AU599786B2 - Process and apparatus for the preparation of synthesis gas - Google Patents
Process and apparatus for the preparation of synthesis gas Download PDFInfo
- Publication number
- AU599786B2 AU599786B2 AU15525/88A AU1552588A AU599786B2 AU 599786 B2 AU599786 B2 AU 599786B2 AU 15525/88 A AU15525/88 A AU 15525/88A AU 1552588 A AU1552588 A AU 1552588A AU 599786 B2 AU599786 B2 AU 599786B2
- Authority
- AU
- Australia
- Prior art keywords
- lockhopper
- slag
- gas
- quench vessel
- valves
- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/52—Ash-removing devices
- C10J3/526—Ash-removing devices for entrained flow gasifiers
-
- 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
- C10J3/485—Entrained flow gasifiers
-
- 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
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- 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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- 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
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/156—Sluices, e.g. mechanical sluices for preventing escape of gas through the feed inlet
-
- 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
- C10J2300/0956—Air or oxygen enriched air
-
- 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
Landscapes
- 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)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Gasification And Melting Of Waste (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
S F Ref: 56051 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: ,pxid~alY" ~smde ad'lc S49.
ad 1z M 11 -OrF'in~li Name and Address of Applicant: Address for Service: Shell Internationale Research Maatschappij B.V.
Carel van Bylandtlaan 2596 HR The Hague THE NETHERLANDS Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Process and Apparatus for the Preparation of Synthesis Gas The following statement is a full description of this best method of performing it known to me/us invention, including the 5845/4 I T 5727
ABSTRACT
PROCESS AND APPARATUS FOR THE PREPARATION OF SYNTHESIS GAS A process for the preparation of synthesis gas by partial S combustion of finely divided solid carbon-containing fuel with an j oxygen-containing gas in a reactor. The liquid slag formed during the partial combustion process falls into a water bath or slag o o. quench vessel where it solidifies and from there falls by gravity into a lockhopper from which the solidified slag is batchwise o sluiced out of the gasification system. A gas bubble or gascap is created and maintained in the lockhopper, the pressure of the gas bubble being lower than the pressure in the slag quench vessel.
Thus an initial downwards flow of water and slag is created during opening of the valves between the lockhopper and the slag quench 0 oo vessel.
0 0RH EKRH04
L.
in- T 5727 PROMSS AND APPARATUS FOR THE PREPARATION OF SYNTHESIS GAS The invention relates to a process for the preparation of synthesis gas by the partial combustion of a finely dividea solid carbon-containing fuel with an oxygen-containing gas in a reactor wherein liquid slag formed during the partial combustion process is removed through an outlet in the bottom of the reactor and passed by gravity through a slag discharge n-eans into a water bath or slag quenching vessel where it is solidified by quenching.
The partial combustion of finely divided solid carbon--containing fuel with substantially pure oxygen as oxygen-containing gas yields synthesis gas mainly consisting of carbon monoxide. and hydrogen. When the oxygen-containing gas is air or oxygen-enriched air, the synthesis gas formed of course also contains a substantial quantity of nitrogen. By finely divided solid carbon-containing fuel is generally me~ant coal or another solid fuel, such as brown coal, peat, wood, coke, soot etc., but mixtures of liquid or gas and particulate solid fuels, are also possible.
Advantageously, a mroderator is also introduced into the reactor, The object of the mroderator is to exercise a mroderating effect on the temperature on the reactor. This is ensured by endothermic reaction between the roderator and the reactants and/or products of the synthesis gab preparation. Suitable mroderators are steam and carbon dioxide.
The gasification is advantageously carried out at a tem-perature in the range from 1200 to 1700 'C and at a pressure in the range from 1 to 200 bar.
The reactor in which the preparation of synthesis gas takes place may have any suitable shape.
1__11-~111111--1 1_ 2- The supply of finely divided solid carbon-containing fuel and oxygen-containing gas to the reactor can take place in any manner suitable for the purpose and will not be described in detail.
Liquid slag formed in the partial combustion reaction drops down and is drained through the outlet located in the reactor bottom.
To remove the slag from the gasifying process, it is already known to arrange a quenching water bath or slag quench vessel located below the reactor and connected therewith in any way 0 o 10 suitable for the purpose, in which water bath or slag quench vessel o the slag descending due to its gravity, is captured, quenched, and forms clinker granules or agglomerations. After such granulation, 0) the clinker is periodically or continuously removed from the said water bath or slag quench vessel by means of conventional arrangements.
This may for example be carried out by means of a lockhopper from which solidified slag is batchwise sluiced out of the gasification system.
