EP0030323B1 - Procédé de fonctionnement d'un réacteur à lit fluidisé pour gazéifier des matières carbonacées - Google Patents
Procédé de fonctionnement d'un réacteur à lit fluidisé pour gazéifier des matières carbonacées Download PDFInfo
- Publication number
- EP0030323B1 EP0030323B1 EP80107380A EP80107380A EP0030323B1 EP 0030323 B1 EP0030323 B1 EP 0030323B1 EP 80107380 A EP80107380 A EP 80107380A EP 80107380 A EP80107380 A EP 80107380A EP 0030323 B1 EP0030323 B1 EP 0030323B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- post
- temperature
- gasification
- fluidised bed
- reaction chamber
- 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
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Images
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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
-
- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/50—Fuel charging devices
- C10J3/503—Fuel charging devices for gasifiers with stationary fluidised bed
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- 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 for operating a fluidized bed reactor for the gasification of solid, carbonaceous material using exothermic and endothermic reactions causing gasification with a post-reaction space located above the fluidized bed, through which the gas mixture emerging from the fluidized bed and carbon-containing solid particles flows, whereby gasifying agents in the fluidized bed and at least three injection areas arranged along the longitudinal axis of the reactor are introduced into the post-reaction space.
- Suitable gasification agents are, for example, air, oxygen and hydrogen as exothermic gasification agents and water vapor and CO 2 as endothermic gasification agents.
- DE-A-27 41 805 discloses a process of the type described in the introduction, in which gasifying agents, e.g., in a fluidized bed reactor with a lower fluidized bed containing the carbon-containing solid particles and an after-reaction space above, in which entrained carbon-containing solid particles are located. Oxygen and water vapor are blown in and the gasifying agents blown into the lower region of the reactor also simultaneously fluidize the fluidized bed.
- the temperature distribution along the longitudinal axis of the reactor in the post-reaction space is influenced by the addition of gasification agents in several areas spaced apart from one another along the longitudinal axis of the reactor with the aim of making the temperature profile dependent on the quality of the gas desired in each case and on the nature of the carbon-containing materials used in each case adjust, the temperature falling from a maximum just above the upper limit of the fluidized bed more or less continuously to a noticeably lower temperature in the upper region of the after-reaction space.
- DE-A-26 43 298 discloses a method for operating a fluidized bed reactor for gasifying solid, carbon-containing material, in which the highest possible temperature is to be maintained in the post-reaction space.
- the temperature profile ie the temperature profile along the longitudinal axis in the after-reaction space, is of great importance for the operation of the reactor and for the quality of the gas produced therein.
- the temperature profile is also important for the greatest possible conversion of the carbonaceous material.
- a high temperature favors the CO and H 2 yield.
- it is necessary to remain at the maximum temperature below the melting point of the ash of the carbon-containing material, since otherwise agglomerates are formed and caking occurs in the reactor and / or in the lines in which the product gas after leaving the reactor is led to subordinate facilities. Such agglomerates and / or caking adversely affect the operation of the reactor and can lead to interruptions in operation.
- a too low temperature avoids difficulties due to melting the ash, but on the other hand leads to a higher CO 2 and H 2 0 content in the product gas.
- the conversion of the solid carbon with C0 2 and H 2 0 to CO and H 2 does not find any particularly favorable conditions.
- the invention has for its object to modify the method of the type described in the introduction so that, taking into account the limits set by the ash melting point, the most complete possible implementation of the carbon-containing material in the after-reaction space is achieved.
- the gasification agents introduced into the reactor should be able to be used in a targeted manner so that the greatest possible effect in terms of extensive gasification of the solid carbon particles with the formation of usable gases can be achieved with the least possible expenditure on gasification agents.
- the invention proposes that the gasifying agents which bring about exothermic reactions and endothermic reactions are distributed and metered into the after-reaction space along the longitudinal axis of the reactor in such a way that a temperature which is as constant as possible along the longitudinal axis of the reactor in the area of the gasifying agent supply is maintained above the fluidized bed and the temperature in the after-reaction space in this area is not lower than the temperature of the gas emerging from the fluidized bed.
- the amount of gasifying agent causing exothermic reactions can be kept constant in each section.
- the invention provides the possibility that both the amount of the gasifying agent causing exothermic reactions and the amount of the gasifying agent causing endothermic reactions decrease in each section from bottom to top. Furthermore, the ratio between gasification agent causing exothermic reactions and gasifying agent causing endothermic reactions can increase in each section from below or else remain constant depending on the respective conditions from bottom to top.
- the implementation of the process according to the invention achieves a reaction in the entire post-reaction space which is directed over the longitudinal extent of the post-reaction space and which leads to clear operating conditions, so that it is easier from the start to determine the desired operating parameters, for example the temperature profile and, depending on this, the addition of gasifying agent to control optimally.
- the desired operating parameters for example the temperature profile and, depending on this, the addition of gasifying agent to control optimally.
- overheating which can lead to caking and thus to malfunctions, can be avoided in this way despite a high mean temperature.
- the gasification agents can be supplied in the usual manner.
- the distances between the individual blowing areas or levels can be constant.
- the solid-gas mixture emerging from the fluidized bed has a temperature which is approximately equal to the temperature in the post-reaction space or in the section thereof above the fluidized bed is to be observed.
- the gasification agents should be introduced into the post-reaction space in at least four, advantageously at least six, spaced apart areas.
- the addition of the gasification agent which brings about an exothermic reaction in the individual blowing regions can be controlled as a function of the temperature determined there and / or of the solids content determined there. Furthermore, it is possible to control the addition of the gasification agent which brings about an endothermic reaction in the individual blowing-in regions as a function of the carbon-containing solid present there in each case.
- a feed device indicated at 12 which can be designed as a screw or otherwise in a suitable manner.
- a fluidized bed 15 is built up, the upper and lower limits of which are designated 16 and 17, respectively.
- a layer 18 Below the lower boundary 17 there is a layer 18, the at least predominantly ash-containing parts of which are discharged through an opening 19 located at the lower end of the reactor 10.
- the gasifying agents which cause the bed 15 to swirl can normally be oxygen-containing gasifying agents, that is to say an exothermic reaction, and steam and / or CO 2 , that is to say gasifying agents which bring about an endothermic reaction.
- the gases can be blown in via nozzles, several of which are arranged distributed over the circumference of the reactor, it being possible to supply gasification agents which bring about endothermic reactions and gasification agents which bring about exothermic reactions also in two separate, for example superimposed, areas or levels.
- the finer solid particles from the fluidized bed 15 are entrained in the post-reaction space 20 located above it by the gas mixture flowing upwards.
- the latter is firstly the gaseous reaction products from the fluidized bed and secondly residues of the unreacted gasifying agents, in particular steam.
- the solid particles still contain carbon, which is to be converted within the post-reaction space.
- the heat required for this is supplied by burning part of the combustible gases contained in the gas mixture, essentially CO and H 2 , and part of the carbon-containing solid.
- the agent required for this for example oxygen, is blown in through lines and nozzles which, distributed along the longitudinal axis of the reactor, open into the after-reaction space 20 above the fluidized bed 15 and are designated by 21, 23, 25 and 27. It also applies here that a plurality of lines or nozzles can flow into the post-reaction space and flow into it. Furthermore, gasification agent is blown into the after-reaction space 20 through the nozzles 21, 23, 25, and 27. It is possible to inject exothermic gases on the one hand and endothermic gases on the other hand as a mixture or through separate supply systems and nozzles. In the temperature profile shown in FIG. 1 in addition to the reactor 10, the levels in which gasification agents are introduced into the after-reaction space 20 are indicated by dashed lines which end at the arrows assigned to the individual injection levels corresponding to the injection levels.
- a high and uniform temperature builds up in the fluidized bed 15 relatively quickly, which should be approximately 1050 ° C. in the exemplary embodiment shown in FIG. 1.
- the first supply of gasification agent into the after-reaction space 20 takes place via the feed lines 21, which are located at a relatively short distance above the upper boundary 16 of the fluidized bed 15.
- a quenching agent is introduced via lines 40 in the level 40a into the post-reaction space, which lowers the temperature of the gas by approximately 80 to 100 ° C. in order to ensure that the gas mixture leaving the reactor does not contain any solid particles contains, whose ashes have softened and could cause caking in the downstream lines.
- the amount of solid carbon in the after-reaction space 20 decreases from bottom to top, so that consequently fewer gasifying agents are required for the conversion from bottom to top. This is taken into account in the exemplary embodiment according to FIG. 1 in that the distances between the blowing levels 21a, 23a, 25a and 27a increase from the bottom up.
- the temperature within the fluidized bed 115 is significantly lower than that in accordance with FIG. 1. It is between approximately 700 and 800 ° C.
- the addition of exothermic gasifying agent immediately above the upper boundary 116 of the fluidized bed 115 in the blowing-in plane 121 must be such that the gas and solid mixture flowing out of the fluidized bed causes a noticeable increase in the temperature from the peak 130 to the peak 136 reaching lower section of consistently high temperature of approx. 1100 ° C.
- the subsequent operating mode corresponds to the blowing level 127a, i.e. to the peak 136 in principle that of the exemplary embodiment according to FIG.
- the blowing in of the endothermally reacting gasification agent along the longitudinal axis of the after-reaction space depends on the desired uniform conversion at a uniform temperature profile. It is the case that depending on the endothermic gasifying agent blown into the lower blowing area Only a more or less large part of the concentration of the carbonaceous material in the after-reaction space is converted, so that the ratio between exothermic and endothermic-reacting amounts of gasifying agent remains constant or can increase at the upper injection areas in the post-reaction space.
- the injection areas in the post-reaction space can be arranged at the same distance from one another.
- the temperature profile resulting from this procedure gives a uniform sawtooth-like up and down of the temperature over the length of the after-reaction space.
- the procedure described above is possible in connection with the exemplary embodiment shown in FIG. 3 of the drawing.
- the temperature in the fluidized bed 215 corresponds approximately to that of the exemplary embodiment according to FIG. 1, although that according to FIG. 2 is also possible.
- the blow-in areas 221 to 227 are arranged at constant intervals. In all blowing levels 221a to 227a, the exothermic and endothermic gasifying agents are blown in at constant ratios to one another and, if appropriate, also in constant amounts. The latter would mean that equal amounts of endothermally reacting and exothermally reacting gasifying agents are blown in from all the blowing areas from bottom to top.
- a quenching agent can be supplied via a feed line 240 shortly before the outlet opening 228 will.
- the implementation of the carbon-containing substances located in the post-reaction space Solid particles should be guided in such a way that heat consumption and heat supply correspond to each other in such a way that a temperature level that is as constant as possible is maintained in the individual sections or, more precisely, the temperature within the post-reaction space or the sections about its or its axial extent by an average value only slightly varied on both sides, the maximum temperature that may occur being just below the temperature limit at which the ash particles soften to form difficulties, ie could lead to caking or formation of larger agglomerates.
- the temperature profile is idealized in all the figures of the drawing.
- the crucial point is that the temperature fluctuations around an average temperature, which in turn can fluctuate to a small extent, are kept as small as possible, and the amplitude does not have to be constant over the entire length of the after-reaction space. Rather, it can fluctuate within limits along the reactor axis, that is, it can become larger or smaller.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Claims (17)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2949533 | 1979-12-08 | ||
DE19792949533 DE2949533A1 (de) | 1979-12-08 | 1979-12-08 | Verfahren zum betreiben eines wirbelbettreaktors zum vergasen von kohlenstoffhaltigem material |
DE19803033115 DE3033115A1 (de) | 1980-09-03 | 1980-09-03 | Verfahren zum betreiben eines wirbelbettreaktors zum vergasen von kohlenstoffhaltigem material |
DE3033115 | 1980-09-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0030323A1 EP0030323A1 (fr) | 1981-06-17 |
EP0030323B1 true EP0030323B1 (fr) | 1986-05-07 |
Family
ID=25782316
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80107380A Expired EP0030323B1 (fr) | 1979-12-08 | 1980-11-26 | Procédé de fonctionnement d'un réacteur à lit fluidisé pour gazéifier des matières carbonacées |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0030323B1 (fr) |
AU (1) | AU536933B2 (fr) |
BR (1) | BR8008022A (fr) |
DD (1) | DD155174A1 (fr) |
DE (1) | DE3071595D1 (fr) |
GR (1) | GR71896B (fr) |
TR (1) | TR21877A (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4340459C1 (de) * | 1993-11-27 | 1995-05-18 | Rheinische Braunkohlenw Ag | Verfahren zum Betreiben eines Wirbelschichtreaktors zum Vergasen von kohlenstoffhaltigen Einsatzstoffen |
DE19548324A1 (de) * | 1994-12-23 | 1996-06-27 | Rheinische Braunkohlenw Ag | Verfahren zum Vergasen von kohlenstoffhaltigen Feststoffen in der Wirbelschicht sowie dafür verwendbarer Vergaser |
DE102007006980A1 (de) * | 2007-02-07 | 2008-08-14 | Technische Universität Bergakademie Freiberg | Verfahren zur Vergasung fester Brennstoffe in der Wirbelschicht unter erhöhtem Druck |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2127394A1 (fr) * | 1993-07-12 | 1995-01-13 | William Martin Campbell | Reacteur de gazeification |
DE59507290D1 (de) * | 1995-02-13 | 1999-12-30 | Thermoselect Ag | Verfahren zum Beseitigen organischer Schadstoffreste in bei der Müllvergasung anfallendem Synthesegas |
DE102006005626B4 (de) * | 2006-02-06 | 2008-02-28 | Rwe Power Ag | Verfahren und Vergasungsreaktor zur Vergasung verschiedenster Brennstoffe mit breitem Körnungsband mit Flüssigschlackeabzug |
CN112745966B (zh) * | 2019-09-16 | 2022-04-15 | 中国科学院工程热物理研究所 | 循环流化床气化装置和循环流化床气化方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1913968A (en) * | 1928-02-09 | 1933-06-13 | Ig Farbenindustrie Ag | Fuel gas |
US2558746A (en) * | 1948-02-10 | 1951-07-03 | Texas Co | Production of carbon monoxide and other gases from carbonaceous materials |
DE937486C (de) * | 1949-09-08 | 1956-01-05 | Rudolf Dr-Ing Drawe | Verfahren und Gaserzeuger zur Vergasung staubfoermiger oder feinkoerniger Brennstoffe |
US3840353A (en) * | 1971-07-30 | 1974-10-08 | A Squires | Process for gasifying granulated carbonaceous fuel |
DE2801574B1 (de) * | 1978-01-14 | 1978-12-21 | Davy Powergas Gmbh, 5000 Koeln | Wirbelschichtschachtgenerator zum Vergasen feinkörniger Brennstoffe |
DE2741805A1 (de) * | 1977-09-16 | 1979-03-29 | Rheinische Braunkohlenw Ag | Verfahren und vorrichtung zum vergasen von festem, kohlenstoffhaltigem material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2643298A1 (de) * | 1976-09-25 | 1978-04-06 | Davy Bamag Gmbh | Verfahren zur kontinuierlichen vergasung von feinteiligem, kohlenstoffhaltigem material |
-
1980
- 1980-11-26 DE DE8080107380T patent/DE3071595D1/de not_active Expired
- 1980-11-26 EP EP80107380A patent/EP0030323B1/fr not_active Expired
- 1980-11-28 GR GR63492A patent/GR71896B/el unknown
- 1980-12-05 AU AU65115/80A patent/AU536933B2/en not_active Ceased
- 1980-12-05 TR TR21877A patent/TR21877A/xx unknown
- 1980-12-08 DD DD80225841A patent/DD155174A1/de unknown
- 1980-12-08 BR BR8008022A patent/BR8008022A/pt unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1913968A (en) * | 1928-02-09 | 1933-06-13 | Ig Farbenindustrie Ag | Fuel gas |
US2558746A (en) * | 1948-02-10 | 1951-07-03 | Texas Co | Production of carbon monoxide and other gases from carbonaceous materials |
DE937486C (de) * | 1949-09-08 | 1956-01-05 | Rudolf Dr-Ing Drawe | Verfahren und Gaserzeuger zur Vergasung staubfoermiger oder feinkoerniger Brennstoffe |
US3840353A (en) * | 1971-07-30 | 1974-10-08 | A Squires | Process for gasifying granulated carbonaceous fuel |
DE2741805A1 (de) * | 1977-09-16 | 1979-03-29 | Rheinische Braunkohlenw Ag | Verfahren und vorrichtung zum vergasen von festem, kohlenstoffhaltigem material |
DE2801574B1 (de) * | 1978-01-14 | 1978-12-21 | Davy Powergas Gmbh, 5000 Koeln | Wirbelschichtschachtgenerator zum Vergasen feinkörniger Brennstoffe |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4340459C1 (de) * | 1993-11-27 | 1995-05-18 | Rheinische Braunkohlenw Ag | Verfahren zum Betreiben eines Wirbelschichtreaktors zum Vergasen von kohlenstoffhaltigen Einsatzstoffen |
DE19548324A1 (de) * | 1994-12-23 | 1996-06-27 | Rheinische Braunkohlenw Ag | Verfahren zum Vergasen von kohlenstoffhaltigen Feststoffen in der Wirbelschicht sowie dafür verwendbarer Vergaser |
DE19548324C2 (de) * | 1994-12-23 | 1998-08-06 | Rheinische Braunkohlenw Ag | Verfahren zum Vergasen von kohlenstoffhaltigen Feststoffen in der Wirbelschicht sowie dafür verwendbarer Vergaser |
DE102007006980A1 (de) * | 2007-02-07 | 2008-08-14 | Technische Universität Bergakademie Freiberg | Verfahren zur Vergasung fester Brennstoffe in der Wirbelschicht unter erhöhtem Druck |
DE102007006980B4 (de) * | 2007-02-07 | 2009-03-19 | Technische Universität Bergakademie Freiberg | Verfahren zur Vergasung fester Brennstoffe in der Wirbelschicht unter erhöhtem Druck |
Also Published As
Publication number | Publication date |
---|---|
AU536933B2 (en) | 1984-05-31 |
AU6511580A (en) | 1981-06-18 |
EP0030323A1 (fr) | 1981-06-17 |
DE3071595D1 (en) | 1986-06-12 |
BR8008022A (pt) | 1981-06-23 |
TR21877A (tr) | 1987-02-13 |
GR71896B (fr) | 1983-08-10 |
DD155174A1 (de) | 1982-05-19 |
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Legal Events
Date | Code | Title | Description |
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