EP0641983B1 - Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff und/oder Stickstoff unter Druck - Google Patents

Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff und/oder Stickstoff unter Druck Download PDF

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Publication number
EP0641983B1
EP0641983B1 EP94401839A EP94401839A EP0641983B1 EP 0641983 B1 EP0641983 B1 EP 0641983B1 EP 94401839 A EP94401839 A EP 94401839A EP 94401839 A EP94401839 A EP 94401839A EP 0641983 B1 EP0641983 B1 EP 0641983B1
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EP
European Patent Office
Prior art keywords
air
pressure
heat exchange
column
turbine
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 - Lifetime
Application number
EP94401839A
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English (en)
French (fr)
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EP0641983A1 (de
Inventor
Alain Guillard
Norbert Rieth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication date
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Publication of EP0641983A1 publication Critical patent/EP0641983A1/de
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
    • F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04296—Claude expansion, i.e. expanded into the main or high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04381—Details relating to the work expansion, e.g. process parameter etc. using work extraction by mechanical coupling of compression and expansion so-called companders
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04393—Details relating to the work expansion, e.g. process parameter etc. using multiple or multistage gas work expansion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/939—Partial feed stream expansion, air

Definitions

  • the invention aims to allow a reduction in the production of liquid for a given production capacity of oxygen and / or nitrogen gas under pressure, without increasing the specific energy of each production.
  • the subject of the invention is a process of the aforementioned type, characterized in that said part of the air is only released to an intermediate pressure, the turbined air is partially heated in the line of heat exchange by heat exchange with air which cools, then it is expanded in a second turbine to medium pressure and introduced into the medium pressure column.
  • the invention also relates to an installation intended for the implementation of such a method.
  • This installation of the type comprising a low pressure column operating under a pressure known as low pressure, and a medium pressure column operating under a pressure known as medium pressure; compression means for bringing all of the air to be distilled to at least one high pressure much higher than the medium pressure, these means comprising a main air compressor; means for withdrawing from the double column and pumping at least one liquid product resulting from the distillation; a heat exchange line bringing the air and said liquid product into heat exchange relationship; and an expansion turbine for part of this air, the intake of this turbine being connected to an intermediate point of the heat exchange line, is characterized in that the heat exchange line comprises partial heating passages, the inlet of which is connected to the exhaust of said turbine, and in that the installation includes a second expansion turbine whose inlet is connected to the outlet of these heating passages and whose exhaust is connected to the medium pressure column.
  • the installation shown in the drawing is intended to produce gaseous oxygen at a high pressure of approximately 10 to 100 bars, liquid oxygen and liquid nitrogen.
  • This installation essentially comprises: a main air compressor 1; a pre-cooler 2; an adsorption purification device 3; a fan-turbine assembly comprising a fan 4 and two turbines 5, 6 whose wheels are fixed on the same shaft; an atmospheric or water cooler 7 for the fan; a heat exchange line 8; a double distillation column 9 comprising a medium pressure column 10 and a low pressure column 11 coupled by a vaporizer-condenser 12 which brings the nitrogen at the top of column 10 into heat exchange relationship and liquid oxygen from the bottom of column 11; a liquid oxygen pump 13; a storage 14 of liquid oxygen at atmospheric pressure; a storage 15 of liquid nitrogen at atmospheric pressure; a separator pot 16; and a sub-cooler 17.
  • column 11 is under a pressure slightly higher than atmospheric pressure and column 10 under the corresponding pressure of approximately 5 to 6 bars.
  • All of the air to be distilled is compressed in 1, pre-cooled in 2 to + 5 to + 20 ° C, purified in water and in CO2 in 3 and boosted in 4 at high pressure. After pre-cooling in 7 and then partial cooling in passages 18 of the heat exchange line to an intermediate temperature T1, part of the air under high pressure continues to cool in passages 19 of the heat line. heat exchange, is liquefied and then divided into two fractions. Each fraction is expanded in a respective expansion valve 20, 21, then introduced into the respective column 10, 11.
  • T1 can be chosen to be around 10 ° C lower than the oxygen vaporization temperature, and T2 close to the knee for liquefying air under high pressure, this knee being below the vaporization temperature of oxygen and also below T1.
  • Liquid oxygen is withdrawn from the tank of column 11. A fraction goes directly to storage 15, via a pipe 24, while the rest is brought by pump 13 to the desired high production pressure, then vaporized and reheated at ambient temperature in passages 25 of the heat exchange line before being recovered via a pipe 26.
  • liquid nitrogen at medium pressure drawn off at the top of column 10 is sub-cooled at 17, expanded at atmospheric pressure in an expansion valve 27, and introduced into the separator pot 16.
  • the phase liquid is sent to storage 15, while the vapor phase is combined with impure nitrogen at the head of column 11, then the mixture is heated at 17 then in passages 28 of the heat exchange line and discharged from the installation as WN2 waste gas via line 29.
  • the invention also applies to the production of nitrogen gas under high pressure, brought by a pump (not shown) to the desired high pressure and then vaporized in the heat exchange line, and / or to the production of oxygen. and / or nitrogen under several pressures, using several high air pressures.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Claims (7)

