EP0610120B1 - Procédé et installation pour le traitement par thermolyse de déchets solides, sans condensation d'hydrocarbures - Google Patents
Procédé et installation pour le traitement par thermolyse de déchets solides, sans condensation d'hydrocarbures Download PDFInfo
- Publication number
- EP0610120B1 EP0610120B1 EP19940400189 EP94400189A EP0610120B1 EP 0610120 B1 EP0610120 B1 EP 0610120B1 EP 19940400189 EP19940400189 EP 19940400189 EP 94400189 A EP94400189 A EP 94400189A EP 0610120 B1 EP0610120 B1 EP 0610120B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermolysis
- boiler
- gases
- area
- pumping means
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
- C10B7/14—Coke ovens with mechanical conveying means for the raw material inside the oven with trucks, containers, or trays
Definitions
- the present invention relates to a method and a installation for thermolysis treatment of products solids the discharge of which is harmful to the environment, and more particularly aims at the treatment of thermolysis that are formed there.
- the Applicant sought, in the document W0-92 / 16599, to overcome the aforementioned drawbacks by allowing treatment by thermolysis at medium temperature, around 600 ° C for example, while allowing control continuous decomposition products.
- Document W0-92 / 16599 thus describes a system for the treatment of solid products whose rejection is harmful to the environment, including a reactor successively integrating a dehydration zone and a thermolysis zone, characterized in that this reactor comprises, downstream of the thermolysis zone, a zone of cooling and in that the dehydration zone is fitted with a watertight entry door, the cooling zone has a watertight exit door, and airlocks isolate the thermolysis zone, on the one hand with respect to the dehydration zone, on the other hand with respect to the cooling so as to limit the entry of air into the thermolysis zone during product introduction and during residue extraction, this thermolysis zone being provided with a gas extraction line whereby it is in depression.
- This areas are therefore separated into isolated rooms.
- thermolysis zone was maintained without free oxygen, and the thermolysis zone was at a temperature between 400 ° C and 750 ° C and at a pressure less than or equal to 800 millibars.
- the products to be treated were preferably introduced into the reactor in passing carriages successively from the dehydration chamber to the chamber thermolysis and from the thermolysis chamber to the cooling using a mechanical system of the kind pinions and rack for example, or even electromagnetic drive.
- the carts were designed so that solid residues - glasses, metals, rubble by example - stay in carts while being removed easily after cooling at the outlet of the cooling.
- thermoreactors also called catalytic radiant panels supplied with pure oxygen or air on the one hand and on the other share of pyrolysis gas from decomposition thermolytic as well as by electrical resistors placed inside the rooms or glued to the walls to the exterior of the rooms.
- Carbon dioxide and water vapor generated in oxidation of pyrolysis gases in radiant panels catalytic could participate in warming up by convection and radiation of products.
- Halogenated and sulfur compounds could be removed in the washer by dissolving in washing.
- the gas flow at the outlet of the reactor entailed advantageously the coal formed in the decomposition thermolytic to the washer where it is cooled.
- Heavy hydrocarbons and coal were preferably recovered by decanting the wash water in the outlet of the washer in a decanter.
- the gas flow at the outlet of the washer was preferably vacuumed by a vacuum pump.
- the gases at the outlet of the vacuum pump were for example sent to a washer containing for example a aqueous potassium carbonate solution to remove carbon dioxide.
- Pyrolysis gases purified from halogenated compounds, sulfur and carbon dioxide were for example used in reactor heating and the excess was for example stored for future use.
- Control of the kinetics of the transformation thermolytic in the thermolysis chamber was for example obtained by regulating electric heating and catalytic heating by the use of systems conventional temperature measurement and regulation gas and electric flow rates.
- the object of the invention is to improve from the point of energetic view (both quantitative and qualitative: lower energy losses, better recovery by-products, and lower requirements as to the nature of the energy to be supplied) the treatment of gases taken from a thermolysis chamber working in practice in depression, without degrading the performance of this treatment.
- the invention applies in particular, but not exclusively, to the system described and taught by document W0-92 / 16599.
- the subject of the invention is to further improve the performance of this treatment.
- thermolysis in a thermolysis zone we extract solid residue from this thermolysis zone, we aspire to by means of pumping thermolysis gases formed in this thermolysis zone so maintain this zone of vacuum thermolysis, characterized in that it maintains these thermolysis gases from this thermolysis zone to at least the entry of the pumping means at a temperature higher than about 100 ° C, and these gases are used as fuel in a boiler and we recover energy thermal at the outlet of this boiler.
- the invention thus teaches to maintain gases pumped into the thermolysis zone at a higher temperature at the temperature of condensation of the tars (approximately 80 ° C) likely to form in the gaseous state during thermolysis: this allows, unlike what was proposed in document W0-92 / 16599, to maintain these tars in the gaseous state and therefore to apply them as fuel in a boiler, which allows recovery direct to generate thermal energy.
- This thermal energy can either be recycled in the installation, either be applied to a turbine which performs one conversion into electrical form, or be used for any other function, possibly foreign to the installation.
- the invention thus goes against the reflex of the skilled person to cool and condense to purify well.
- thermolysis gases Preferably, not only is it not cooled not the thermolysis gases but we heat them beyond 850 ° C (or even 1250 ° C and above) to improve the degradation of these thermolysis gases, in the sense of the regulations indicated above.
- the boiler also uses fuel (coal) contained in solid residues.
- fuel coal
- the invention offers a facility for processing products solids the discharge of which is harmful to the environment, with a dehydration zone where the solid products, a thermolysis zone downstream of the zone dewatering, a solid residue outlet area and pumping means communicating by an extraction line with the thermolysis zone to maintain it in depression and suck thermolysis gases into it, characterized in that the pumping means have a range of operating temperatures at least partly above about 100 ° C, in this that the extraction line is insulated over its entire length to the pumping means, and in that these means pumps communicate via a gas supply line fuel with a boiler capable of burning these gases thermolysis.
- the installation in Figure 1 has a zone dehydration 1 where solid products penetrate to be at least partially dehydrated first, then an area of thermolysis 2 in which the solid products, partially or totally dehydrated, are brought to their temperature thermal decomposition (commuted and fixed in advance) for example around 600 ° C (typically between 400 ° C and 750 ° C).
- this thermolysis chamber is followed by a cooling zone 3 where solid residues of the heat treatment are brought to the temperature ambient.
- thermolytic transformation is advantageously performed in the total absence of free oxygen at a average temperature of 600 ° C.
- zones 1, 2 and 3 are chambers insulated from each other substantially watertight, for example by guillotine doors (not shown) actuated by cylinders; the door between the rooms 1 and 2 and the door between rooms 2 and 3 are movable transversely in watertight housings, the crossing lifting cylinders by cable gland.
- watertight doors are provided at the entrance to bedroom 1 and at the exit of room 3 thanks to which the zones of dehydration 1 and cooling are, at will, isolated from the outside and / or from the thermolysis zone 2; they can be moved vertically or horizontally or around a joint according to the reactor dimensions, available space and free choice of the designer.
- Chambers 1 and 2 of the reactor are insulated to limit heat loss.
- Bedrooms 1 and 2 are provided with means of heating of all suitable known types.
- the temperature of chamber 2 is for example maintained at around 600 ° C. while that of chamber 1, lower, is maintained above 100 ° C, for example around 120 ° C.
- Heating means can be, as in the document supra, catalytic radiant panels. They can also be flame burners using the gases of thermolysis and / or commercial combustible gases (good market) arriving by line 101.
- enclosures 1A and 2A of these chambers 1 and 2 is provided by the radiation from the wall interior of the rooms heated by the flames of the burners according to technological arrangements similar to those retained in the aforementioned document.
