HK56792A - Gas-phase fluorination process - Google Patents
Gas-phase fluorination processInfo
- Publication number
- HK56792A HK56792A HK567/92A HK56792A HK56792A HK 56792 A HK56792 A HK 56792A HK 567/92 A HK567/92 A HK 567/92A HK 56792 A HK56792 A HK 56792A HK 56792 A HK56792 A HK 56792A
- Authority
- HK
- Hong Kong
- Prior art keywords
- tetrahaloethylene
- metal
- catalyst
- chromium
- content
- Prior art date
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- 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
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Claims (10)
1. Verfahren zur Herstellung von 1,1,1-Trifluorodichlorethan und 1,1,1,2-Tetrafluorochlorethan durch Fluorierung eines Tetrahalogenethylens, C2Cl4-xFx, worin x = 0 bis 3 ist, bei dem man das Tetrahalogenethylen und HF in der Gasphase bei 300 °C bis 450 °C mit einem Katalysator in Kontakt bringt, der mindestens ein Metall in einem Oxidationszustand von mehr als 0 enthält, wobei das Metall ausgewählt wird aus der Gruppe, bestehend aus Chrom, Mangan, Nickel und Kobalt, und im Falle von Chrom dieses in der Form von Chromfluorid oder Chromoxyfluorid enthalten ist, auf einem Träger, der Aluminium, Sauerstoff und Fluor in solchen Mengenanteilen enthält, daß der Fluorgehalt einem AlF3-Gehalt von mindestens 90 Gew.-% der Katalysatorzusammensetzung, ausschießend das Metall, entspricht und der A1F3-Gehalt durch Vorbehandlung mit HF erhalten wurde.
2. Verfahren nach Anspruch 1, worin das Tretrahalogenethylen Tetrachlorethylen ist.
3. Verfahren nach Anspruch 1 oder 2, bei dem der Katalysator 0,02 bis 20 Gew.-% Metall, ausgedrückt als zweiwertiges Oxid, enthält.
4. Verfahren nach Anspruch 3, bei dem der Katalysator 0,1 bis 5 Gew.-% Metall enthält, ausgedrückt als zweiwertiges Oxid.
5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das HF mit dem Tetrahalogenethylen bei einem Molverhältnis von 1:1 bis 20:1 bei einer Temperatur von 300 °C bis 400 °C und einer Kontaktzeit von 5 bis 100 Sekunden kontaktiert wird.
6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Umwandlung des Tetrahalogenethylens in fluorierte Produkte zwischen 30 % und 95 % liegt.
7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Metall ausgewählt wird aus der Gruppe, bestehend aus Mangan, Nickel und Kobalt.
8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Temperatur, das Molverhältnis von HF zu Tetrahalogenethylen und die Kontaktzeit so gelenkt werden, daß ein Produktstrom entsteht, der einen CF3CHCI2-Gehalt von mehr als dem von CF3CHCIF hat und die kombinierte Gesamtmenge von CF3CHCI2 und CF3CHCIF größer ist als die von CF3CHF2 im Produktstrom ist.
9. Verfahren nach einem dervorhergehenden Ansprüche, bei dem die Menge an CF3CHF2 im Produktstrom niedriger ist als 10 %.