During the sluicing cycle the lockhopper is isolated from the gasification system by closing one or more valves in the connecting line between the slag quench vessel and the lockhopper.
However, the slag which is produced in the meantime in the So o partial combustion process collects in the slag quench vessel above these valves where it shows a tendency for bridging at the narrow space just above the said valves.
However, it has appeared very difficult to have the slag to fall into the lockhopper after reconnecting the lockhopper to the gasification system.
Even water jet nozzles for agitation purposes proved to be not successful. Therefore, it is an object of the invention to provide a process and an apparatus for producing synthesis gas by the partial combustion of finely divided solid carbon-containing fuel wherein the liquid slag formed during the partial combustion process can be removed from the slag quench vessel easily in a very effective and efficient manner.
3- It is another object of the invention to provide a quick performance test of the valves between the slag quench vessel and the lockhopper.
The invention therefore provides a process for the preparation of synthesis gas by partial combustion of finely divided solid carbon-containing fuel with an oxygen-containing gas in a reactor, wherein liquid slag formed during the partial combustion process falls into a water bath or slag quench vessel where it solidifies and from there falls by gravity into a lockhopper from which the o 10 solidified slag is batchwise sluiced out of the gasification system, said lockhopper and slag quench vessel being connected through one or more valves, comprising the steps of creating and maintaining a permanent gas bubble or gascap in the lockhopper, the pressure of the said gas bubble being lower than the pressure in the slag quench vessel, thus creating an initial downwards flow of water and slag during opening of the valves between the lockhopper and the slag quench vessel.
The invention also provides an apparatus for carrying out the above process comprising a slag quench vessel, connected through one or more valves to a lockhopper provided at its bottom with an outlet comprising one or more valves, and means for creating and maintaining a permanent gas bubble or gascap in the lockhopper.
In an advantageous embodiment of the invention the gas bubble in the lockhopper can be created by inserting downwardly a pipe of a certain length into the top of the lockhopper.
In another advantageous embodiment the gas bubble consists of an inert gas such as nitrogen.
The invention will now be described in more detail by way of example with reference to the accompanying drawings, in which figs.
1 and 2 schematically represent advantageous embodiments of the apparatus of the invention.
Referring now to figs. 1 and 2 a cross-section of a slag quench vessel 1 provided with an outlet 2 has been represented. The slag quench vessel 1 is part of a gasification system and is located below a reactor or gasification zone wherein the partial -4combustion process is carried out, and is connected thereto in any manner suitable for the purpose.
The gasification zone has not been represented for reasons of clarity. The outlet 2 of the slag quench vessel 1 is connected by any suitable connecting line 3 to a lockhopper 4 located below the said slag quench vessel. In the line 3 one or more valves 3a are provided.
In the lockhopper 4 a permanent gas bubble or gascap 5 is maintained, at a pressure lower than the pressure in the slag quench vessel 1. The gas bubble may for example consist of an inert gas such as nitrogen.
The lockhopper 4 is provided with an outlet 7 at its bottom and one or more valves 7a for discharging the solidified slag from the gasification system during a sluicing cycle. The slag can be discharged to any means suitable for the purpose (not shown for reasons of clarity). The gas bubble 5 in the lockhopper may be maintained by supplying inert gas (such as nitrogen) to the lockhopper 4 by means of a conduit or pipe 6 penetrating into the upper interior space of the lockhupper, as shown in fig. 1, or advantageously by means of a pipe 6a in fluid comunication with the vertically disposed conduit between the slag quench vessel 1 and the lockhopper 4, as shown in fig. 2, and wherein said vertical conduit penetrates into the interior of said lockhopper a distance sufficient to maintain the gas bubble in the uppermost part of the lockhopper.
The operation of the system of the invention is as follows: the liquid slag which is formed in the gasification system during the partial combustion process falls into the water bath or slag quench vessel 1 where it solidifies.
From the slag quench vessel 1 it falls by gravity into the lockhopper 4 from which the solidified slag is batchwise sluiced out of the gasification system. It will be clear to those skilled in the art that at appropriate times the valves 3a and 7a should be opened and closed respectively.
During the sluicing cycle the lockhopper 4 is isolated from i the gasification system since the valves 3a between the slag quench vessel and the lockhopper are closed, whereas the valves 7a at the outlet 7 of the lockhopper 4 are opened. Thus, slag which is produced in the meantime, will collect in the slag quench vessel 1 above the valves 3a and has a tendency for bridging at the narrow space just above these valves schematically represented by the bridging region A).
