CA1226116A - Process for the production of carbon monoxide - Google Patents
Process for the production of carbon monoxideInfo
- Publication number
- CA1226116A CA1226116A CA000467461A CA467461A CA1226116A CA 1226116 A CA1226116 A CA 1226116A CA 000467461 A CA000467461 A CA 000467461A CA 467461 A CA467461 A CA 467461A CA 1226116 A CA1226116 A CA 1226116A
- Authority
- CA
- Canada
- Prior art keywords
- generator
- carbon
- process according
- mixed gas
- carbon monoxide
- 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
Links
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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
- C10J3/08—Continuous processes with ash-removal in liquid state
-
- 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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
- C10J3/30—Fuel charging devices
-
- 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
- C10J3/72—Other features
- C10J3/86—Other features combined with waste-heat boilers
-
- 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
- C10J2300/0943—Coke
-
- 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
Abstract
Process for the production of carbon monoxide Abstract of the Disclosure Carbon monoxide is produced in an improved process in a carbon-filled, water-cooled generator in the con-figuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide, wherein the improvement comprises injecting the mixed gas into the generator through at least one downwardly-directed, coolable nozzle arranged in the generator sidewall and removing the car-bon monoxide formed.
-c-
-c-
Description
;~26~
Process for the production of carbon monoxide BACKGROUND OF THE INVENTION
This invention relates to a process for the pro-diction of carbon monoxide in a water-cooled generator which has the form of a truncated cone in longitudinal section. The generator is filled with carbon and by gasification of carbon with a mixture of oxygen and carbon dioxide, carbon monoxide is produced.
The production of carbon monoxide from coal and oxygen has long been known and is practiced on a large industrial scale. In most cases truncated, cone-shaped generators are used hazing a volume of, for example, 4 my which are fed with coke from above through a gate and subjected to oxygen through one or more water-cooled nozzles at the bottom of the generator. If coke is present in excess, most of the carbon monoxide is formed in a combustion zone, which is at a temperature above 1800C, surrounding toe stream of oxygen emerging from the nozzles at high velocity The carbon monoxide is withdrawn at the top of the generator. The heat of reaction is in most cases removed by cooling water in the cooling jacket surrounding the generator. Steam generation is also possible, as described in DEMOS No.
1,95~,517.
The process descried above was the disa~vanta~e, firstly, that the slag left from combustion of the coke accumulates at the bottom of the venerator. This may considerably impair the efficiency of the nozzle(s) also located at the bottom. damage by burning causes water to enter the generator and hydrogen appears in the production gas causing subsequent processing to be very e A 22 499 -c-31 aye difficult or even dangerous. In any case, continuous removal of slag is not possible.
Another disadvantage is that the volumetric output of a conventional generator is limited by heat genera-lion as a result of the highly exothermic reaction of carbon with oxygen. Thus, for example, in a generator having a volume of 4 my supplied with pure oxygen, the maximum carbon monoxide production achieved is 140 m3/h, which corresponds to a volumetric output of 35 my of CO/h x my of generator volume. An improvement in the heat transfer may be achieved by the introduction of a truncated cone-shaped hollow core which may be cooled, as described in DEMOS No. 2,046,172. Considerably more effective is the addition of carbon dioxide to the oxygen fed into the generator since the reaction between carbon dioxide and carbon is highly endothermic.
The output of a generator of 4 my capacity may in this way be increased to a volumetric output of 60 my CO/h x my generator volume. The meld gas used in this case may have an OKAY ratio of 2:1. With this method, however, the output is still limited by the rate at which heat may be removed in the region of the nozzle.
SUMMARY OF THE INVENTION
It is therefore an object ox the present inane-lion to provide a process for the production of carbon monoxide which may be carried out more efficiently and does not kayo the above-described disadvantages ox the known processes.
A process which fulfill all these requirements in -30 a particularly advantageous manner has now surprisingly lo A 22 499 been found. The present invention departs from the method invariably employed in the past (i.e. arranging the nozzle(s) at the bottom of the generator and, instead, introduces the nozzles laterally through the generator jacket and directed downwardly. By this change in the nozzle location, the abo~e-described disadvantages may be overcome and a considerable increase in the volumetric output of the generator may be achieved with optimum utilization of the heat of reaction of carbon combustion.
