KR920016399A - 테레프탈산의 생산방법 - Google Patents
테레프탈산의 생산방법 Download PDFInfo
- Publication number
- KR920016399A KR920016399A KR1019920001597A KR920001597A KR920016399A KR 920016399 A KR920016399 A KR 920016399A KR 1019920001597 A KR1019920001597 A KR 1019920001597A KR 920001597 A KR920001597 A KR 920001597A KR 920016399 A KR920016399 A KR 920016399A
- Authority
- KR
- South Korea
- Prior art keywords
- mother liquor
- precipitate
- terephthalic acid
- solution
- indirectly
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims 10
- 239000012452 mother liquor Substances 0.000 claims 9
- 239000002244 precipitate Substances 0.000 claims 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 238000004508 fractional distillation Methods 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 3
- 239000007787 solid Substances 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000012429 reaction media Substances 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000002638 heterogeneous catalyst Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
Claims (8)
- 수성 모액을 처리하여 테레프탈산과 제2의 모액으로 이루어진 덜 순순한 침전물을 만든뒤, a) 덜순수한 침전물을 직접 또는 간접적으로 반응 매질로 되돌려 보내는 단계, b)최소한 일부분의 상기 제2모액의 물을 사용하여 직접 또는 처리한 후에 간접적으로 크루드한 고체를 용해시키는 단계; c)상기 제2모액을 분별 증류기를 통과시키거나 또는 리플럭스 시키고 처리된 물을 상기 증류기에서 회수한뒤 환원단계 이후에 나온 용액에서부터 회수한 침전물을 사용하여 세척하는 단계;중 최소한 한 단계를 거치는 것을 특징으로하는 아세트산으로 이루어진 액상 반응 매질내에서 파라크실렌을 산화시켜 테레프탈산을 만들고 이를 액상매질에서부터 크루드한 생성물로 분리해낸다음 물로 이루어진 액체에 용해시켜 용액을 만든뒤 이를 환원조건하에서 불균질한 촉매 및 수소와 접촉시켜 최소한 약간의 불순물들을 제거한뒤 이 용액을 냉각시켜 정제된 고체 침전물 테레프탈산을 침전시키고 이 침전물에서부터 수성 모액을 분리해내는 것으로 구성되는 테레프탈산의 제조방법.
- 제1항에 있어서, 단계 a)의 덜순수한 침점물이 수성 모액으로 더 냉각시켜 제조된 방법.
- 제2항에 있어서, 수성 모액을 15~100°C의 온도까지 냉각시킨 방법.
- 전기항중 어느 한 항에 있어서, 단계 c)의 분별증류가 환류비를 2~10으로 하여 행해진 방법.
- 제4항에 있어서, 25~125의 이론단을 사용한 방법.
- 제4항 또는 제5항에 있어서, 분별증류하기 위해 되돌려보낸 모액이 컬럼의 탑상으로부터 0-30%의 이론단으로 공급되는 방법.
- 전기한 항의 어느 한 항에 있어서, 순수한 테레프탈산을 제조하기위한 침전단계가 최소한 3bar의 압력에서 실시되는 방법.
