EP0600923B1 - Procede de production de gaz synthetiques ou combustibles a partir de residus et de dechets solides ou pateux ou de combustibles a faible pouvoir calorifique dans un reacteur de gazeification - Google Patents

Procede de production de gaz synthetiques ou combustibles a partir de residus et de dechets solides ou pateux ou de combustibles a faible pouvoir calorifique dans un reacteur de gazeification Download PDF

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Publication number
EP0600923B1
EP0600923B1 EP92916028A EP92916028A EP0600923B1 EP 0600923 B1 EP0600923 B1 EP 0600923B1 EP 92916028 A EP92916028 A EP 92916028A EP 92916028 A EP92916028 A EP 92916028A EP 0600923 B1 EP0600923 B1 EP 0600923B1
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EP
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Prior art keywords
gas
fraction
gasifying reactor
gasification
solid
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Expired - Lifetime
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EP92916028A
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German (de)
English (en)
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EP0600923A1 (fr
Inventor
Karl-Heinz Redepenning
H. Peter Wenning
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Veba Oel Technologie und Automatisierung GmbH
John Brown Deutsche Engineering GmbH
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Veba Oel Technologie und Automatisierung GmbH
John Brown Deutsche Engineering GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1606—Combustion processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1643—Conversion of synthesis gas to energy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water