The present invention therefore relates to a process for the production of carbon monoxide in a water-cooled generator which is in the form of a truncated cone in longitudinal section and is filled with carbon, and by gasification of the carbon with a mixed gas of oxygen and carbon dioxide, said mixed gas being injected into the generator through one or more downwardly directed, callable nozzles provided on the jointer jacket, while the carbon monoxide formed is remove din the opposite direction at the side and/or head of the generator. The callable nozzles which extend through the generator jacket sidewall are spaced from the bottom of the generator and are dow~wardly-directed Jo that the gas stream prom the nozzle is also directed downwardly. The nozzle spacing prom the bottom of the generator should be sufficient to avoid contact with and interference from slag which forms and collects at the bottom of the generator. Otherwise the spacing from the bottom it not particularly critical.
lo A 22 I
~2~6~
The carbon used in this process is preferably coke.
If additives, which depress the melting point of the slay are added to the coke, then liquid slag can be removed continuously or intermittently at the bottom of the generator.
The process can be carried out particularly effective-lye if the volumetric ratio of oxygen to carbon dioxide in the mixed gas is adjusted to a value of down 1:1, prefer-ably somewhere in the range of from 1.2:1 to 1.3:1. This results in a significantly improved utilization of the heat of reaction of carbon combustion and a further increase in the volumetric output to over 400 my CO/h x my of reaction volume.
Particularly complete conversion to carbon monoxide may be achieved by injecting oxygen through one or more additional nozzles situated above the downwardly-directed mixed gas nozzles.
It is found particularly advantageous for carrying out the process to equip the nozzles with a double-walled cooling jacket cooled wit water. A further advantage is obtained by drawing off the product carton monoxide gas laterally since this considerably reduces the thermal stress on the mechanical equipment for intro-during coke at the head of the generator.
grief DESCRIPTION Of THE DRAWING
A carbon monoxide generator fox carrying out the process according to the present invention is illustrated schematically by the accompanying figure. This is only one of many possible designs of such a carbon monoxide generator.
lo A 22 499 ~2~6~
Through inlet (2), carbon is introduced into the generator chamber (3) from a gate (1). This generator chamber is surrounded by a cooling water system (4) and has a mixed gas (OKAY) nozzle (5) and an outlet (6) for the discharge of product gas. The slag (7) is removed through a slag outlet (8) at the bottom of the generator.
An access hole (9) is provided for servicing the generator.
The process described may be applied analogously to other gas-solid reactions to similar advantage. Examples include the production of generator gas:
4N2 2 + 2C 4N2 t KIWI Q
or synthesis gas:
Q HO t C ` Ho CO
The present invention will now be explained with reference to a non-limiting Example.
Example Crushed coke is introduced at the rate of 780 kg/h into a carbon monoxide generator as illustrated in the accompanying figure having a volume of 4 my through a gate at the head of the generator and about 13 ugh of slag (with additive) are removed it the bottom. 438 Nm3/h of oxygen and 362 Nm3/h of carbon dioxide are injected through nozzles in the generator jacket and 1600 Nm3fh of 98 % pure carbon monoxide are withdrawn as crude gas with fly ash through a nozzle on the opposite side of the generator to be conveyed to the downstream gas purification steps.
lo A 22 499
Process for the production of carbon monoxide BACKGROUND OF THE INVENTION
This invention relates to a process for the pro-diction of carbon monoxide in a water-cooled generator which has the form of a truncated cone in longitudinal section. The generator is filled with carbon and by gasification of carbon with a mixture of oxygen and carbon dioxide, carbon monoxide is produced.
The production of carbon monoxide from coal and oxygen has long been known and is practiced on a large industrial scale. In most cases truncated, cone-shaped generators are used hazing a volume of, for example, 4 my which are fed with coke from above through a gate and subjected to oxygen through one or more water-cooled nozzles at the bottom of the generator. If coke is present in excess, most of the carbon monoxide is formed in a combustion zone, which is at a temperature above 1800C, surrounding toe stream of oxygen emerging from the nozzles at high velocity The carbon monoxide is withdrawn at the top of the generator. The heat of reaction is in most cases removed by cooling water in the cooling jacket surrounding the generator. Steam generation is also possible, as described in DEMOS No.