According to the invention, after reconnecting the lockhopper 4 to the gasification system by closing the valves 7a and opening the valves 3a the gas bubble in the lockhopper having a lower o pressure than the pressure in the slag quench vessel creates an initial downwards flow of water and slag thus resulting in a debridging action in the region A.
It will be appreciated that the gas bubble also allows a quick S 15 performance test of the valves. If the volume of the gas bubble changes with time this is an indication of valve leakages.
It will further be appreciated that the pressure of the gas bubble in the lockhopper can be higher than the pressure of the S0° discharge means outside the lockhopper. In this manner unloading of a 20 the lockhopper is facilitated and possible bridging at the outlet 7 of the lockhopper is reduced.
Various modifications of the present invention will become 0o apparent to those skilled in the art from the foregoing description and accompanying drawing. Such modifications are intended to fall within the scope of the appended claims.
1 1
Claims (9)
1. A process for the preparation of synthesis gas by partial combustion of finely divided solid carbon-containing fuel with an oxygen-containing gas in a reactor, wherein liquid slag formed during the partial combustion process falls into a water bath or slag quench vessel where it solidifies and from there falls by gravity into a lockhopper from which the solidified slag is batchwise sluiced out of the gasification system said lockhopper and slag quench vessel being connected through one or more valves, comprising the steps of creating and maintaining a permanent gas bubble or gas cap in the lockhopper, the pressure of the gas bubble being lower than the pressure in the slag quench vessel, thus creating an initial downwards flow of water and slag during opening of the valves between the lockhopper and the slag quench vessel.
2. The process as claimed in claim 1 wherein the gas bubble is maintained by supplying gas to the lockhopper by means of a conduit or pipe extending into the upper interior space within the lockhopper.
3. The process as claimed in claim 1 or 2 wherein the gas bubble consists of an inert gas.
4. The process as claimed in claim 3 wherein the inert gas is nitrogen.
A process for the preparation of synthesis gas by partial combustion of finely divided solid carbon-containing fuel with an o1 O oxygen-containing gas in a reactor, wherein liquid slag formed during the partial combustion process falls into a water bath or slag quench vessel where it solidifies and from there falls by gravity into a lockhopper from which the solidified slag is batchwise sluiced out of the gasification system said lockhopper and slag quench vessel being connected through one or more valves, substantially as hereinbefore described with reference to any one of the accompanying drawings.
6. An apparatus for carrying out the process as claimed in any one o of claims 1 5 comprising a slag quench vessel, connected through one or more valves to a lockhopper provided at its bottom with an outlet, comprising one or more valves, and means for creating and maintaining a permanent gas bubble in the lockhopper. KNK:769y -7
7. The apparatus as claimed in claim 6 comprising a conduit or pipe extending into the upper interior space within the lockhopper.
8. An apparatus for carrying out the process of claim substantially as described in the description by reference to figs. 1 and 2 of the accompanying drawings.
9. Synthesis gas whenever produced by the process of any one of claims 1 to DATED this NINETEENTH day of APRIL 1990 Shell Internationale Research Maatschappij B.V. Patent Attorneys for the Applicant SPRUSON FERGUSON L u KNK:769y
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873714915 DE3714915A1 (en) | 1987-05-05 | 1987-05-05 | METHOD AND DEVICE FOR THE PRODUCTION OF SYNTHESIS GAS |
| DE3714915 | 1987-05-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1552588A AU1552588A (en) | 1988-11-10 |
| AU599786B2 true AU599786B2 (en) | 1990-07-26 |
Family
ID=6326856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU15525/88A Expired AU599786B2 (en) | 1987-05-05 | 1988-05-03 | Process and apparatus for the preparation of synthesis gas |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0290087B1 (en) |
| JP (1) | JP2609533B2 (en) |
| CN (1) | CN1018187B (en) |
| AU (1) | AU599786B2 (en) |