- the heating is also provided by convection of the gases in the mass of products to be treated, convection ensured by expansion of the combustion in the rooms.
- Chamber 2 is kept under vacuum, typically at a pressure less than or equal to 800 mbar, even 500 mbar. Preferably, the same set pressure is chosen in rooms 1, 2 and 3.
- This depression is maintained by means of pumping 10 communicating with the thermolysis zone by a extraction line 11.
- these pumping means 10 have an operating temperature range at least in part higher than about 100 ° C, which allows these means to pumping to be crossed by gases of higher temperatures at 80 ° C (temperature of condensation of the tars).
- the extraction line 11 is provided on all of its length of means capable of maintaining the gases circulating therein at a temperature at least equal to around 100 ° C (there may be sufficient for good insulation, shown schematically in 11A, of which the sizing is within the reach of the skilled person).
- the installation comprises a boiler 12 provided with a 12A burner communicating with the output of the pumping means 10 by a fuel gas inlet line 13 and regulated in sort of being able to use thermolysis gases as combustible.
- thermolysis including the tars they may contain
- pumping means which allows very good degradation while providing energy thermal.
- the boiler preferably communicates by a solid fuel inlet line 14, with a reactor 15 of any type known per se where inert, separated, are separated by a line 16, and in practice pulverulent coal.
- This reactor is for example of the rotary drum type.
- This boiler 12 has a discharge line 17 smoke which communicates advantageously with chambers of bedrooms 1 and 2 to participate in their heater.
- this boiler has an entry power supply 18A, and an output 18B which can be connected to a turbine 19 intended for example to convert into electricity hot gas (in practice steam) supplied by this boiler.
- the input 18A is for example connected to a tank gas or water (not shown in this figure 1).
- this boiler can include a third input 12B for make-up fuel, solid or gaseous depending on availability.
- the extraction line is not direct but goes through a heater 50 whereby the temperature thermolysis gas is raised to a temperature of preferably above 850 ° C (case of solid products of household origin) or even above 1250 ° C (case of solid products of hospital origin).
- the total length of line 11 and the reheating temperature in the heater 50 are preferably chosen so that the gases remain at least two seconds above these levels, so as to ensure good thermal purification.
- This heater 50 is for example a heat exchanger heat traversed, in a sense, by these thermolysis gases and, in the other direction, by part of the fumes from the boiler.
- the means of pumping are formed by a vacuum pump operating at dry, such as, for example, those developed by DEGUSSA. It can easily, as we know, operate at temperatures up to 150 ° C, i.e. higher at 100 ° C.
- FIG. 2 shows a preferred form of realization, where elements similar to those of the figure 1 are designated by the same reference signs.
- thermolysis gases which may contain water
- thermolysis still containing the tars The liquid fraction from this separator in practice contains acids (notably hydrochloric, hydrofluoric, sulfuric) so that it is advantageously passed through a reactor of neutralization 23 where a line 24 is injected reagents intended to reduce the pH to 7 (this injection can vary depending on the instantaneous pH value).
- acids notably hydrochloric, hydrofluoric, sulfuric
- thermolysis even in solid residues
- this solution ensures good purification of soluble compounds at high temperature thanks to the intimate mixture of thermolysis gases and water vapor.
- the water vapor applied to the ejector 20 (there may of course be several) is at a pressure of 10 bars for a flow rate depending on the quantity treated and at a temperature of 200 ° C.
- the thermolysis gases are taken from the thermolysis chamber at a temperature of 600 ° C. at a flow rate of 20% of the water vapor flow rate and reach the ejector with a temperature at least equal to 850 ° C. after heater 50, neutralization in reactor 23 is obtained by injection of reagents consisting of CO 3 Ca.
- the vacuum pump of figure 1 is advantageously supplied by electrical energy supplied by the turbine 19.
- the vapor from the ejector of FIG. 2 can be obtained by cogeneration or withdrawal in this turbine
- the heater 50 may include burners using part of the thermolysis gases.