1,95~,517.
The process descried above was the disa~vanta~e, firstly, that the slag left from combustion of the coke accumulates at the bottom of the venerator. This may considerably impair the efficiency of the nozzle(s) also located at the bottom. damage by burning causes water to enter the generator and hydrogen appears in the production gas causing subsequent processing to be very e A 22 499 -c-31 aye difficult or even dangerous. In any case, continuous removal of slag is not possible.
Another disadvantage is that the volumetric output of a conventional generator is limited by heat genera-lion as a result of the highly exothermic reaction of carbon with oxygen. Thus, for example, in a generator having a volume of 4 my supplied with pure oxygen, the maximum carbon monoxide production achieved is 140 m3/h, which corresponds to a volumetric output of 35 my of CO/h x my of generator volume. An improvement in the heat transfer may be achieved by the introduction of a truncated cone-shaped hollow core which may be cooled, as described in DEMOS No. 2,046,172. Considerably more effective is the addition of carbon dioxide to the oxygen fed into the generator since the reaction between carbon dioxide and carbon is highly endothermic.
The output of a generator of 4 my capacity may in this way be increased to a volumetric output of 60 my CO/h x my generator volume. The meld gas used in this case may have an OKAY ratio of 2:1. With this method, however, the output is still limited by the rate at which heat may be removed in the region of the nozzle.
SUMMARY OF THE INVENTION
It is therefore an object ox the present inane-lion to provide a process for the production of carbon monoxide which may be carried out more efficiently and does not kayo the above-described disadvantages ox the known processes.
A process which fulfill all these requirements in -30 a particularly advantageous manner has now surprisingly lo A 22 499 been found. The present invention departs from the method invariably employed in the past (i.e. arranging the nozzle(s) at the bottom of the generator and, instead, introduces the nozzles laterally through the generator jacket and directed downwardly. By this change in the nozzle location, the abo~e-described disadvantages may be overcome and a considerable increase in the volumetric output of the generator may be achieved with optimum utilization of the heat of reaction of carbon combustion.
The present invention therefore relates to a process for the production of carbon monoxide in a water-cooled generator which is in the form of a truncated cone in longitudinal section and is filled with carbon, and by gasification of the carbon with a mixed gas of oxygen and carbon dioxide, said mixed gas being injected into the generator through one or more downwardly directed, callable nozzles provided on the jointer jacket, while the carbon monoxide formed is remove din the opposite direction at the side and/or head of the generator. The callable nozzles which extend through the generator jacket sidewall are spaced from the bottom of the generator and are dow~wardly-directed Jo that the gas stream prom the nozzle is also directed downwardly. The nozzle spacing prom the bottom of the generator should be sufficient to avoid contact with and interference from slag which forms and collects at the bottom of the generator. Otherwise the spacing from the bottom it not particularly critical.
lo A 22 I
~2~6~
The carbon used in this process is preferably coke.
If additives, which depress the melting point of the slay are added to the coke, then liquid slag can be removed continuously or intermittently at the bottom of the generator.
The process can be carried out particularly effective-lye if the volumetric ratio of oxygen to carbon dioxide in the mixed gas is adjusted to a value of down 1:1, prefer-ably somewhere in the range of from 1.2:1 to 1.3:1. This results in a significantly improved utilization of the heat of reaction of carbon combustion and a further increase in the volumetric output to over 400 my CO/h x my of reaction volume.
Particularly complete conversion to carbon monoxide may be achieved by injecting oxygen through one or more additional nozzles situated above the downwardly-directed mixed gas nozzles.
It is found particularly advantageous for carrying out the process to equip the nozzles with a double-walled cooling jacket cooled wit water. A further advantage is obtained by drawing off the product carton monoxide gas laterally since this considerably reduces the thermal stress on the mechanical equipment for intro-during coke at the head of the generator.
grief DESCRIPTION Of THE DRAWING
A carbon monoxide generator fox carrying out the process according to the present invention is illustrated schematically by the accompanying figure. This is only one of many possible designs of such a carbon monoxide generator.
lo A 22 499 ~2~6~
Through inlet (2), carbon is introduced into the generator chamber (3) from a gate (1). This generator chamber is surrounded by a cooling water system (4) and has a mixed gas (OKAY) nozzle (5) and an outlet (6) for the discharge of product gas. The slag (7) is removed through a slag outlet (8) at the bottom of the generator.
