EP0151399B1 - Hydrogen gas distribution in coal liquefaction plants - Google Patents
Hydrogen gas distribution in coal liquefaction plants Download PDFInfo
- Publication number
- EP0151399B1 EP0151399B1 EP85100277A EP85100277A EP0151399B1 EP 0151399 B1 EP0151399 B1 EP 0151399B1 EP 85100277 A EP85100277 A EP 85100277A EP 85100277 A EP85100277 A EP 85100277A EP 0151399 B1 EP0151399 B1 EP 0151399B1
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- EP
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- Prior art keywords
- hydrogenation
- hydrogen
- refining
- gas
- coal
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- 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.)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
Definitions
- the invention relates to a hydrogenation gas flow in coal liquefaction plants, wherein the coal oils coming from the hydrogenation are freed from hydrogenation S, N, 0 by hydrogenation in a refining.
- Such a hydrogenation gas guide is known from DE-A-31 141 649.
- the refining stage has the task of removing the heteroatoms S, N, 0 from coal oil by hydrogenation, since they are disadvantageous in marketable products (gasoline / heating oil).
- the hydrogen coming from the hydrogenation reactor is partially exhausted when it reaches the refining stage.
- the invention is therefore based on the object of reducing the hydrogen consumption. According to the invention, this is achieved by first leading the fresh hydrogen into the refining stages.
- the invention is based on the consideration that the "cleanest" product is produced in the refining stage. It is therefore advantageous if the fresh hydrogen in the refining stage is not burdened with the work result from the hydrogenation reactor.
- These loads are formed in particular by H 2 S and NH 3 multicaptans.
- the cold separator's gas phase In accordance with the division of the cold separator's gas phase into recycle and discharge gas, they are discharged or extracted with the same gaseous compounds that are additionally formed during the hydrogenation of the coal via gas scrubbing and low-temperature separation.
- the hydrogenation gas guide according to the invention is shown in the form of a flow diagram.
- Dried coal is mashed with solvent in a slurry (1) and hydrogenated in a reactor (2) with the addition of hydrogen.
- a phase separation is carried out in the hot separator (3) downstream of the hydrogenation reactor (2).
- the gases and vapors are drawn off overhead.
- a liquid phase, which contains the solids, is removed from the sump into the vacuum distillation (5).
- the top product of the hot separator (3) is passed into the cold separator (4).
- water is produced here, which is pumped off separately to recover valuable ingredients (ammonia, phenol).
- coal oil is drawn off and atmospheric with the addition of stripping steam in one atm.
- Distillation (6) distilled. Light and medium oil of atm. Distillation is fed to separate refining stages (21 and 22).
- the gas phase leaving the cold separator at the top is divided in an oil scrubber (7) into recycle gas and discharge gas.
- the discharge gas is cleaned in a gas scrubber (8) and broken down into hydrogen, heating gas, SNG and LPG in a low-temperature separation plant (9).
- the solid-containing liquid phase obtained in the hot separator is topped in vacuum distillation (5).
- the resulting heavy oil is extracted from the atm together with heavy and medium oil. Distillation as solvent in the slurry (1).
- Hydrogen hydrogen is obtained from the residue from the vacuum distillation in a gasification stage (10) synthesis gas (CO + H 2 ) or in a conversion and gas scrubbing (11).
- the tar-containing wastewater of the atmospheric cold separator. Distillation (6) are fed to an ammonia recovery (23) and a phenol recovery (24). After biological treatment (25), the wastewater is discharged into the public wastewater network. Likewise, the wastewater from gasification (12) and the wastewater from residue gasification (10) are discharged into the public sewage network after neutralization (26).
- the cycle gas obtained from the oil wash (7) is compressed to the necessary operating pressure by a cycle gas compressor (27).
- the cycle gas and the fresh hydrogen obtained from the low-temperature decomposition (9) the total amount of hydrogen-rich gases emerging from the refining stages (21 + 22) is fed in again.
- the refining stages have the task of removing the heteroatoms SNO from the coal oil by hydrogenation, since they are disadvantageous in marketable products (gasoline / heating oil).
- the unit t (waf) coal / d denotes ton of coal (water and ash free) per day.
- the light coal oil is refined in two stages with the addition of 3,138 kg / h (stage I) and 2,587 kg / h (stage 11) of hydrogen with a purity of 98.5% by volume at 60 bar.
- stage I 3,138 kg / h
- stage 11 2,587 kg / h
- the hydrogen-rich gas phase total amount 5,629 kg / h
- This amount of gas is fed directly to the hydrogenation gas.
- the crude oil is refined in one stage with the addition of 9,873 kg / h of hydrogen (98.5% by volume), also at 60 bar.
- the gas produced in the downstream separator (9,565 kg / h is in turn fed directly to the coal hydrogenation.
- the hydrogen content of the hydrogenation gas flowing through the refining stages drops to 98.0 vol.% In the case of the light oil or to 97.5 vol .-% for middle oil.