- 전기한 항중 어느 한 항에 있어서, 최소한 일부분의 수성 모액을 사용하여 그 자체로서 직접 또는 처리한 후 간접적으로 크루드 고체를 용해 시키고 및/또는 분별증류기에 통과시킨후 처리된 물을 분별증류기로부터 회수하고 환원 단계후 용액으로부터 회수한 침전물을 세척하는데 사용하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개되는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9102393.7 | 1991-02-05 | ||
GB919102393A GB9102393D0 (en) | 1991-02-05 | 1991-02-05 | Production of terephthalic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
KR920016399A true KR920016399A (ko) | 1992-09-24 |
KR100214397B1 KR100214397B1 (ko) | 1999-08-02 |
Family
ID=10689524
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019920001597A KR100214397B1 (ko) | 1991-02-05 | 1992-02-01 | 테레프탈산의 생산방법 |
Country Status (12)
Country | Link |
---|---|
US (2) | US5304676A (ko) |
EP (1) | EP0498591B2 (ko) |
JP (1) | JPH0558948A (ko) |
KR (1) | KR100214397B1 (ko) |
CN (2) | CN1038580C (ko) |
CA (1) | CA2059719C (ko) |
DE (1) | DE69201978T3 (ko) |
ES (1) | ES2070586T5 (ko) |
GB (2) | GB9102393D0 (ko) |
IN (1) | IN185008B (ko) |
MX (1) | MX9200478A (ko) |
TW (1) | TW326037B (ko) |
Families Citing this family (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9104776D0 (en) * | 1991-03-07 | 1991-04-17 | Ici Plc | Process for the production of terephthalic acid |
GB9310070D0 (en) * | 1992-05-29 | 1993-06-30 | Ici Plc | Process for the production of purified terephthalic acid |
EG20284A (en) * | 1993-02-17 | 1998-07-30 | Ici Plc | Separation process |
GB9303191D0 (en) * | 1993-02-17 | 1993-03-31 | Ici Plc | Separation process |
US5612007A (en) * | 1994-10-14 | 1997-03-18 | Amoco Corporation | Apparatus for preparing aromatic carboxylic acids with efficient energy recovery |
US5961942A (en) * | 1995-06-05 | 1999-10-05 | E. I. Du Pont De Nemours And Company | Effluent gas treatment |
TR199701529T1 (xx) * | 1995-06-05 | 1998-03-21 | E.I. Du Pont De Nemours And Company | ��k�� gaz�n�n i�lemden ge�irilmesi. |
US5929274A (en) | 1995-06-07 | 1999-07-27 | Hfm International, Inc. | Method to reduce carboxybenzaldehyde isomers in terephthalic acid or isophthalic acid |
US6054610A (en) | 1995-06-07 | 2000-04-25 | Hfm International, Inc. | Method and apparatus for preparing purified terephthalic acid and isophthalic acid from mixed xylenes |
US5767311A (en) * | 1995-06-07 | 1998-06-16 | Glitsch International, Inc. | Method and apparatus for preparing purified terephtalic acid |
US6013835A (en) | 1995-06-07 | 2000-01-11 | Hfm International, Inc. | Method and apparatus for preparing purified terephthalic acid |
US6310239B1 (en) * | 1995-12-30 | 2001-10-30 | Sunkyong Industries Co., Ltd. | Process for manufacturing terephthalic acid |
GB9705349D0 (en) | 1997-03-14 | 1997-04-30 | Ici Plc | Treatment of effluent streams |
AU6509398A (en) * | 1997-03-14 | 1998-10-12 | Imperial Chemical Industries Plc | Treatment of effluent streams containing organic acids |
US6137001A (en) * | 1998-02-11 | 2000-10-24 | Bp Amoco Corporation | Process for preparing aromatic carboxylic acids with efficient treatments of gaseous effluent |
US6765113B2 (en) | 2000-07-19 | 2004-07-20 | E.I. Du Pont De Nemours And Company | Production of aromatic carboxylic acids |
EP1402942B8 (en) * | 2001-05-15 | 2010-04-14 | Mitsubishi Chemical Corporation | Process for producing a compound |
US7196215B2 (en) * | 2001-06-04 | 2007-03-27 | Eastman Chemical Company | Process for the production of purified terephthalic acid |
US7485747B2 (en) * | 2001-06-04 | 2009-02-03 | Eastman Chemical Company | Two stage oxidation process for the production of aromatic dicarboxylic acids |
ITMI20021423A1 (it) * | 2002-06-27 | 2003-12-29 | Eurotecnica Dev & Licensing S | Processo per la separazione dell'acqua prodotta nella ossidazione catalitica di idrocarburi aromatici ad acidi aromatici policarbossilici |
EP1542958B1 (en) * | 2002-07-09 | 2007-10-17 | INVISTA Technologies S.à.r.l. | Process for producing aromatic dicarboxylic acids under supercritical conditions |