An access hole (9) is provided for servicing the generator.
The process described may be applied analogously to other gas-solid reactions to similar advantage. Examples include the production of generator gas:
4N2 2 + 2C 4N2 t KIWI Q
or synthesis gas:
Q HO t C ` Ho CO
The present invention will now be explained with reference to a non-limiting Example.
Example Crushed coke is introduced at the rate of 780 kg/h into a carbon monoxide generator as illustrated in the accompanying figure having a volume of 4 my through a gate at the head of the generator and about 13 ugh of slag (with additive) are removed it the bottom. 438 Nm3/h of oxygen and 362 Nm3/h of carbon dioxide are injected through nozzles in the generator jacket and 1600 Nm3fh of 98 % pure carbon monoxide are withdrawn as crude gas with fly ash through a nozzle on the opposite side of the generator to be conveyed to the downstream gas purification steps.
lo A 22 499
Claims (11)
1. In the process for the production of carbon mon-oxide in a carbon-filled, water-cooled generator in the configuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide, wherein the improve-ment comprises injecting the mixed gas into the generator through at least one downwardly-directed, coolable nozzle arranged in the generator sidewall and removing the carbon monoxide formed.
2. The process according to claim 1 wherein the carbon monoxide formed is removed in a direction opposite to the nozzle orientation at the side or head of the generator.
3. The process according to claim 1 wherein the carbon is in the form of coke.
4. The process according to claim 3 wherein addi-tives are mixed with the coke.
5. The process according to claim 1 wherein the volumetric ratio of oxygen to carbon dioxide in the mixed gas is down to 1:1.
6. The process according to claim 5 wherein the ratio is in the range of 1.2:1 to 1.3:1.
7. The process according to claim 1 wherein oxygen is injected through an additional nozzle arranged above the mixed gas nozzle.
8. The process according to claim 1 wherein the nozzle is equipped with a double jacket supplied with water for cooling.
9. The process according to claim 8 wherein the nozzles are copper.
10. The process according to claim 1 wherein liquid slag is removed intermittently at the bottom of the generator.
11. The process according to claim 1 wherein liquid slag is removed continuously at the bottom of the genera-tor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833340929 DE3340929A1 (en) | 1983-11-11 | 1983-11-11 | METHOD FOR PRODUCING CARBON MONOXIDE |
| DEP3340929.3 | 1983-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226116A true CA1226116A (en) | 1987-09-01 |
Family
ID=6214137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467461A Expired CA1226116A (en) | 1983-11-11 | 1984-11-09 | Process for the production of carbon monoxide |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4564513A (en) |
| EP (1) | EP0142097B1 (en) |
| JP (1) | JPS60118619A (en) |
| BR (1) | BR8405724A (en) |
| CA (1) | CA1226116A (en) |
| DE (2) | DE3340929A1 (en) |
| ES (1) | ES8507420A1 (en) |
| ZA (1) | ZA848768B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235056B2 (en) * | 1996-05-17 | 2007-06-26 | Amira Medical | Body fluid sampling device and methods of use |
| EP1579814A3 (en) * | 1996-05-17 | 2006-06-14 | Roche Diagnostics Operations, Inc. | Methods and apparatus for sampling and analyzing body fluid |
| US7828749B2 (en) * | 1996-05-17 | 2010-11-09 | Roche Diagnostics Operations, Inc. | Blood and interstitial fluid sampling device |
| US20020010406A1 (en) | 1996-05-17 | 2002-01-24 | Douglas Joel S. | Methods and apparatus for expressing body fluid from an incision |
| US6706000B2 (en) * | 1997-11-21 | 2004-03-16 | Amira Medical | Methods and apparatus for expressing body fluid from an incision |