10. Verfahren nach einem der vorhergehenden Ansprüche, weiter umfassend die Stufe des Recyclen von mindestens einem Teil von CF3CHCI2, das in der Kontaktierstufe erzeugt wurde, für die Umwandlung zu weiterem CF3CHCIF.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/070,826 US4766260A (en) | 1987-07-07 | 1987-07-07 | Gas-phase fluorination process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK56792A true HK56792A (en) | 1992-08-07 |
Family
ID=22097611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HK567/92A HK56792A (en) | 1987-07-07 | 1992-07-30 | Gas-phase fluorination process |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4766260A (de) |
| EP (1) | EP0298662B2 (de) |
| JP (1) | JP2578923B2 (de) |
| KR (1) | KR890001916A (de) |
| CN (1) | CN1014404B (de) |
| AR (1) | AR244651A1 (de) |
| AT (1) | ATE73748T1 (de) |
| AU (1) | AU600212B2 (de) |
| BR (1) | BR8803356A (de) |
| CA (1) | CA1308743C (de) |
| DE (1) | DE3869242D1 (de) |
| ES (1) | ES2033432T3 (de) |
| GR (1) | GR3004106T3 (de) |
| HK (1) | HK56792A (de) |
| MX (1) | MX166813B (de) |
| RU (1) | RU1799375C (de) |
| SG (1) | SG54092G (de) |
| ZA (1) | ZA884845B (de) |
Families Citing this family (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008475A (en) * | 1987-07-07 | 1991-04-16 | E. I. Du Pont De Nemours And Company | Gas-phase fluorination process |
| JPH01108292A (ja) * | 1987-10-19 | 1989-04-25 | Daikin Ind Ltd | 冷媒 |
| US4843181A (en) * | 1987-10-22 | 1989-06-27 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1-trifluorodichloroethane and 1,1,1,2-tetrafluorochloroethane |
| IN170774B (de) * | 1988-05-23 | 1992-05-16 | Du Pont | |
| AU616284B2 (en) * | 1988-06-23 | 1991-10-24 | E.I. Du Pont De Nemours And Company | Catalyzed hydrofluorination process |
| US5094773A (en) * | 1988-08-01 | 1992-03-10 | E. I. Du Pont De Nemours And Company | Azeotropes of HF and process for the separation of HF via azeotropic distillation |
| EP0366404B1 (de) * | 1988-10-25 | 1993-01-20 | E.I. Du Pont De Nemours And Company | Verfahren zur Herstellung von 1,1,1,2-Tetrafluorethan |
| GB8828544D0 (en) * | 1988-12-07 | 1989-01-11 | Ici Plc | Chemical process |
| IT1230779B (it) * | 1989-07-12 | 1991-10-29 | Ausimont Srl | Procedimento per preparare 1,1,1,2 tetrafluoroetano. |
| IT1230780B (it) * | 1989-07-12 | 1991-10-29 | Ausimont Srl | Procedimento per la preparazione di 1,2 dicloro 1,1,2 trifluoroetano. |
| DE69031344D1 (de) * | 1989-10-04 | 1997-10-02 | Du Pont | Verfahren zur reinigung von fluorkohlenwasserstoffen |
| US5171901A (en) * | 1990-02-14 | 1992-12-15 | Bayer Aktiengesellschaft | Process for the preparation of 1,1,1,3,3,3-hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropane |
| FR2661906B1 (fr) * | 1990-05-11 | 1993-10-01 | Atochem | Procede de fabrication du 1,1,1,2-tetrafluoro-chloroethane et du pentafluoroethane. |
| US5030372A (en) * | 1990-07-31 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Catalytic equilibration to improve the relative yield of selected halocarbons |
| JPH06501921A (ja) * | 1990-07-31 | 1994-03-03 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 選択されたハロカーボンの触媒平衡化 |
| MX9201219A (es) * | 1991-03-20 | 1992-10-01 | Du Pont | Procedimiento para la produccion de 2-cloro-1,1,1-trifluoro etano. |
| US5321170A (en) * | 1991-03-20 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US5300711A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| 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 |
| JP2748720B2 (ja) * | 1991-05-23 | 1998-05-13 | ダイキン工業株式会社 | ハロゲン化炭化水素のフッ素化方法 |
