EP0379435B2 - Procédé et installation de séparation d'air et de production d'oxygène ultra-pur - Google Patents

Procédé et installation de séparation d'air et de production d'oxygène ultra-pur Download PDF

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Publication number
EP0379435B2
EP0379435B2 EP90400145A EP90400145A EP0379435B2 EP 0379435 B2 EP0379435 B2 EP 0379435B2 EP 90400145 A EP90400145 A EP 90400145A EP 90400145 A EP90400145 A EP 90400145A EP 0379435 B2 EP0379435 B2 EP 0379435B2
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EP
European Patent Office
Prior art keywords
column
auxiliary column
auxiliary
level
low pressure
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
EP90400145A
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German (de)
English (en)
French (fr)
Other versions
EP0379435B1 (fr
EP0379435A1 (fr
Inventor
Maurice Grenier
Philippe Mazieres
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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Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to AT90400145T priority Critical patent/ATE74421T1/de
Publication of EP0379435A1 publication Critical patent/EP0379435A1/fr
Publication of EP0379435B1 publication Critical patent/EP0379435B1/fr
Application granted granted Critical
Publication of EP0379435B2 publication Critical patent/EP0379435B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04709—Producing crude argon in a crude argon column as an auxiliary column system in at least a dual pressure main column system
    • F25J3/04715—The auxiliary column system simultaneously produces 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
    • F25J3/04406—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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F25J2200/06—Processes or apparatus using separation by rectification in a dual pressure main column system in a classical double column flow-sheet, 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/34—Processes or apparatus using separation by rectification using a side column fed by a stream from the low 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/90—Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
    • F25J2215/52—Oxygen production with multiple purity O2
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
    • F25J2215/56—Ultra high purity oxygen, i.e. generally more than 99,9% O2
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/58—Processes or apparatus involving steps for recycling of process streams the recycled stream being argon or crude argon
    • 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
    • Y10S62/923—Inert gas
    • Y10S62/924—Argon