| CA (1) | CA1336645C (en) |
| DE (2) | DE3714915A1 (en) |
| ZA (1) | ZA883134B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021736A1 (en) * | 1999-09-21 | 2001-03-29 | Shell Internationale Research Maatschappij B.V. | Process to remove solid slag particles from a mixture of solid slag particles and water |
| US6755980B1 (en) | 2000-09-20 | 2004-06-29 | Shell Oil Company | Process to remove solid slag particles from a mixture of solid slag particles and water |
| US8317885B2 (en) | 2004-11-22 | 2012-11-27 | Shell Oil Company | Apparatus for gasifying fuel with a dripper edge and heat shield |
| CN1994865B (en) | 2006-12-12 | 2011-05-18 | 华东理工大学 | Gasification device for two-stage gasification coupled with heat recovery and washing and its uses |
| CN101003358B (en) | 2006-12-12 | 2011-05-18 | 华东理工大学 | Multi nozzle gasification furnace feeding in hydrocarbon-including plasma or powder state |
| DE102008005704A1 (en) | 2008-01-24 | 2009-07-30 | Uhde Gmbh | Process and installation for the removal of slag from a slag bath tank, in particular in synthesis gas recovery |
| US8349170B2 (en) * | 2008-05-14 | 2013-01-08 | Exxonmobil Research And Engineering Company | FCC reactor and riser design for short contact-time catalytic cracking of hydrocarbons |
| DE102008033095A1 (en) * | 2008-07-15 | 2010-01-28 | Uhde Gmbh | Apparatus for slag removal from a coal gasification reactor |
| DE102008033094A1 (en) | 2008-07-15 | 2010-01-28 | Uhde Gmbh | Gasification device with continuous solids discharge |
| DE102008035386A1 (en) | 2008-07-29 | 2010-02-11 | Uhde Gmbh | Slag discharge from reactor for syngas recovery |
| CN118667586B (en) * | 2024-08-21 | 2024-10-29 | 国家电投集团山西电力有限公司 | Auxiliary component of biomass gasification furnace |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235313A (en) * | 1964-05-18 | 1966-02-15 | Koppers Co Inc | Sluicing solid materials from spaces under superatmospheric pressure |
| EP0215857A1 (en) * | 1985-03-05 | 1987-04-01 | Veba Oel Entwicklungs Gmbh | Process for the evacuation of particles of residue from a pressure gasification reactor. |
| AU582267B2 (en) * | 1986-08-06 | 1989-03-16 | Destec Energy, Inc. | Slag removal system for a solid fuels gasification reactor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2455127C2 (en) * | 1974-11-21 | 1986-02-27 | Shell Internationale Research Maatschappij B.V., Den Haag | Process for discharging residues from a gasification chamber under increased pressure |
| BR8105270A (en) * | 1980-11-12 | 1982-08-31 | Texaco Development Corp | PROCESS FOR THE PRODUCTION OF SYNTHESIS GAS SUBSTANTIALLY FREE OF PARTICLES |
| US4533363A (en) * | 1984-01-20 | 1985-08-06 | Texaco Development Corporation | Production of synthesis gas |
| JPS61243896A (en) * | 1985-04-23 | 1986-10-30 | Mitsubishi Heavy Ind Ltd | Method of discharging slag in gasifying oven |
-
1987
- 1987-05-05 DE DE19873714915 patent/DE3714915A1/en not_active Withdrawn
-
1988
- 1988-04-20 CA CA000564586A patent/CA1336645C/en not_active Expired - Lifetime
- 1988-04-27 DE DE8888200829T patent/DE3860637D1/en not_active Expired - Lifetime
- 1988-04-27 EP EP88200829A patent/EP0290087B1/en not_active Expired - Lifetime
- 1988-05-02 JP JP63107781A patent/JP2609533B2/en not_active Expired - Lifetime
- 1988-05-03 ZA ZA883134A patent/ZA883134B/en unknown
- 1988-05-03 AU AU15525/88A patent/AU599786B2/en not_active Expired
- 1988-05-03 CN CN88102581A patent/CN1018187B/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235313A (en) * | 1964-05-18 | 1966-02-15 | Koppers Co Inc | Sluicing solid materials from spaces under superatmospheric pressure |
| EP0215857A1 (en) * | 1985-03-05 | 1987-04-01 | Veba Oel Entwicklungs Gmbh | Process for the evacuation of particles of residue from a pressure gasification reactor. |
| AU582267B2 (en) * | 1986-08-06 | 1989-03-16 | Destec Energy, Inc. | Slag removal system for a solid fuels gasification reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA883134B (en) | 1988-11-08 |
| EP0290087B1 (en) | 1990-09-19 |
| CN1018187B (en) | 1992-09-09 |
| AU1552588A (en) | 1988-11-10 |
| EP0290087A2 (en) | 1988-11-09 |
| CA1336645C (en) | 1995-08-15 |
| JPS63286493A (en) | 1988-11-24 |
| JP2609533B2 (en) | 1997-05-14 |
| DE3714915A1 (en) | 1988-11-24 |
| EP0290087A3 (en) | 1989-02-08 |
| DE3860637D1 (en) | 1990-10-25 |
| CN88102581A (en) | 1988-11-16 |
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