| US5243106A (en) * | 1991-06-03 | 1993-09-07 | E. I. Du Pont De Nemours And Company | Processes using aluminum fluoride catalyst compositions for preparing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| US5243108A (en) * | 1991-06-03 | 1993-09-07 | E. I. Du Pont De Nemours And Company | Aluminum fluoride catalyst compositions and use thereof in a chlorofluorination process for preparing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| IT1251951B (it) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | Procedimento per purificare 1,1,1-trifluoro-,2,2 dicloroetano dall`isomero 1,1,2-trifluoro-1,2-dicloroetano. |
| IT1251957B (it) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | Procedimento per isomerizzare 1,1,2-trifluoro-1,2-dicloroetano a 1,1,1- trifluoro-2,2,-dicloroetano |
| US5334785A (en) * | 1991-10-25 | 1994-08-02 | Allied-Signal Inc. | Process for the manufacture of 1,1,1,2-tetrafluoroethane |
| JP2661441B2 (ja) * | 1991-11-27 | 1997-10-08 | ダイキン工業株式会社 | 1,1,1−トリフルオロ−2−クロロエタンおよび/または1,1,1,2−テトラフルオロエタンの製法 |
| JPH05194287A (ja) * | 1992-01-13 | 1993-08-03 | Daikin Ind Ltd | ハロゲン化ブテンおよびブタンの製造方法 |
| JP3369604B2 (ja) * | 1992-09-04 | 2003-01-20 | ダイキン工業株式会社 | 1,1,1,2,3,3−ヘキサフルオロプロパンの製造方法及びテトラフルオロクロロプロペンの製造方法 |
| US5345017A (en) * | 1992-12-08 | 1994-09-06 | E. I. Du Pont De Nemours And Company | Process for reducing the fluorine content of halocarbons |
| US5523498A (en) | 1992-12-08 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Process for reducing the fluorine content of hydrofluorocarbons and hydrohalofluorocarbons |
| FR2700766B1 (fr) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Procédé de fluoration de perchloréthylène ou du pentachloréthane. |
| FR2700770B1 (fr) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Procédé de fabrication du 1,1,1,2-tétrafluoro-2-chloroéthane et du pentafluoroéthane. |
| US5827492A (en) * | 1993-01-28 | 1998-10-27 | E. I. Du Pont De Nemours And Company | Hydrogen chloride purification process |
| US5866730A (en) * | 1993-04-02 | 1999-02-02 | E. I. Du Pont De Nemours And Company | Process for enriching 1,2-dichloro-1,1,2,2-tetrafluoroethane from a mixture of dichlorotetrafluoroethane isomers |
| US5274190A (en) * | 1993-05-24 | 1993-12-28 | E. I. Du Pont De Nemours And Company | Process for the manufacture of linear hydrofluorocarbons containing end group hydrogen substituents |
| US5396000A (en) * | 1993-05-24 | 1995-03-07 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1,2,3,-pentafluoropropane |
| US5409625A (en) * | 1993-05-24 | 1995-04-25 | E. I. Du Pont De Nemours And Company | Azeotropic mixture of linear hydrofluorocarbon and HF |
| US5274189A (en) * | 1993-05-24 | 1993-12-28 | E. I. Du Pont De Nemours And Company | Process for the manufacture of linear hydrofluorocarbons containing end group hydrogen substituents |
| WO1995011875A1 (en) * | 1993-10-28 | 1995-05-04 | Alliedsignal Inc. | Process for purifying 1,1-dichloro-2,2,2-trifluoroethane and 1-chloro-1,2,2,2-tetrafluoroethane |
| US5411583A (en) * | 1993-11-15 | 1995-05-02 | E. I. Du Pont De Nemours And Company | HF-resistant ceramics and use thereof |
| JP2865554B2 (ja) * | 1994-04-08 | 1999-03-08 | セントラル硝子株式会社 | フルオロメチル−1,1,1,3,3,3−ヘキサフルオロイソプロピルエーテルのガスクロマトグラフ分析 |
| US5545778A (en) * | 1994-05-25 | 1996-08-13 | Alliedsignal Inc. | Single stage process for producing hydrofluorocarbons from perchloroethylene |
| US5569794A (en) * | 1994-05-24 | 1996-10-29 | Alliedsignal Inc. | Vapor phase process for producing hydroflourocarbons from perchloroethylene having a phenolic inhibitor |
| US5563304A (en) | 1994-05-26 | 1996-10-08 | E. I. Du Pont De Nemours And Company | Production of 1,2-dihydro and 2,2-dihydro hexafluoropropanes and azeotropes thereof with HF |
| WO1996011176A1 (en) * | 1994-10-07 | 1996-04-18 | Daikin Industries, Ltd. | Method of separating pentafluoroethane and process for producing pentafluoroethane by utilizing said method |
| JP3558385B2 (ja) * | 1994-10-13 | 2004-08-25 | 昭和電工株式会社 | クロム系フッ素化触媒、及びフッ素化方法 |
| US5847242A (en) * | 1995-05-19 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use |
| RU2141467C1 (ru) * | 1997-03-25 | 1999-11-20 | Товарищество с ограниченной ответственностью Научно-техническая фирма "Комкон" | Способ получения пентафторэтана |
| IT1303074B1 (it) | 1998-05-07 | 2000-10-23 | Ausimont Spa | Catalizzatore per la fluorurazione di composti organici alogenati |
| US6365544B2 (en) | 1998-05-22 | 2002-04-02 | Conoco Inc. | Fischer-Tropsch processes and catalysts using fluorided alumina supports |
| US6368997B2 (en) * | 1998-05-22 | 2002-04-09 | Conoco Inc. | Fischer-Tropsch processes and catalysts using fluorided supports |
| US6472574B2 (en) | 1999-12-10 | 2002-10-29 | E. I. Du Pont Nemours And Company | Production of 1,2-dihydro and 2,2-dihydro hexafluoropropanes and azeotropes thereof with HF |
| US6333440B1 (en) | 2000-04-07 | 2001-12-25 | E. I. Du Pont De Nemours And Company | Process for perfluorocyclobutane purification |
| US7897823B2 (en) * | 2004-10-29 | 2011-03-01 | E. I. Du Pont De Nemours And Company | Process for production of azeotrope compositions comprising hydrofluoroolefin and hydrogen fluoride and uses of said azeotrope compositions in separation processes |
| US7476771B2 (en) | 2005-11-01 | 2009-01-13 | E.I. Du Pont De Nemours + Company | Azeotrope compositions comprising 2,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof |
| GB0525700D0 (en) * | 2005-12-17 | 2006-01-25 | Ineos Fluor Holdings Ltd | Process |
| GB0525699D0 (en) | 2005-12-17 | 2006-01-25 | Ineos Fluor Holdings Ltd | Process |
| GB0525702D0 (en) * | 2005-12-17 | 2006-01-25 | Ineos Fluor Holdings Ltd | Process |
| GB0525701D0 (en) * | 2005-12-17 | 2006-01-25 | Ineos Fluor Holdings Ltd | Process |
| ES2392591T3 (es) * | 2006-03-31 | 2012-12-12 | E.I. Du Pont De Nemours And Company | Coproducción de hidrofluoroolefinas |
| CN101578252B (zh) * | 2006-09-05 | 2013-11-27 | 纳幕尔杜邦公司 | 1,2,3,3,3-五氟丙烯生产方法 |
| CN101522597B (zh) | 2006-10-03 | 2013-05-29 | 墨西哥化学阿玛科股份有限公司 | 通过脱卤化氢制备c3-c6(氢)氟烯烃的方法 |
| CN103755519A (zh) * | 2014-02-24 | 2014-04-30 | 山东联创节能新材料股份有限公司 | 六氟丁烯的合成方法 |
| CN112946126B (zh) * | 2021-02-02 | 2022-07-15 | 福建德尔科技有限公司 | 高纯三氟化氯中杂质定量、定性装置及方法 |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2755313A (en) * | 1951-08-03 | 1956-07-17 | Allied Chem & Dye Corp | Manufacture of saturated halocarbons |
| US2669590A (en) * | 1951-08-03 | 1954-02-16 | Allied Chem & Dye Corp | Production of fluorine compounds |
| US2744147A (en) * | 1952-02-04 | 1956-05-01 | Dow Chemical Co | Fluorination of haloalkanes with a catalyst containing gamma alumina |
| US2744148A (en) * | 1952-02-04 | 1956-05-01 | Dow Chemical Co | Process for fluorination of haloalkanes using a hydrogen fluoride activated catalyst containing alumina, a metal fluoride and basic aluminum fluoride |
| US2724004A (en) * | 1952-04-08 | 1955-11-15 | Goodrich Co B F | Preparation of 1, 1-difluoro-1, 2, 2-trichloroethane |
| US2850543A (en) * | 1954-02-17 | 1958-09-02 | Allied Chem | Manufacture of 1, 2, 2-trichloro-1, 1, 2-trifluoroethane |
| GB805503A (en) * | 1956-03-15 | 1958-12-10 | Dow Chemical Co | Improved fluorination catalyst and process |
| US3258500A (en) * | 1959-08-17 | 1966-06-28 | Du Pont | Process for fluorinating halohydro-carbons |
| US3157707A (en) * | 1961-02-20 | 1964-11-17 | Union Carbide Corp | Method of reacting tetrachloroethylene, chlorine and hydrogen fluoride |
| NL274475A (de) * | 1962-02-07 | |||