- thermolysis by-products thermolysis are enhanced by obtaining a mixture that can be sent directly to a recovery boiler, in good thermodynamic conditions and without going through the recovery stage of heavy hydrocarbon products.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Treating Waste Gases (AREA)
Description
- on chauffe ces gaz avec des fumées de la chaudière,
- on aspire les gaz de thermolyse en les faisant passer dans un éjecteur à vapeur d'eau utilisant de la vapeur d'eau formée dans la chaudière, puis dans un séparateur d'où sort, en outre de ces gaz de thermolyse, de l'eau alimentant la chaudière,
- on neutralise l'eau sortant du séparateur avant de la faire rentrer dans la chaudière pour être transformée en vapeur d'eau,
- on utilise les fumées de la chaudière pour chauffer la zone de déshydratation.
- elle comporte un réacteur disposé en aval de la zone de thermolyse dans lequel pénètrent les résidus solides, et communiquant avec la chaudière par une ligne d'arrivée de combustible solide,
- la ligne d'extraction traverse un réchauffeur,
- ce réchauffeur est un échangeur de chaleur alimenté par les fumées de la chaudière,
- les moyens de pompage comportent une pompe à vide à fonctionnement à sec,
- les moyens de pompage comportent un éjecteur à vapeur d'eau muni d'une arrivée de vapeur d'eau communiquant avec une sortie de la chaudière, et en ce que cette installation comporte en outre, en aval de cet éjecteur, un séparateur muni d'une sortie de gaz reliée à la ligne d'arrivée de gaz combustible, et d'une sortie d'eau reliée par une ligne d'arrivée à une entrée d'eau de la chaudière,
- un réservoir de neutralisation est disposé sur la ligne d'arrivée d'eau, et est muni d'une ligne d'arrivée de réactifs de neutralisation,
- les zones de déshydratation et de thermolyse sont munies d'enceintes communiquant par une ligne avec la sortie de fumées de la chaudière,
- une turbine est montée à la sortie de la chaudière.
- la figure 1 est un schéma de principe d'une installation conforme à l'invention, et
- la figure 2 est un schéma d'une forme préférée de réalisation de cette installation.
Claims (17)
- Procédé pour le traitement de produits solides dont le rejet est préjudiciable pour l'environnement, selon lequel on déshydrate dans une zone de déshydratation (1) des produits solides à traiter, on les thermolyse dans une zone de thermolyse (2), on extrait des résidus solides de cette zone de thermolyse, on aspire à l'aide de moyens de pompage (10, 20) des gaz de thermolyse formés dans cette zone de thermolyse en sorte de maintenir cette zone de thermolyse en dépression, caractérisé en ce qu'on maintient ces gaz de thermolyse depuis cette zone de thermolyse jusqu'à au moins l'entrée des moyens de pompage (10, 20) à une température supérieure à 100°C environ, et on utilise ces gaz comme combustible dans une chaudière (12) et on récupère de l'énergie thermique à la sortie de cette chaudière.
- Procédé selon la revendication 1, caractérisé en ce qu'on applique en outre (14) à la chaudière du combustible récupéré dans les résidus solides.
- Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce qu'on chauffe (50) les gaz de thermolyse aspirés dans la zone de thermolyse, à une température supérieure à 850°C environ, avant de les appliquer à l'entrée des moyens de pompage (10, 20).
- Procédé selon la revendication 3, caractérisé en ce qu'on chauffe ces gaz de thermolyse à une température au moins égale à 1250°C environ.
- Procédé selon la revendication 3 ou la revendication 4, caractérisé en ce qu'on chauffe (17) ces gaz avec des fumées de la chaudière (12).
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on aspire les gaz de thermolyse en les faisant passer dans un éjecteur à vapeur d'eau (20) utilisant de la vapeur d'eau formée dans la chaudière (12), puis dans un séparateur (22) d'où sort, en outre de ces gaz de thermolyse, de l'eau alimentant la chaudière.
- Procédé selon la revendication 6, caractérisé en ce qu'on neutralise (23)l'eau sortant du séparateur avant de la faire rentrer dans la chaudière pour être transformée en vapeur d'eau.
- Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'on utilise (17)les fumées de la chaudière pour chauffer la zone de déshydratation.
- Installation pour le traitement de produits solides dont le rejet est préjudiciable à l'environnement, comportant une zone de déshydratation (1) où pénètrent les produits solides, une zone de thermolyse (12) en aval de la zone de déshydratation, une zone de sortie de résidus solides et des moyens de pompage (10, 20) communiquant par une ligne d'extraction (11) avec la zone de thermolyse pour la maintenir en dépression et y aspirer des gaz de thermolyse, caractérisée en ce que les moyens de pompage (10, 20) ont une gamme de températures de fonctionnement au moins en partie supérieure à 100°C environ, en ce que la ligne d'extraction (11) est calorifugée (11A) sur toute sa longueur jusqu'aux moyens de pompage (10, 20), et en ce que ces moyens de pompage communiquent par une ligne d'arrivée de gaz combustible (13) avec une chaudière (12) apte à brûler ces gaz de thermolyse.
- Installation selon la revendication 9, caractérisée en ce qu'elle comporte un réacteur (15) disposé en aval de la zone de thermolyse dans lequel pénètrent les résidus solides, et communiquant avec la chaudière (12) par une ligne d'arrivée de combustible solide (14).
- Installation selon la revendication 9 ou la revendication 10, caractérisée en ce que la ligne d'extraction (11) traverse un réchauffeur (50).
- Installation selon la revendication 11, caractérisée en ce que ce réchauffeur (50) est un échangeur de chaleur alimenté par les fumées de la chaudière (12).
- Installation selon l'une quelconque des revendications 9 à 12, caractérisée en ce que les moyens de pompage (10) comportent une pompe à vide à fonctionnement à sec.
- Installation selon l'une quelconque des revendications 9 à 12, caractérisée en ce que les moyens de pompage (20) comportent un éjecteur à vapeur d'eau (20A) muni d'une arrivée de vapeur d'eau communiquant avec une sortie de la chaudière, et en ce que cette installation comporte en outre, en aval de cet éjecteur, un séparateur (22) muni d'une sortie de gaz reliée à la ligne d'arrivée de gaz combustible, et d'une sortie d'eau reliée par une ligne d'arrivée à une entrée d'eau de la chaudière.
- Installation selon la revendication 14, caractérisée en ce qu'un réservoir de neutralisation est disposé sur la ligne d'arrivée d'eau, et est muni d'une ligne (24) d'arrivée de réactifs de neutralisation.
- Installation selon l'une quelconque des revendications 9 à 15, caractérisée en ce que les zones de déshydratation et de thermolyse sont munies d'enceintes (1A, 2A) communiquant par une ligne avec la sortie de fumées de la chaudière.