Definitions

  • the invention relates to a method according to the preamble of patent claim 1.
  • the disposal of carbon-containing waste materials of varying composition, such as domestic and industrial waste, is known from EP-A3-0 120 397.
  • the aim of this process is the production of fuel gas.
  • the carbon-containing waste material is smoldered in a rotary tube reactor above 200 ° C to obtain a carbonization gas and a pyrolysis coke.
  • the pyrolysis coke is then gasified in a fluidized bed or fluidized bed gasifier.
  • the gasification products leave the carburetor at relatively low Temperatures between 400 ° C and 1000 ° C.
  • the liquid and gaseous components released from the smoldering stage and the gasification stage are subsequently burned, while the ashes that have to be disposed of have to be disposed of. -
  • This process is unsatisfactory for environmentally friendly disposal of the input materials, since both the final incineration and the disposal of the ashes lead to new environmental problems.
  • a process similar to that described in EP 0 120 397 A3 is also known from WO 90/02162, in which essentially the same problems as described in connection with EP 0 120 397 A3 arise.
  • both the pyrolysis step and the gasification step are carried out allothermally.
  • WO 90/02162 also provides for the combustion of the solid gasification residue in a gasification residue combustion chamber, the step of burning the gasification residue being an essential step for the overall process.
  • the process management there aims at a particularly advantageous use of heat within the overall process, and in order to provide sufficient quantities of heat in the individual process stages, it is also intended to supply the process with coal as well as waste as a raw material.
  • the object of the invention is to ensure the most environmentally compatible disposal of residues and waste materials which are difficult to handle and contain organic constituents, in particular the light shredder fraction, in the recycling of motor vehicles, and thereby to obtain a synthesis gas.
  • a mechanical and thermal (drying) pretreatment of the biomass is carried out.
  • a combined process of entrained flow pyrolysis takes place and entrained-flow gasification, both of which are carried out in the so-called downdraft, the entrained-flow pyrolysis taking place in an outer zone and the gasification in an inner zone of a common, concentrically constructed entrained-flow reactor in which the pyrolysis is carried out at a temperature of up to 1600 ° F, corresponding to 870 ° C is done.
  • the temperature of the pyrolysis step is therefore extremely high.
  • the hot carrier gas for pyrolysis also contains water vapor and CO 2 .
  • GB-A-2 109 400 which describes synthesis gas production from a fibrous biomass, such as wood chips.
  • a so-called slurry gasification is carried out after a pyrolytic pretreatment of the starting material.
  • This type of gasification requires a relatively high liquid carrier content of approx. 40%.
  • the gasification apparently takes place at relatively low process temperatures, namely below the ash softening.
  • This known process is not very suitable for feedstocks of the type that are to be disposed of in accordance with the present invention.
  • Gasification reactors operating according to the entrained flow principle are well known and therefore do not require any special description at this point; reference is made, for example, to DE-C2 27 21 047 and EP-B1-0 011 151. Grain bandwidths of approximately 0.001 mm to 5 mm are used for use in so-called entrained flow gasifiers.
  • the particle size of the solid fraction obtained after the pyrolysis treatment stage according to the invention is adjusted after the pyrolysis treatment and before the entrained flow gasification by grinding, sieving and / or sifting, the particle size range being reduced.
  • the gas fraction obtained after the pyrolysis treatment stage is preferably first subjected to a condensation step.
  • the gas fraction obtained after the coding stage is then further used in the synthesis gas production process according to the invention.
  • this gas fraction is fed to the gasification reactor or the pyrolysis treatment stage for introducing heat for the endothermic pyrolysis or gasification step or admixed to the product gas obtained behind the gasification reactor as part of the synthesis gas.
  • the liquid fraction obtained after the condensation stage can possibly be used in another process, but is preferably used in the gasification reactor for gasification and / or supplied for the introduction of heat for the endothermic gasification process.
  • the solid fraction obtained after the pyrolysis treatment stage and the liquid fraction obtained after the condensation stage are mixed and fed together to the gasification reactor, a pump or a screw machine being used, depending on the consistency of the mixture. Suitable funding bodies and procedures for this are known from DE-C2-27 21 047 and EP-B1-0 011 151 as examples.
  • the gasification is generally carried out under a pressure of preferably 10 to 100 bar. Basically, higher gasification pressures are possible.
  • the gasification can also be carried out at atmospheric pressure or in a slightly reduced pressure (if suction fans are used).
  • Fig. 1 is a block diagram.
  • FIG. 1 The block diagram shown in FIG. 1 is explained below in connection with the use of an entrained-flow gasification reactor. Alternative procedures are shown in dashed lines. Process steps that are preferably used are additionally outlined with a dashed line.
  • a residual or waste material containing organic constituents hereinafter referred to as feed material
  • a pyrolysis treatment stage 101 such as an indirectly heated rotary kiln (drum wall temperature up to 900 ° C.).
  • the feed material is pretreated, largely without oxygen, with the addition of heat and essentially avoiding the burning of constituents of the feed material at temperatures between approximately 300 and 650 ° C.
  • extraneous gas, product gas accumulating behind the gasification reactor 102 and / or pyrolysis gas accumulating behind a condensation stage 103 downstream of the pyrolysis stage, preferably accumulating in a pyrolysis gas purification stage 104 can be used.
  • the intermediate product obtained in the pyrolysis treatment stage 101 from the starting material is discharged separately as steam (gas fraction) and coke (solid fraction).
  • the solid fraction is adjusted, if necessary after setting the grain size range in a grinding, sieving and / or classifying stage 105, to the level which is compatible with the respective gasification reactor type (gasification reactor 102), and the gasification reactor 102, e.g. B. pneumatically supplied.
  • Recyclables contained in the solid fraction, e.g. Metals can be separated in a separation stage 106, e.g. a screening device, before the solid fraction is fed to the gasification reactor 102.
  • the gas fraction obtained behind the pyrolysis treatment stage 101 is either fed as vapor to the gasification reactor for the gasification and / or introduction of heat of reaction or is first passed through a condensation stage 103.
  • the residual gas deposited therein, which is obtained under the condensation conditions, is fed to the pyrolysis treatment stage for introducing process heat either, preferably after passing through a pyrolysis gas purification stage 104.
  • the pyrolysis gas can be supplied to the gasification reactor 102 or the product gas stream occurring behind it to introduce gasification heat. In these cases, a pyrolysis gas cleaning stage may not be necessary.
  • the oil (liquid fraction) obtained behind the condensation stage 103 is recycled in other processes or, as is preferred, introduced into the gasification reactor 102. Especially when this oil is to be gasified together with the solid fraction from the pyrolysis treatment stage 101, the two fractions can first be combined and fed to the gasification reactor 102 by means of a pump or screw machine 107.
  • the product gas obtained behind the gasification reactor 102 will generally be cleaned in a gas cleaning stage 108.
  • the constituents removed from the product gas can be fed to the gasification reactor 102 at least as a partial stream, so that they are divided there into product gas or inorganic constituents.
  • enriched harmful gas components such as sulfur, salts and heavy metals can be reused.
  • the product gas obtained behind the gas purification stage 108 can, as is preferred, be fired in a power plant 109, which may be already present, or, if appropriate partially, in the pyrolysis treatment stage 101 or used as synthesis gas or other fuel gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Gasification And Melting Of Waste (AREA)

Abstract

Un procédé permet de produire des gaz synthétiques et/ou combustibles à partir de résidus et de déchets contenant des éléments organiques et ou de combustibles à faible pouvoir calorifique (matières chargées) avec des gaz contenant de l'oxygène, dans un gazéificateur vertical ou à courant volant. Afin d'obtenir un gaz ayant une qualité uniforme malgré les difficultés de traitement des matières chargées, qui peuvent notamment être constituées par des matières légères produites par un shredder de récupération de véhicules à moteur, un étage de traitement par pyrolyse précède le réacteur de gazéification. Les matières solides sortant de l'étage de traitement par pyrolyse sont gazéifiées dans le réacteur de gazéification et la fraction gazeuse sortant de l'étage de traitement par pyrolyse est utilisée pour apporter de la chaleur au processus de production et/ou pour produire davantage de gaz.

Claims (8)

  1. Procédé pour la fabrication de gaz de synthèse à partir de déchets et de résidus contenant des composants organiques pâteux ou solides, difficiles à manipuler, en particulier de la fraction légère de Shredder provenant du recyclage de carrosserie automobile à l'aide d'azote ou de gaz contenant de l'azote, et éventuellement de la vapeur d'eau, en utilisant un réacteur de gazéification, fonctionnant selon le principe des poussières en suspension, à des températures de 800°C à 1700°C et éventuellement plus élevées, dans lequel
    a) tout d'abord, par un prétraitement thermique par apport de chaleur et en évitant essentiellement une cuisson des composants de la charge employée (traitement par pyrolyse) dans un four tubulaire rotatif chauffé, on sépare en une fraction solide et en une fraction gazeuse en conditions de fonctionnement, en particulier sous forme de vapeur,
    b) la fraction solide étant délivrée au réacteur de gazéification, fonctionnant selon le principe des poussières en suspension, en tant que charge solide à gazéifier, éventuellement après la séparation de substances de valeur en vue de la transformation en gaz de synthèse et
    c) la fraction gazeuse est utilisée du moins partiellement dans le processus de fabrication, en particulier en vue de l'apport de chaleur pour le processus de gazéification endothermique.
  2. Procédé selon la revendication 1, caractérisé en ce que la fraction gazeuse, résultant du traitement par pyrolyse, est soumise à un opération de condensation avant d'être utilisée.
  3. Procédé selon la revendication 2, caractérisé en ce que la fraction gazeuse, résultant de l'étape de condensation, est directement purifiée, en tant que partie du gaz de combustion et/ou de synthèse, avec le courant gazeux de produit se manifestant derrière le réacteur de gazéification ou bien est amenée au réacteur de gazéification ou à l'étape de traitement par pyrolyse en vue d'amener de la chaleur pour le processus endothermique.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que les fractions liquides, résultant de l'étape de condensation, sont utilisées dans un autre processus ou sont amenées au réacteur de gazéification en vue de la gazéification et/ou en vue de l'apport de chaleur pour le processus de gazéification endothermique.
  5. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la largeur de bande granulométrique de la fraction solide, résultant derrière l'étape de traitement par pyrolyse, est diminuée avant la gazéification dans un réacteur de gazéification de courant volant par broyage, par tamisage et/ou criblage.
  6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la fraction solide, résultant derrière l'étape de traitement par pyrolyse et la fraction liquide résultant derrière l'étape de condensation sont mélangées et sont amenées au réacteur de gazéification, de préférence au moyen d'une pompe ou d'une machine à vis sans fin.
  7. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le produit gazeux, résultant derrière le réacteur de gazéification et éventuellement derrière l'étape de condensation est utilisé, après élimination éventuelle de substances nocives (composants de gaz nocifs), en tant que combustible gazeux, pour le fonctionnement d'une centrale électrique éventuellement déjà existante, en particulier d'une centrale électrique de chauffage monobloc.
  8. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la substance chargée est mélangée à des déchets ou résidus anorganiques.
EP92916028A 1991-07-15 1992-07-15 Procede de production de gaz synthetiques ou combustibles a partir de residus et de dechets solides ou pateux ou de combustibles a faible pouvoir calorifique dans un reacteur de gazeification Expired - Lifetime EP0600923B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914123406 DE4123406C2 (de) 1991-07-15 1991-07-15 Verfahren zum Vergasen von minderwertigen festen Brennstoffen in einem schachtförmigen Vergasungsreaktor
DE4123406 1991-07-15
PCT/EP1992/001607 WO1993002162A1 (fr) 1991-07-15 1992-07-15 Procede de production de gaz synthetiques ou combustibles a partir de residus et de dechets solides ou pateux ou de combustibles a faible pouvoir calorifique dans un reacteur de gazeification

Publications (2)

Publication Number Publication Date
EP0600923A1 EP0600923A1 (fr) 1994-06-15
EP0600923B1 true EP0600923B1 (fr) 1996-08-28

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EP92916028A Expired - Lifetime EP0600923B1 (fr) 1991-07-15 1992-07-15 Procede de production de gaz synthetiques ou combustibles a partir de residus et de dechets solides ou pateux ou de combustibles a faible pouvoir calorifique dans un reacteur de gazeification
EP92202501A Pending EP0523815A1 (fr) 1991-07-15 1992-07-15 Procédé de fabrication de gaz de synthèse ou de combustion à partir de matériaux pâteux ou solides de restes ou de déchets ou de combustibles de moindre valeur dans un réacteur de gazéification

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EP92202501A Pending EP0523815A1 (fr) 1991-07-15 1992-07-15 Procédé de fabrication de gaz de synthèse ou de combustion à partir de matériaux pâteux ou solides de restes ou de déchets ou de combustibles de moindre valeur dans un réacteur de gazéification

Country Status (7)

Country Link
EP (2) EP0600923B1 (fr)
JP (1) JP3203580B2 (fr)
AU (1) AU2344492A (fr)
CA (1) CA2113636A1 (fr)
DE (2) DE4123406C2 (fr)
FI (1) FI106314B (fr)
WO (1) WO1993002162A1 (fr)

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DE19853717A1 (de) * 1998-11-20 2000-05-31 Krc Umwelttechnik Gmbh Vorrichtung zur Vergasung kompaktierter organischer Materialien
DE19853713A1 (de) * 1998-11-20 2000-05-31 Krc Umwelttechnik Gmbh Verfahren zur stofflichen und energetischen Verwertung von Rest- und Abfallstoffen

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EP0545241B1 (fr) * 1991-11-29 1996-02-28 Noell Energie- und Entsorgungstechnik GmbH Procédé pour la valorisation thermique de déchets
DE4308551A1 (de) * 1993-03-17 1994-01-05 Siemens Ag Verfahren und Einrichtung zum Entsorgen von Abfall
GR1001615B (el) * 1993-06-04 1994-07-29 Viokat Anonymos Techniki & Vio Μέ?οδος αεριοποίησης στερεών καυσίμων χαμηλού ?ερμικού περιεχομένου με ωφέλιμη αξιοποίηση στην παραγωγή ηλεκτρικής ενέργειας χωρίς δημιουργία ρύπανσης περιβάλλοντος.
DE4404673C2 (de) * 1994-02-15 1995-11-23 Entec Recycling Und Industriea Verfahren zur Erzeugung von Brenngas
DE19513832B4 (de) * 1995-04-12 2005-08-11 Future Energy Gmbh Verfahren zur Verwertung von Rest- und Abfallstoffen durch Kombination einer Wirbelschichtthermolyse mit einer Flugstromvergasung
DE19608093C2 (de) * 1996-03-02 2000-08-10 Krc Umwelttechnik Gmbh Verfahren zur Verwertung von Rest- und Abfallstoffen sowie heizwertarmen Brennstoffen in einem Zementofen
DE19925316A1 (de) * 1999-05-27 2000-11-30 Technip Benelux B V Verfahren und Anlage zur autothermen Vergasung von festen Brennstoffen
DE19936971C1 (de) * 1999-08-05 2001-03-01 Krupp Uhde Gmbh Mehrstufiges Beschickungsverfahren für stückiges Einsatzgut und Stoffgemische in Druckräume
DE19936972C1 (de) * 1999-08-05 2001-02-15 Krupp Uhde Gmbh Mehrstufiges Beschickungsverfahren für stückiges Einsatzgut und Stoffgemische in Druckräume
DE10010358A1 (de) * 2000-03-07 2001-09-27 Bsbg Bremer Sonderabfall Berat Verfahren und Vorrichtung zum Vergasen von brennbarem Material
DE10151054A1 (de) * 2001-10-16 2003-04-30 Karlsruhe Forschzent Verfahren zur Behandlung von Biomasse
DE10258485A1 (de) * 2002-12-10 2004-07-08 Innovativer Anlagenbau E&H Gmbh Verfahren und Vorrichtung zur Gewinnung von Wärmeenergie und/oder motortauglichem Gas durch Vergasung von Feststoffen
FR2859216B1 (fr) * 2003-08-27 2008-07-04 Inst Francais Du Petrole Procede et installation de production a haut rendement d'un gaz de synthese depollue a partir d'une charge riche en matiere organique
DE10345672B4 (de) * 2003-10-01 2005-12-29 Forschungszentrum Karlsruhe Gmbh Verfahren zur Vergasung von Pyrolysekondensaten
GR20080100221A (el) * 2008-04-02 2009-11-19 Μεθοδος αναβαθμισης αεριων προερχομενων απο θερμικη αποδομηση οργανικης μαζας
SE532711C2 (sv) * 2008-06-11 2010-03-23 Cortus Ab Förfarande och anläggning för framställning av syntesgas
EP2236587A1 (fr) * 2009-04-02 2010-10-06 General Electric Company Boues biologiques modifiées et procédé pour sa production et sa gazéification
IT1398667B1 (it) * 2009-06-18 2013-03-08 Vaiani Procedimento e impianto per la produzione di gas di sintesi da biomasse e/o rifiuti in genere
CZ2010807A3 (cs) * 2010-11-08 2010-12-22 Key@Group@Holding@@s@r@o Zpusob@zpracování@organického@odpadu@@zarízení@najeho@zpracování@a@použití@zpracovaných@produktu
ES2558318T3 (es) * 2011-02-14 2016-02-03 Zbb Gmbh Aparato y método de carbonización termoquímica y gasificación de biomasa húmeda

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19853717A1 (de) * 1998-11-20 2000-05-31 Krc Umwelttechnik Gmbh Vorrichtung zur Vergasung kompaktierter organischer Materialien
DE19853713A1 (de) * 1998-11-20 2000-05-31 Krc Umwelttechnik Gmbh Verfahren zur stofflichen und energetischen Verwertung von Rest- und Abfallstoffen
DE19853717C2 (de) * 1998-11-20 2000-12-21 Krc Umwelttechnik Gmbh Verfahren und Vorrichtungen zur Vergasung kompaktierter organischer Materialien
DE19853713C2 (de) * 1998-11-20 2003-03-13 Bbp Power Plants Gmbh Verfahren zur stofflichen und energetischen Verwertung von Rest- und Abfallstoffen

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JPH07502766A (ja) 1995-03-23
WO1993002162A1 (fr) 1993-02-04
JP3203580B2 (ja) 2001-08-27
FI106314B (fi) 2001-01-15
FI940184A0 (fi) 1994-01-14
DE59207017D1 (de) 1996-10-02
CA2113636A1 (fr) 1993-02-04
DE4123406A1 (de) 1993-01-21
EP0600923A1 (fr) 1994-06-15
FI940184A (fi) 1994-03-11
EP0523815A1 (fr) 1993-01-20
DE4123406C2 (de) 1995-02-02
AU2344492A (en) 1993-02-23

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