| GB1000485A (en) * | 1962-02-07 | 1965-08-04 | Sicedison Spa | Improvements in or relating to the fluorination of halo-olefines |
| NL301934A (de) * | 1962-12-28 | 1900-01-01 | ||
| US3607955A (en) * | 1968-04-08 | 1971-09-21 | Phillips Petroleum Co | Hydrofluorination and dehydrofluorination and catalysts therefor |
| NL169036C (nl) * | 1968-07-25 | 1982-06-01 | Montedison Spa | Werkwijze voor het bereiden van gefluoreerde of gechloorfluoreerde koolwaterstoffen door middel van fluorerings- of chloorfluoreringsreacties in de gasfase. |
| DK138673B (da) * | 1968-10-10 | 1978-10-16 | Montedison Spa | Katalysator til fremstilling af chlorfluorerede ethaner. |
| DE1910529C3 (de) * | 1969-03-01 | 1978-09-28 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur katalytischen Hydrofluorierung von bestimmten gesattigten und ungesättigten halogenierten Kohlenwasserstoffen |
| GB1307224A (en) * | 1969-06-27 | 1973-02-14 | Ici Ltd | Chromium oxide catalyst |
| SE374675B (de) * | 1970-06-10 | 1975-03-17 | Montedison Spa | |
| US3752850A (en) * | 1970-12-24 | 1973-08-14 | Hoechst Ag | Fluorination of aliphatic compounds |
| BE613582A (de) * | 1973-09-24 | 1900-01-01 | ||
| US4147733A (en) * | 1978-05-22 | 1979-04-03 | The Dow Chemical Company | Fluorination of chlorinated hydrocarbons |
| DE3009760A1 (de) * | 1980-03-14 | 1981-09-24 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von hochreinen teilfluorierten aethanen |
| IT1202652B (it) * | 1987-03-09 | 1989-02-09 | Ausimont Spa | Processo per la preparazione di 1,1,1-trifluoro-2,2-dicloroetano mediante idrofluorurazione in presenza di catalizzatori |
-
1987
- 1987-07-07 US US07/070,826 patent/US4766260A/en not_active Expired - Lifetime
-
1988
- 1988-06-30 EP EP88305956A patent/EP0298662B2/de not_active Expired - Lifetime
- 1988-06-30 DE DE8888305956T patent/DE3869242D1/de not_active Expired - Lifetime
- 1988-06-30 ES ES198888305956T patent/ES2033432T3/es not_active Expired - Lifetime
- 1988-06-30 AT AT88305956T patent/ATE73748T1/de not_active IP Right Cessation
- 1988-07-05 CA CA000571133A patent/CA1308743C/en not_active Expired - Lifetime
- 1988-07-06 KR KR1019880008379A patent/KR890001916A/ko not_active Withdrawn
- 1988-07-06 AR AR88311354A patent/AR244651A1/es active
- 1988-07-06 AU AU18771/88A patent/AU600212B2/en not_active Ceased
- 1988-07-06 BR BR8803356A patent/BR8803356A/pt not_active Application Discontinuation
- 1988-07-06 ZA ZA884845A patent/ZA884845B/xx unknown
- 1988-07-06 RU SU884356113A patent/RU1799375C/ru active
- 1988-07-07 MX MX012191A patent/MX166813B/es unknown
- 1988-07-07 CN CN88104212A patent/CN1014404B/zh not_active Expired
- 1988-07-07 JP JP63167898A patent/JP2578923B2/ja not_active Expired - Fee Related
-
1992
- 1992-03-19 GR GR920400461T patent/GR3004106T3/el unknown
- 1992-05-15 SG SG540/92A patent/SG54092G/en unknown
- 1992-07-30 HK HK567/92A patent/HK56792A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0298662A1 (de) | 1989-01-11 |
| JPH01221338A (ja) | 1989-09-04 |
| MX166813B (es) | 1993-02-08 |
| AU600212B2 (en) | 1990-08-02 |
| SG54092G (en) | 1992-07-24 |
| US4766260A (en) | 1988-08-23 |
| KR890001916A (ko) | 1989-04-06 |
| EP0298662B1 (de) | 1992-03-18 |
| RU1799375C (ru) | 1993-02-28 |
| EP0298662B2 (de) | 1999-08-11 |
| AU1877188A (en) | 1989-01-12 |
| DE3869242D1 (de) | 1992-04-23 |
| BR8803356A (pt) | 1989-01-24 |
| CA1308743C (en) | 1992-10-13 |
| ZA884845B (en) | 1990-03-28 |
| JP2578923B2 (ja) | 1997-02-05 |
| AR244651A1 (es) | 1993-11-30 |
| CN1014404B (zh) | 1991-10-23 |
| ES2033432T3 (es) | 1993-03-16 |
| GR3004106T3 (de) | 1993-03-31 |
| ATE73748T1 (de) | 1992-04-15 |
| CN1031073A (zh) | 1989-02-15 |
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