  1. Verfahren zur Herstellung von gasförmigem Sauerstoff und/oder gasförmigem Stickstoff unter Druck, bei dem:
    - Luft in einer Doppel-Destillationskolonne (9) destilliert wird, die eine Niederdruckkolonne (11), die unter einem Druck arbeitet, der Niederdruck genannt wird, und eine Mitteldruckkolonne (10), die unter einem Druck arbeitet, der Mitteldruck genannt wird, umfaßt;
    - die gesamte zu destillierende Luft auf zumindest einen hohen Druck, der deutlich höher ist als der Mitteldruck, verdichtet wird (bei 1, 4);
    - die verdichtete Luft in einer Wärmeaustauschleitung (8) auf eine Zwischentemperatur (T1) abgekühlt wird und ein Teil davon in einer ersten Turbine (5) vor Einleiten in die Mitteldruckkolonne (10) entspannt wird;
    - die nicht durch die Turbine geleitete Luft in der Wärmeaustauschleitung verflüssigt wird, dann nach Entspannung (bei 20, 21) in die Doppelkolonne eingeleitet wird; und
    - zumindest ein aus der Doppelkolonne entnommenes flüssiges Produkt auf den Produktionsdruck gebracht wird (bei 13) und dieses flüssige Produkt in der Wärmeaustauschleitung (8) durch Wärmeaustausch mit der Luft verdampft wird, wobei die Verflüssigungatemperatur der Luft niedriger ist als die Verdampfungstemperatur des flüssigen Produkts, dadurch gekennzeichnet, daß der genannte Teil der Luft nur bis zu einem Zwischendruck entspannt wird, die durch die Turbine geleitete Luft in der Wärmeaustauschleitung durch Wärmeaustausch mit Luft, die sich abkühlt, teilweise erwärmt wird (bei 22), dann in einer zweiten Turbine (6) auf den Mitteldruck entspannt wird und in die Mitteldruckkolonne eingeleitet wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Zwischentemperatur (T1) niedriger ist, insbesondere um etwa 10°C, als die Verdampfungstemperatur des genannten flüssigen Produkts.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Eintrittstemperatur (T2) der zweiten Turbine in der Nähe des Verflüssigungspunktes der Luft liegt.
  4. Verfahren nach einem der vorangehenden Ansprüche, bei dem die in der ersten Turbine (5) entspannte Luft anschließend durch Wärmeaustausch mit der nicht durch die Turbine geleiteten Luft, die zur Verflüssigung vorgesehen ist, erwärmt wird.
  5. Vorrichtung zur Herstellung von gasförmigem Sauerstoff und/oder gasförmigem Stickstoff unter Druck, umfassend eine Doppel-Destillationskolonne (9), die eine Niederdruckkolonne (11), die unter einem Druck arbeitet, der Niederdruck genannt wird, und eine Mitteldruckkolonne (10), die unter einem Druck arbeitet, der Mitteldruck genannt wird, umfaßt, wobei diese Vorrichtungen einen Lufthauptverdichter (1), Verdichtungsvorrichtungen (1, 4), um die gesamte zu destillierende Luft auf zumindest einen hohen Druck, der deutlich höher ist als der Mitteldruck, zu bringen, Vorrichtungen (13) zum Entnehmen zumindest eines nach der Destillation erhaltenen flüssigen Produkts aus der Doppelkolonne und Pumpvorrichtungen dafür, eine Wärmeaustauschleitung (8), die die Luft und das flüssige Produkt in Wärmeaustausch bringt, und eine Turbine (5) zur Entspannung eines Teils dieser Luft umfassen, wobei der Einlaß dieser Turbine mit einem Zwischenpunkt der Wärmeaustauschleitung verbunden ist, dadurch gekennzeichnet, daß die Wärmeaustauschleitung (8) Durchlässe (22) zum teilweisen Erwärmen umfaßt, deren Einlaß mit der Austrittsöffnung der genannten Turbine (5) verbunden ist, und dadurch gekennzeichnet, daß die Vorrichtung eine zweite Turbine (6) zur Entspannung umfaßt, deren Eintrittsöffnung mit dem Auslaß dieser Durchlässe zum Erwärmen verbunden ist und deren Austrittsöffnung mit der Mitteldruckkolonne (10) verbunden ist.
  6. Vorrichtung nach Anspruch 5, dadurch gekennzeichnet, daß die beiden Turbinen (5, 6) auf derselben Welle sitzen.
  7. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß die Welle der beiden Turbinen (5, 6) mit dem Rad eines Verdichters (4) zur Nachverdichtung der aus dem Lufthauptverdichter (1) austretenden Luft starr verbunden ist.
EP94401839A 1993-09-01 1994-08-10 Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff und/oder Stickstoff unter Druck Expired - Lifetime EP0641983B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9310417A FR2709537B1 (fr) 1993-09-01 1993-09-01 Procédé et installation de production d'oxygène et/ou d'azote gazeux sous pression.
FR9310417 1993-09-01

Publications (2)

Publication Number Publication Date
EP0641983A1 EP0641983A1 (de) 1995-03-08
EP0641983B1 true EP0641983B1 (de) 1997-04-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP94401839A Expired - Lifetime EP0641983B1 (de) 1993-09-01 1994-08-10 Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff und/oder Stickstoff unter Druck

Country Status (8)

Country Link
US (1) US5477689A (de)
EP (1) EP0641983B1 (de)
JP (1) JPH07151458A (de)
CN (1) CN1102701A (de)
CA (1) CA2131120A1 (de)
DE (1) DE69402643T2 (de)
ES (1) ES2102790T3 (de)
FR (1) FR2709537B1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5355682A (en) † 1993-09-15 1994-10-18 Air Products And Chemicals, Inc. Cryogenic air separation process producing elevated pressure nitrogen by pumped liquid nitrogen
FR2730172B1 (fr) * 1995-02-07 1997-03-21 Air Liquide Methode et appareil de surveillance de fonctionnement d'une installation de separation d'air
US5758515A (en) * 1997-05-08 1998-06-02 Praxair Technology, Inc. Cryogenic air separation with warm turbine recycle
US5979440A (en) * 1997-06-16 1999-11-09 Sequal Technologies, Inc. Methods and apparatus to generate liquid ambulatory oxygen from an oxygen concentrator
FR2776760B1 (fr) * 1998-03-31 2000-05-05 Air Liquide Procede et appareil de separation d'air par distillation cryogenique
FR2795495B1 (fr) * 1999-06-23 2001-09-14 Air Liquide Procede et installation de separation d'un melange gazeux par distillation cryogenique
JP4594360B2 (ja) * 2007-08-27 2010-12-08 神鋼エア・ウォーター・クライオプラント株式会社 深冷空気液化分離装置およびその運転方法
FR2928446A1 (fr) * 2008-03-10 2009-09-11 Air Liquide Procede de modification d'un appareil de separation d'air par distillation cryogenique
WO2011018207A2 (de) * 2009-08-11 2011-02-17 Linde Aktiengesellschaft Verfahren und vorrichtung zur erzeugung eines gasförmigen sauerstoff-druckprodukts durch tieftemperaturzerlegung von luft
CN104406365B (zh) * 2014-11-27 2017-04-05 苏州制氧机股份有限公司 一种双膨胀机中压液体设备
JP6546504B2 (ja) * 2015-10-20 2019-07-17 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード 酸素製造システム及び酸素製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2652409A1 (fr) * 1989-09-25 1991-03-29 Air Liquide Procede de production frigorifique, cycle frigorifique correspondant et leur application a la distillation d'air.
JP2909678B2 (ja) * 1991-03-11 1999-06-23 レール・リキード・ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード 圧力下のガス状酸素の製造方法及び製造装置
FR2674011B1 (fr) * 1991-03-11 1996-12-20 Maurice Grenier Procede et installation de production d'oxygene gazeux sous pression.
US5365741A (en) * 1993-05-13 1994-11-22 Praxair Technology, Inc. Cryogenic rectification system with liquid oxygen boiler

Also Published As

Publication number Publication date
ES2102790T3 (es) 1997-08-01
CA2131120A1 (fr) 1995-03-02
FR2709537A1 (fr) 1995-03-10
DE69402643T2 (de) 1997-10-02
DE69402643D1 (de) 1997-05-22
US5477689A (en) 1995-12-26
JPH07151458A (ja) 1995-06-16
FR2709537B1 (fr) 1995-10-13
CN1102701A (zh) 1995-05-17
EP0641983A1 (de) 1995-03-08

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