| US20020188223A1 (en) * | 2001-06-08 | 2002-12-12 | Edward Perez | Devices and methods for the expression of bodily fluids from an incision |
| JP2003028577A (en) * | 2001-07-19 | 2003-01-29 | Nippon Soda Co Ltd | Oxygen-blowing nozzle |
| EP1423049A2 (en) * | 2001-08-29 | 2004-06-02 | Roche Diagnostics GmbH | Wicking methods and structures for use in sampling bodily fluids |
| US20080149524A1 (en) * | 2003-03-27 | 2008-06-26 | Rademaker William B | Food containers including dental cleaning devices and other personal care items |
| DE10348116B4 (en) * | 2003-10-16 | 2015-02-19 | Bayer Intellectual Property Gmbh | CO generator and method of producing carbon monoxide-containing gas by reacting a carbonaceous fuel |
| US8372171B2 (en) * | 2009-11-23 | 2013-02-12 | Louis Herrington | CO generator and process for desulfurizing solid carbon-based fuels |
| CN103253665B (en) * | 2013-04-15 | 2015-01-07 | 内蒙古包钢钢联股份有限公司 | Method for preparing carbon monoxide by using carbon dioxide in laboratory |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE387292C (en) * | 1921-03-04 | 1923-12-28 | Wilhelm Hoffmann | Tapping gas generator |
| DE916447C (en) * | 1942-07-12 | 1954-08-09 | Koppers Gmbh Heinrich | Process for producing pure carbon dioxide gas |
| GB1070009A (en) * | 1963-01-31 | 1967-05-24 | Gas Council | Improvements in and relating to the gasification of solid carbonaceous fuel |
| US3325253A (en) * | 1963-05-29 | 1967-06-13 | Allied Chem | Process for producing carbon monoxide |
| US3635672A (en) * | 1969-03-25 | 1972-01-18 | Total Energy Corp | Method of gasifying carbonaceous materials to a carbon monoxide fuel gas product |
| DE1950517A1 (en) * | 1969-10-07 | 1971-04-29 | Bamag Verfahrenstechnik Gmbh | Gasification of coke |
| DE2001844B2 (en) * | 1970-01-16 | 1980-01-10 | Krupp-Koppers Gmbh, 4300 Essen | Method and device for producing carbon monoxide by reacting glowing coke with oxygen and carbon dioxide |
| DE2046172C3 (en) * | 1970-09-18 | 1980-01-17 | Dr. C. Otto & Comp. Gmbh, 4630 Bochum | Gas generator |
| GB1569409A (en) * | 1975-11-27 | 1980-06-11 | British Gas Corp | Slag taps and to coal gasification plants incorporating such slag taps |
| DE2738932C2 (en) * | 1977-08-30 | 1986-02-06 | Metallgesellschaft Ag, 6000 Frankfurt | Process for continuous slag removal in the gasification of solid fuels |
| US4244180A (en) * | 1979-03-16 | 1981-01-13 | Rasor Associates, Inc. | Process for producing fuel gases from carbonaceous material |
| US4436530A (en) * | 1982-07-02 | 1984-03-13 | Texaco Development Corporation | Process for gasifying solid carbon containing materials |
-
1983
- 1983-11-11 DE DE19833340929 patent/DE3340929A1/en not_active Withdrawn
-
1984
- 1984-10-29 US US06/665,724 patent/US4564513A/en not_active Expired - Fee Related
- 1984-10-30 EP EP84113032A patent/EP0142097B1/en not_active Expired
- 1984-10-30 DE DE8484113032T patent/DE3480849D1/en not_active Expired - Lifetime
- 1984-11-07 JP JP59233371A patent/JPS60118619A/en active Granted
- 1984-11-08 ES ES537535A patent/ES8507420A1/en not_active Expired
- 1984-11-09 CA CA000467461A patent/CA1226116A/en not_active Expired
- 1984-11-09 BR BR8405724A patent/BR8405724A/en not_active IP Right Cessation
- 1984-11-09 ZA ZA848768A patent/ZA848768B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0142097B1 (en) | 1989-12-27 |
| EP0142097A2 (en) | 1985-05-22 |
| ES537535A0 (en) | 1985-09-16 |
| BR8405724A (en) | 1985-09-17 |
| DE3480849D1 (en) | 1990-02-01 |
| JPH0563407B2 (en) | 1993-09-10 |
| ZA848768B (en) | 1985-07-31 |
| DE3340929A1 (en) | 1985-05-23 |
| ES8507420A1 (en) | 1985-09-16 |
| EP0142097A3 (en) | 1987-09-30 |
| US4564513A (en) | 1986-01-14 |
| JPS60118619A (en) | 1985-06-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |