DE69404518T2 - Verfahren für die Stabilisierung von Rhodiumverbindungen - Google Patents
Verfahren für die Stabilisierung von RhodiumverbindungenInfo
- Publication number
- DE69404518T2 DE69404518T2 DE69404518T DE69404518T DE69404518T2 DE 69404518 T2 DE69404518 T2 DE 69404518T2 DE 69404518 T DE69404518 T DE 69404518T DE 69404518 T DE69404518 T DE 69404518T DE 69404518 T2 DE69404518 T2 DE 69404518T2
- Authority
- DE
- Germany
- Prior art keywords
- catalyst solution
- rhodium
- iodide
- carbon monoxide
- carbonylation
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 39
- 150000003284 rhodium compounds Chemical class 0.000 title claims description 31
- 230000006641 stabilisation Effects 0.000 title 1
- 238000011105 stabilization Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 141
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 91
- 238000005810 carbonylation reaction Methods 0.000 claims description 63
- 230000006315 carbonylation Effects 0.000 claims description 42
- -1 aluminum compound Chemical class 0.000 claims description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 36
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 36
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 33
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 31
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 16
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 description 124
- 239000010948 rhodium Substances 0.000 description 63
- 229910052703 rhodium Inorganic materials 0.000 description 53
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 50
- 238000004821 distillation Methods 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 12
- 239000011630 iodine Substances 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 150000001340 alkali metals Chemical class 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 150000003283 rhodium Chemical class 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940071870 hydroiodic acid Drugs 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- DMGNPLVEZUUCBT-UHFFFAOYSA-K aluminum;propanoate Chemical compound [Al+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O DMGNPLVEZUUCBT-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WFSULZXQWNUZPF-UHFFFAOYSA-N ethoxyaluminum Chemical compound CCO[Al] WFSULZXQWNUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FTWKTOVWPKRLHM-UHFFFAOYSA-N methoxyaluminum Chemical compound CO[Al] FTWKTOVWPKRLHM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/82—Metals of the platinum group
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/12—Acetic anhydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP07337593A JP3349542B2 (ja) | 1993-03-31 | 1993-03-31 | ロジウム化合物の安定化法 |
Publications (2)
Publication Number | Publication Date |
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DE69404518D1 DE69404518D1 (de) | 1997-09-04 |
DE69404518T2 true DE69404518T2 (de) | 1997-12-04 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DE69404518T Expired - Fee Related DE69404518T2 (de) | 1993-03-31 | 1994-03-30 | Verfahren für die Stabilisierung von Rhodiumverbindungen |
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Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3349542B2 (ja) * | 1993-03-31 | 2002-11-25 | ダイセル化学工業株式会社 | ロジウム化合物の安定化法 |
CN1047329C (zh) * | 1995-07-21 | 1999-12-15 | 中国科学院化学研究所 | 多齿杂键合型铑催化剂及其制法和用途 |
GB9625335D0 (en) * | 1996-12-05 | 1997-01-22 | Bp Chem Int Ltd | Process |
GB9806527D0 (en) | 1998-03-26 | 1998-05-27 | Bp Chem Int Ltd | Process |
ATE453612T1 (de) * | 2001-02-13 | 2010-01-15 | Eastman Chem Co | Verfahren zur reduzierung von eda bei der essigsäureanhydridproduktion |
US20040152516A1 (en) * | 2002-09-18 | 2004-08-05 | Incredible Technologies, Inc. | Data delivery and management system and method for game machines |
CN104276939B (zh) * | 2013-07-09 | 2016-09-07 | 上海华谊工程有限公司 | 一种醋酐的生产工艺 |
US9340481B1 (en) | 2014-11-14 | 2016-05-17 | Celanese International Corporation | Process for flashing a reaction medium comprising lithium acetate |
US10450652B2 (en) | 2016-04-14 | 2019-10-22 | University of Pittsburgh—of the Commonwealth System of Higher Education | Synthesis of structured carbon material from organic materials |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US4363765A (en) * | 1979-08-27 | 1982-12-14 | Union Carbide Corporation | Rhodium recovery process |
JPH0234656B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) † | 1980-11-24 | 1990-08-06 | Eastman Kodak Co | |
US4476238A (en) * | 1981-05-28 | 1984-10-09 | The Halcon Sd Group, Inc. | Separation of tars from carbonylation reaction mixtures |
US4446074A (en) * | 1981-12-24 | 1984-05-01 | Union Carbide Corporation | Preparation of rhodium complex compounds |
JPS60199852A (ja) * | 1984-03-22 | 1985-10-09 | Daicel Chem Ind Ltd | アセチル化合物の製造方法 |
DE3515396A1 (de) * | 1985-04-29 | 1986-10-30 | Hoechst Ag, 6230 Frankfurt | Verfahren zur reinigung und rueckgewinnung der bei der carbonylierung von methylacetat und/oder dimethylether anfallenden verunreinigten katalysatorloesung |
US4578368A (en) * | 1985-05-06 | 1986-03-25 | Eastman Kodak Company | Catalyst recovery process |
US4976947A (en) † | 1990-02-20 | 1990-12-11 | Eastman Kodak Company | Process for the recovery of elemental iodine from alkyl iodides |
JP3349542B2 (ja) * | 1993-03-31 | 2002-11-25 | ダイセル化学工業株式会社 | ロジウム化合物の安定化法 |
-
1993
- 1993-03-31 JP JP07337593A patent/JP3349542B2/ja not_active Expired - Lifetime
- 1993-10-22 TW TW082108815A patent/TW279814B/zh not_active IP Right Cessation
-
1994
- 1994-01-24 US US08/184,981 patent/US5385875A/en not_active Expired - Lifetime
- 1994-02-14 KR KR1019940002562A patent/KR970002901B1/ko not_active Expired - Lifetime
- 1994-03-30 DE DE69404518T patent/DE69404518T2/de not_active Expired - Fee Related
- 1994-03-30 EP EP94105086A patent/EP0618009B2/en not_active Expired - Lifetime
- 1994-03-30 CN CN94103447A patent/CN1079288C/zh not_active Expired - Lifetime
- 1994-10-21 US US08/327,330 patent/US5516735A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69404518D1 (de) | 1997-09-04 |
US5516735A (en) | 1996-05-14 |
US5385875A (en) | 1995-01-31 |
CN1104931A (zh) | 1995-07-12 |
CN1079288C (zh) | 2002-02-20 |
JPH06277516A (ja) | 1994-10-04 |
EP0618009B1 (en) | 1997-07-30 |
KR970002901B1 (ko) | 1997-03-12 |
JP3349542B2 (ja) | 2002-11-25 |
KR940021426A (ko) | 1994-10-17 |
EP0618009B2 (en) | 2009-08-05 |
EP0618009A1 (en) | 1994-10-05 |
TW279814B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1996-07-01 |
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