- Installation selon l'une quelconque des revendications 9 à 16, caractérisée en ce qu'une turbine (19) est montée à la sortie de la chaudière.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9301043A FR2701035B1 (fr) | 1993-02-01 | 1993-02-01 | Procédé et installation pour le traitement par thermolyse de déchets solides, sans condensation d'hydrocarbures. |
FR9301043 | 1993-02-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0610120A1 EP0610120A1 (fr) | 1994-08-10 |
EP0610120B1 true EP0610120B1 (fr) | 1998-06-10 |
Family
ID=9443585
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19940400189 Expired - Lifetime EP0610120B1 (fr) | 1993-02-01 | 1994-01-28 | Procédé et installation pour le traitement par thermolyse de déchets solides, sans condensation d'hydrocarbures |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0610120B1 (fr) |
DE (2) | DE69410841T2 (fr) |
ES (1) | ES2065296T3 (fr) |
FR (1) | FR2701035B1 (fr) |
GR (1) | GR940300098T1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2200014T3 (es) * | 1995-01-25 | 2004-03-01 | I.T.B. S.R.L. | Procedimiento y planta para el tratamiento pirotilico de desechos que contienen material organico, en particular para el tratamiento de desechos solidos municipales. |
JP3376439B2 (ja) * | 1995-11-22 | 2003-02-10 | 日立造船株式会社 | 廃プラスチック油化装置 |
FR2754539B1 (fr) * | 1996-10-15 | 1998-12-31 | Thermolyse Soc France | Procede de traitement de dechets par injection de gaz chauds directement dans la charge a traiter, installation et chariot pour la mise en oeuvre de ce procede |
FR2754540B1 (fr) * | 1996-10-15 | 1998-12-31 | Thermolyse Soc France | Procede et installation pour le traitement de dechets solides par thermolyse |
KR100282759B1 (ko) * | 1996-10-15 | 2001-05-02 | 쏘시에뜨 프랑세즈 드 떼르몰리즈 | 처리 물질로의 고온 가스 주입 및 생성된 열분해 가스의 재순환에 의한 폐기물 처리 설비 |
BR9909883A (pt) * | 1999-02-25 | 2000-12-26 | Nexus Technologies | Instalação de tratamento termolìtico de dejetos |
FR2822527B1 (fr) * | 2001-03-20 | 2003-10-10 | Maillot Sarl | Procede de traitement des dechets industriels et/ou menagers et installation de traitement des dechets industriels et/ou menagers |
GB0604907D0 (en) | 2006-03-10 | 2006-04-19 | Morgan Everett Ltd | Pyrolysis apparatus and method |
DE102010049379A1 (de) | 2010-10-26 | 2012-04-26 | Mioba Mitteldeutscher Industrie-Ofenbau Gmbh & Co. Kg | Vorrichtung zum energetischen Verwerten von festen organischen Abfällen |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2350550A1 (fr) * | 1976-05-07 | 1977-12-02 | Rousseau Louis | Procede et installation de traitement thermique de dechets par pyrolyse et incineration |
DE3811820A1 (de) * | 1987-08-03 | 1989-02-16 | Siemens Ag | Verfahren und anlage zur thermischen abfallentsorgung |
FR2674149B1 (fr) * | 1991-03-20 | 1994-04-15 | Pierre Chaussonnet | Systeme pour le traitement par thermolyse, en absence totale d'oxygene des produits solides dont le rejet est prejudiciable pour l'environnement. |
FR2679009B1 (fr) * | 1991-07-09 | 1997-12-12 | Inst Francais Du Petrole | Procede et dispositif de traitement de dechets par contact direct |
-
1993
- 1993-02-01 FR FR9301043A patent/FR2701035B1/fr not_active Expired - Fee Related
-
1994
- 1994-01-28 ES ES94400189T patent/ES2065296T3/es not_active Expired - Lifetime
- 1994-01-28 DE DE1994610841 patent/DE69410841T2/de not_active Expired - Fee Related
- 1994-01-28 EP EP19940400189 patent/EP0610120B1/fr not_active Expired - Lifetime
- 1994-01-28 DE DE1994400189 patent/DE610120T1/de active Pending
-
1995
- 1995-01-31 GR GR940300098T patent/GR940300098T1/el unknown
Also Published As
Publication number | Publication date |
---|---|
GR940300098T1 (en) | 1995-01-31 |
EP0610120A1 (fr) | 1994-08-10 |
ES2065296T3 (es) | 1998-08-01 |
FR2701035B1 (fr) | 1995-04-21 |
DE610120T1 (de) | 1995-07-06 |
DE69410841T2 (de) | 1999-03-18 |
ES2065296T1 (es) | 1995-02-16 |
DE69410841D1 (de) | 1998-07-16 |
FR2701035A1 (fr) | 1994-08-05 |
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