Definitions

  • the present invention relates to a method and an installation for producing oxygen ultra-pure from a main distillation apparatus double column air.
  • ultra-pure oxygen oxygen practically free of methane (and therefore of hydrocarbons) and argon, for example containing less 0.1 ppm oil and less than 10 ppm argon, these contents being fixed in advance and being able vary depending on the application. Ultra-pure oxygen is especially intended for industries electronic.
  • the object of the invention is to enable production ultra-pure oxygen at the cost of a modification inexpensive of the main distillation apparatus and, above all, without additional energy expenditure.
  • Preferential execution allows production substantially free of high purity oxygen of hydrocarbons.
  • the installation shown in Figure 1 is intended to separate air into its constituents to produce : nitrogen gas under oxygen pressure gaseous to about 99.5% purity; and oxygen ultra-pure with a predetermined maximum content methane and argon, for example less than 0.1 ppm methane and less than 10 ppm argon.
  • the production ultra-pure oxygen corresponds to a small fraction, preferably between 5 and 10%, of the oxygen production of the installation.
  • the installation includes a main unit of air distillation 1 itself comprising a double distillation column 2.
  • the double column includes a medium pressure column 3 surmounted by a low pressure column 4.
  • a condenser-vaporizer 5 connects indirect heat exchange with nitrogen at the top of column 3 and the tank liquid (oxygen at approximately 99.5% purity) from column 4.
  • the air to be treated, purified and cooled to its point of dew is mostly introduced under the medium pressure, approximately 6 bar absolute, at bottom of column 3 via line 6.
  • Some cash poor "LP, consisting mainly of nitrogen, is taken at the head of column 3 then, after expansion in an expansion valve 8, is introduced at the head of column 4.
  • Double column 2 also includes a line 9 producing gaseous oxygen at 99.5% purity, at the bottom of column 4, a line 10 for producing nitrogen gas under 6 bars, at the top of column 3, and a pipe 11 exhaust gas W (impure nitrogen) leaving from the top of column 4.
  • a second auxiliary column 17 is supplied at an intermediate location, via a pipe 18, by the overhead vapor of the column 12.
  • It has n + n 1 theoretical plates below the pipe 18.
  • Its tank has a vaporizer 19 and its top a condenser 20.
  • the vaporizer is heated by a line 21, and the condenser 20 is cooled by the rest of the rich liquid LR, expanded in an expansion valve 22.
  • the rich liquid vaporized in the condensers 15 and 20 is returned to column 4 via a common pipe 23.
  • the liquefied fluid leaving the vaporizer 19 can be returned to the corresponding level in column 4 or, as shown, be combined with the rich liquid withdrawn from the tank of column 4, since its flow is low compared to that of this rich liquid.
  • a pipe 24 connects the top of the column 17 at an intermediate point in column 4.
  • the oxygen conveyed through line 13 contains argon and methane as impurities. Methane separates from oxygen and argon in column 12 with n theoretical plates, all the more completely as the number n is large. The calculation shows that a number less than or equal to 8 is sufficient for the usual applications of ultra-pure oxygen.
  • the invention applies in the same way to main air distillation apparatuses producing oxygen with a purity of less than 99.5%, for example 95 or 97%.
  • the gas drawn off through line 13 then contains nitrogen, which easily separates from the oxygen in the auxiliary column 17.
  • a vaporizer 19 is used to heat oxygen-depleted gas taken from the lower or intermediate part of column 3.
  • the oxygen content of the heating gas must, however, remain sufficient to ensure, by the condensation of this gas, the vaporization of ultra-pure oxygen . In fact, this vaporization takes place at a pressure higher than that of the tank of column 4 due to the presence of the n1 additional plates of column 17.
  • FIG. 2 shows how the invention can be applied to a device main air distillation 1A provided with a column 26 of oxygen-argon separation.
  • a device main air distillation 1A provided with a column 26 of oxygen-argon separation.
  • a pipe 13A called "argon tapping" starts from an intermediate location of the column 4, N theoretical plates above the tank.
  • This pipe opens into the tank of column 26 and conveys a gas essentially consisting of oxygen and argon, and a return pipe 14A starts from the lowest point of column 26 and opens into column 4 at approximately the level 13A argon stitching.
  • the column 26 is equipped with a head condenser 15A supplied by the portion of the rich liquid LR which is not expanded in the valve 17, this liquid being expanded in an expansion valve 16A.
  • the rich liquid vaporized leaving the condenser 15A is returned to the column 4, a little below the rich liquid coming from the valve 17.
  • the raw argon produced at the top of the column 26 is discharged through a pipe 27.
  • the main distillation apparatus 1A is modified in the following way to produce ultra-pure oxygen.
  • a 19A vaporizer is placed in the tank column 17A. This steamer is heated as previously by the line 21 and combined with the rich liquid LR after condensation.
  • the oxygen-argon gas mixture conveyed through line 13A contains methane as an impurity. Methane separates from oxygen and argon in the lower section 12A with n theoretical plates of column 26, all the more completely as the number n is large. The calculation shows that a number n less than or equal to 8 is sufficient for the usual applications of ultra-pure oxygen.
  • N of the order of 30 to 40 and n 1 of the order of 15 to 30 we can choose N of the order of 30 to 40 and n 1 of the order of 15 to 30.
  • a line 29 for drawing off liquid oxygen at approximately 99.5% purity can, as shown, from an intermediate location of the column 17A situated substantially N + n trays theoretical below the top of this column 17A.
  • This oxygen is practically free of hydrocarbons and can therefore be used for certain applications where hydrocarbons are undesirable, for example in the medical field.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP90400145A 1989-01-20 1990-01-19 Procédé et installation de séparation d'air et de production d'oxygène ultra-pur Expired - Lifetime EP0379435B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90400145T ATE74421T1 (de) 1989-01-20 1990-01-19 Verfahren und vorrichtung zur lufttrennung und herstellung von ultrareinem sauerstoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8900670 1989-01-20
FR8900670 1989-01-20

Publications (3)

Publication Number Publication Date
EP0379435A1 EP0379435A1 (fr) 1990-07-25
EP0379435B1 EP0379435B1 (fr) 1992-04-01
EP0379435B2 true EP0379435B2 (fr) 1998-05-20

Family

ID=9377912

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90400145A Expired - Lifetime EP0379435B2 (fr) 1989-01-20 1990-01-19 Procédé et installation de séparation d'air et de production d'oxygène ultra-pur

Country Status (7)

Country Link
US (1) US4977746A (ja)
EP (1) EP0379435B2 (ja)
JP (1) JPH0672740B2 (ja)
AT (1) ATE74421T1 (ja)
CA (1) CA2008187C (ja)
DE (1) DE69000047D1 (ja)
ES (1) ES2030311T5 (ja)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2693220B2 (ja) * 1989-04-24 1997-12-24 テイサン株式会社 超高純度酸素製造方法
US5049173A (en) * 1990-03-06 1991-09-17 Air Products And Chemicals, Inc. Production of ultra-high purity oxygen from cryogenic air separation plants
US5129932A (en) * 1990-06-12 1992-07-14 Air Products And Chemicals, Inc. Cryogenic process for the separation of air to produce moderate pressure nitrogen
US5231837A (en) * 1991-10-15 1993-08-03 Liquid Air Engineering Corporation Cryogenic distillation process for the production of oxygen and nitrogen
FR2689223B1 (fr) * 1992-03-24 1994-05-06 Air Liquide Procede et installation de transfert de fluide en provenance d'une colonne de distillation, notamment d'air.
JP2966999B2 (ja) † 1992-04-13 1999-10-25 日本エア・リキード株式会社 超高純度窒素・酸素製造装置
US5528906A (en) * 1995-06-26 1996-06-25 The Boc Group, Inc. Method and apparatus for producing ultra-high purity oxygen
FR2739438B1 (fr) * 1995-09-29 1997-10-24 Air Liquide Procede et installation de production d'argon par distillation cryogenique
US5799508A (en) * 1996-03-21 1998-09-01 Praxair Technology, Inc. Cryogenic air separation system with split kettle liquid
GB9607200D0 (en) * 1996-04-04 1996-06-12 Boc Group Plc Air separation
US5596886A (en) * 1996-04-05 1997-01-28 Praxair Technology, Inc. Cryogenic rectification system for producing gaseous oxygen and high purity nitrogen
US5628207A (en) * 1996-04-05 1997-05-13 Praxair Technology, Inc. Cryogenic Rectification system for producing lower purity gaseous oxygen and high purity oxygen
US5682763A (en) * 1996-10-25 1997-11-04 Air Products And Chemicals, Inc. Ultra high purity oxygen distillation unit integrated with ultra high purity nitrogen purifier
DE19817794A1 (de) 1998-04-21 1999-10-28 Basf Ag Hochreine wässrige Wasserstoffperoxid-Lösungen, Verfahren zu ihrer Herstellung und ihre Verwendung
JP4242507B2 (ja) * 1999-04-05 2009-03-25 日本エア・リキード株式会社 超高純度ガスの製造方法及び製造装置
US6173586B1 (en) * 1999-08-31 2001-01-16 Praxair Technology, Inc. Cryogenic rectification system for producing very high purity oxygen
US6263701B1 (en) 1999-09-03 2001-07-24 Air Products And Chemicals, Inc. Process for the purification of a major component containing light and heavy impurities
JP5878310B2 (ja) * 2011-06-28 2016-03-08 大陽日酸株式会社 空気分離方法及び装置
CN103062991B (zh) * 2013-01-24 2015-07-08 成都深冷液化设备股份有限公司 深冷空分装置高纯氧生产系统及高纯氧制备工艺
DE102016011084A1 (de) 2016-09-13 2018-03-15 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung eines Hochreinsauerstoffproduktstroms durch Tieftemperaturzerlegung von Luft
EP3327393A1 (de) 2016-11-25 2018-05-30 Linde Aktiengesellschaft Verfahren und vorrichtung zur gewinnung eines hochreinsauerstoffproduktstroms durch tieftemperaturzerlegung von luft

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59150286A (ja) * 1983-02-15 1984-08-28 日本酸素株式会社 アルゴンの製造方法
US4615716A (en) * 1985-08-27 1986-10-07 Air Products And Chemicals, Inc. Process for producing ultra high purity oxygen
DE3600835A1 (de) * 1986-01-14 1989-01-05 Porsche Design Gmbh Telefonapparat
US4756731A (en) * 1986-02-20 1988-07-12 Erickson Donald C Oxygen and argon by back-pressured distillation
JPS62210386A (ja) * 1986-03-12 1987-09-16 株式会社日立製作所 空気分離装置
JPS61259077A (ja) * 1986-05-08 1986-11-17 株式会社神戸製鋼所 空気分離方法
US4715874A (en) * 1986-09-08 1987-12-29 Erickson Donald C Retrofittable argon recovery improvement to air separation
US4769055A (en) * 1987-02-03 1988-09-06 Erickson Donald C Companded total condensation reboil cryogenic air separation
US4762542A (en) * 1987-03-20 1988-08-09 The Boc Group, Inc. Process for the recovery of argon
DE3722746A1 (de) * 1987-07-09 1989-01-19 Linde Ag Verfahren und vorrichtung zur luftzerlegung durch rektifikation

Also Published As

Publication number Publication date
DE69000047D1 (de) 1992-05-07
ES2030311T3 (es) 1992-10-16
JPH0672740B2 (ja) 1994-09-14
EP0379435B1 (fr) 1992-04-01
JPH02233984A (ja) 1990-09-17
US4977746A (en) 1990-12-18
ATE74421T1 (de) 1992-04-15
CA2008187C (fr) 1999-12-07
CA2008187A1 (fr) 1990-07-20
EP0379435A1 (fr) 1990-07-25
ES2030311T5 (es) 1998-07-16

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