AU2003289482A1 (en) * | 2003-01-07 | 2004-07-29 | Mitsubishi Chemical Corporation | Process for producing high-purity terephthalic acid |
AU2003292740A1 (en) * | 2003-01-10 | 2004-08-10 | Mitsubishi Chemical Corporation | Process for producing aromatic carboxylic acid and process for producing terephthalic acid |
US20050256335A1 (en) * | 2004-05-12 | 2005-11-17 | Ovidiu Marin | Providing gases to aromatic carboxylic acid manufacturing processes |
WO2005115957A1 (ja) * | 2004-05-28 | 2005-12-08 | Mitsubishi Chemical Corporation | 高純度テレフタル酸の製造方法 |
US7582793B2 (en) | 2004-09-02 | 2009-09-01 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7615663B2 (en) * | 2004-09-02 | 2009-11-10 | Eastman Chemical Company | Optimized production of aromatic dicarboxylic acids |
US7495125B2 (en) * | 2004-09-02 | 2009-02-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7390921B2 (en) * | 2004-09-02 | 2008-06-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7589231B2 (en) * | 2004-09-02 | 2009-09-15 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7568361B2 (en) * | 2004-09-02 | 2009-08-04 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7683210B2 (en) * | 2004-09-02 | 2010-03-23 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7504535B2 (en) * | 2004-09-02 | 2009-03-17 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7371894B2 (en) * | 2004-09-02 | 2008-05-13 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7692036B2 (en) | 2004-11-29 | 2010-04-06 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7692037B2 (en) | 2004-09-02 | 2010-04-06 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7608732B2 (en) * | 2005-03-08 | 2009-10-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7910769B2 (en) * | 2004-09-02 | 2011-03-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7399882B2 (en) * | 2004-09-02 | 2008-07-15 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7741515B2 (en) * | 2004-09-02 | 2010-06-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7563926B2 (en) | 2004-09-02 | 2009-07-21 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7608733B2 (en) * | 2004-09-02 | 2009-10-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7507857B2 (en) * | 2004-09-02 | 2009-03-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7381836B2 (en) * | 2004-09-02 | 2008-06-03 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7586000B2 (en) * | 2004-09-02 | 2009-09-08 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7572932B2 (en) * | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7361784B2 (en) * | 2004-09-02 | 2008-04-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US20060047153A1 (en) * | 2004-09-02 | 2006-03-02 | Wonders Alan G | Optimized liquid-phase oxidation |
US7572936B2 (en) | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7482482B2 (en) * | 2004-09-02 | 2009-01-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
BRPI0609328B1 (pt) | 2005-03-21 | 2016-04-12 | Bp Corp North America Inc | processos de produção de ácidos carboxílicos aromáticos e equipamentos de separação dos componentes de gás |
CN101146759B (zh) * | 2005-03-22 | 2011-05-18 | 三菱化学株式会社 | 高纯度对苯二甲酸的制造方法 |
US7884232B2 (en) * | 2005-06-16 | 2011-02-08 | Eastman Chemical Company | Optimized liquid-phase oxidation |
US7402694B2 (en) * | 2005-08-11 | 2008-07-22 | Eastman Chemical Company | Process for removal of benzoic acid from an oxidizer purge stream |
US7358389B2 (en) * | 2006-01-04 | 2008-04-15 | Eastman Chemical Company | Oxidation system employing internal structure for enhanced hydrodynamics |
US7355068B2 (en) | 2006-01-04 | 2008-04-08 | Eastman Chemical Company | Oxidation system with internal secondary reactor |
CN100368370C (zh) * | 2006-03-29 | 2008-02-13 | 中国石化仪征化纤股份有限公司 | 对二甲苯氧化母液中悬浮物的回收系统装置 |
CN101152969B (zh) * | 2006-09-29 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | 对苯二甲酸生产废水的处理方法 |
WO2009141968A1 (ja) * | 2008-05-20 | 2009-11-26 | 株式会社日立プラントテクノロジー | 精製テレフタル酸分離母液の処理方法 |
