP0609124B1 (fr) | 1996-07-31 |
EP0609124A1 (fr) | 1994-08-03 |
TW258727B (ko) | 1995-10-01 |
BR9400338A (pt) | 1994-08-16 |
DE69400342D1 (de) | 1996-09-05 |
JPH06247883A (ja) | 1994-09-06 |
CA2113511A1 (fr) | 1994-07-28 |
JP2510126B2 (ja) | 1996-06-26 |
DE69400342T2 (de) | 1997-01-23 |
CA2113511C (fr) | 1999-01-12 |
ES2091097T3 (es) | 1996-10-16 |
GR3021203T3 (en) | 1996-12-31 |
FR2700770B1 (fr) | 1995-03-24 |
US5616820A (en) | 1997-04-01 |
AU663816B2 (en) | 1995-10-19 |
CN1101337A (zh) | 1995-04-12 |
CN1035323C (zh) | 1997-07-02 |
FR2700770A1 (fr) | 1994-07-29 |
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