MX2011011148A (es) | 2009-04-24 | 2012-01-27 | Invista Tech Sarl | Metodos, procesos y sistemas para el tratamiento y purificacion de acido tereftalico crudo y corrientes de proceso asociadas. |
WO2013025105A1 (en) | 2011-08-16 | 2013-02-21 | /Purac Biochem B.V. | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
EP2744747B1 (en) | 2011-08-16 | 2020-11-18 | Purac Biochem B.V. | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
CN102798679B (zh) * | 2012-09-03 | 2014-01-15 | 绍兴汉青环保科技有限公司 | 一种pta 生产装置气体中有机物的气相色谱分析方法 |
KR20160098471A (ko) | 2013-12-18 | 2016-08-18 | 비피 코포레이션 노쓰 아메리카 인코포레이티드 | 방향족 카르복시산의 생산을 위한 개선된 공정 및 장치 |
WO2017081610A1 (en) | 2015-11-13 | 2017-05-18 | Sabic Global Technologies B.V. | Process using ion exchange resins for the treatment of wastewater emanating from purified terephthalic acid production |
CN113318471B (zh) * | 2021-07-08 | 2024-05-31 | 山东友道化学有限公司 | 二甲苯氧化反应液的处理方法及系统 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2849483A (en) * | 1954-07-30 | 1958-08-26 | Chemstrand Corp | Method of purifying aromatic dicarboxylic acids |
GB970492A (en) * | 1960-10-18 | 1964-09-23 | Standard Oil Co | Production of aromatic carboxylic acids |
GB970491A (en) * | 1960-10-18 | 1964-09-23 | Standard Oil Co | Production of aromatic carboxylic acids |
NL6606774A (ko) * | 1965-05-17 | 1966-11-18 | ||
FR1569704A (ko) * | 1968-02-26 | 1969-06-06 | ||
US3592847A (en) * | 1968-05-02 | 1971-07-13 | Allied Chem | Process for the purification of terephthalic acid |
GB1373230A (en) * | 1971-12-23 | 1974-11-06 | Mitsui Petrochemical Ind | Process for producing terephthalic acid |
JPS52128344A (en) * | 1976-04-20 | 1977-10-27 | Mitsubishi Gas Chem Co Inc | Preparation of high-purity terephthalic acid |
US4467111A (en) * | 1981-10-29 | 1984-08-21 | Standard Oil Company (Indiana) | Process for purification of crude terephthalic acid |
US5166420A (en) * | 1986-10-20 | 1992-11-24 | Mitsui Petrochemical Industries, Ltd. | Process for the production of high purity terephthalic acid |
US4933492A (en) * | 1988-10-13 | 1990-06-12 | Amoco Corporation | Purification of crude isophthalic acid |
-
1991
- 1991-02-05 GB GB919102393A patent/GB9102393D0/en active Pending
-
1992
- 1992-01-30 CA CA002059719A patent/CA2059719C/en not_active Expired - Lifetime
- 1992-01-30 US US07/827,205 patent/US5304676A/en not_active Ceased
- 1992-02-01 KR KR1019920001597A patent/KR100214397B1/ko not_active IP Right Cessation
- 1992-02-03 CN CN92101420A patent/CN1038580C/zh not_active Ceased
- 1992-02-03 DE DE69201978T patent/DE69201978T3/de not_active Expired - Lifetime
- 1992-02-03 EP EP92300888A patent/EP0498591B2/en not_active Expired - Lifetime
- 1992-02-03 GB GB929202241A patent/GB9202241D0/en active Pending
- 1992-02-03 IN IN75DE1992 patent/IN185008B/en unknown
- 1992-02-03 ES ES92300888T patent/ES2070586T5/es not_active Expired - Lifetime
- 1992-02-04 MX MX9200478A patent/MX9200478A/es unknown
- 1992-02-05 JP JP4019980A patent/JPH0558948A/ja active Pending
- 1992-02-26 TW TW081101427A patent/TW326037B/zh active
-
1996
- 1996-04-19 US US08/634,991 patent/USRE36008E/en not_active Expired - Lifetime
- 1996-08-15 CN CN96109973A patent/CN1130328C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
MX9200478A (es) | 1992-08-01 |
CA2059719C (en) | 2002-10-08 |
KR100214397B1 (ko) | 1999-08-02 |
US5304676A (en) | 1994-04-19 |
DE69201978D1 (de) | 1995-05-18 |
GB9202241D0 (en) | 1992-03-18 |
EP0498591B2 (en) | 2004-10-13 |
EP0498591A2 (en) | 1992-08-12 |
DE69201978T2 (de) | 1995-08-24 |
CN1064675A (zh) | 1992-09-23 |
CN1130328C (zh) | 2003-12-10 |
JPH0558948A (ja) | 1993-03-09 |
EP0498591B1 (en) | 1995-04-12 |
GB9102393D0 (en) | 1991-03-20 |
CN1038580C (zh) | 1998-06-03 |
ES2070586T3 (es) | 1995-06-01 |
EP0498591A3 (en) | 1993-01-27 |
ES2070586T5 (es) | 2005-05-01 |
DE69201978T3 (de) | 2005-03-10 |
IN185008B (ko) | 2000-10-21 |
CN1150944A (zh) | 1997-06-04 |
TW326037B (en) | 1998-02-01 |
USRE36008E (en) | 1998-12-22 |
CA2059719A1 (en) | 1992-08-06 |
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