- H2 partial pressures are substantially higher than that of the hydrogenation gas from the coal hydrogenation (216,252 kg / h, 85% by volume), so that feeding is possible without any problems.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft eine Hydriergasführung in Kohleverflüssigungsanlagen, wobei die aus der Hydrierung kommenden Kohleöle in einer Raffination von Heteroatomen S, N, 0 durch Hydrierung befreit werden.The invention relates to a hydrogenation gas flow in coal liquefaction plants, wherein the coal oils coming from the hydrogenation are freed from hydrogenation S, N, 0 by hydrogenation in a refining.
Eine derartige Hydriergasführung ist aus der DE-A-31 141 649 bekannt. Darin ist ein Kohleverflüssigungsverfahren offenbart, bei dem im wesentlichen reiner Wasserstoff erzeugt wird bzw. wiedergewonnen und anschließend dem Hydrierreaktor zugeführt wird. Das hat zur Folge, daß der Wasserstoff aus dem Reaktor in die Raffination gelangt. Die Raffinationsstufe hat die Aufgabe, aus Kohleöl die Heteroatome S, N, 0 durch Hydrierung zu entfernen, da sie in marktfähigen Produkten (Benzin/Heizöl) von Nachteil sind.Such a hydrogenation gas guide is known from DE-A-31 141 649. This discloses a coal liquefaction process in which essentially pure hydrogen is generated or recovered and then fed to the hydrogenation reactor. The consequence of this is that the hydrogen from the reactor reaches the refining. The refining stage has the task of removing the heteroatoms S, N, 0 from coal oil by hydrogenation, since they are disadvantageous in marketable products (gasoline / heating oil).
Der aus dem Hydrierreaktor kommende Wasserstoff ist teilweise abgearbeitet, wenn er in die Raffinationsstufe gelangt. Im Ergebnis ist auf diesem Wege eine beträchtliche Menge Wasserstoff notwendig, um marktfähige Produkte zu erzeugen. Der Erfindung liegt daher die Aufgabe zugrunde, den Wasserstoffverbrauch zu reduzieren. Nach der Erfindung wird das dadurch erreicht, daß der Frischwasserstoff zunächst in die Raffinationsstufen geführt wird. Dabei geht die Erfindung von der Überlegung aus, daß in der Raffinationsstufe das "sauberste" Produkt erzeugt wird. Deshalb ist es von Vorteil, wenn der Frischwasserstoff in der Raffinationsstufe nicht mit dem Arbeitsergebnis aus dem Hydrierreaktor belastet ist. Diese Belastungen werden insbesondere durch Mehrkaptane H2S und NH3 gebildet. U. h. es wird keine Aufteilung des aus den Raffinationsstufen austretenden, wasserstoffreichen Gases in Kreislauf- und Überschußgas vorgenommen, sondern der Gesamtmenge der Hydrierung zugeführt. Die im Gas neben dem Wasserstoff enthaltenen, bei der Raffination entstehenden organischen (C1-C4) und anorganischen (CO, C02, H2S) gasförmigen Verbindungen beeinträchtigen in der vorliegenden Konzentration die Hydrierung der Kohle nicht.The hydrogen coming from the hydrogenation reactor is partially exhausted when it reaches the refining stage. As a result, a considerable amount of hydrogen is required in this way to produce marketable products. The invention is therefore based on the object of reducing the hydrogen consumption. According to the invention, this is achieved by first leading the fresh hydrogen into the refining stages. The invention is based on the consideration that the "cleanest" product is produced in the refining stage. It is therefore advantageous if the fresh hydrogen in the refining stage is not burdened with the work result from the hydrogenation reactor. These loads are formed in particular by H 2 S and NH 3 multicaptans. U. h. there is no division of the hydrogen-rich gas emerging from the refining stages into recycle gas and excess gas, but instead the total amount of the hydrogenation is supplied. The organic (C 1 -C 4 ) and inorganic (CO, C0 2 , H 2 S) gaseous compounds contained in the gas in addition to the hydrogen produced during refining do not impair the hydrogenation of the coal in the present concentration.
Entsprechend der Aufteilung der Gasphase des Kaltabscheiders in Kreislauf- und Auschleusgas werden sie mit den zusätzlich bei der Hydrierung der Kohle entstehenden, gleichen gasförmigen Verbindungen über die Gaswäsche und Tieftemperaturzerlegung ausgeschleust bzw. gewonnen.In accordance with the division of the cold separator's gas phase into recycle and discharge gas, they are discharged or extracted with the same gaseous compounds that are additionally formed during the hydrogenation of the coal via gas scrubbing and low-temperature separation.
Der Fortfall eigener Kreislaufgaskompressoren, Gaswäscher und Wasserstoffrückgewinnungsstufen für die Raffination des Leicht- und Mittelöls bedeutet ein wesentlicher Vorteil für Investition und Betrieb.The elimination of our own cycle gas compressors, gas scrubbers and hydrogen recovery stages for the refining of light and medium oil means a significant advantage for investment and operation.
In der Zeichnung ist die erfindungsgemäße Hydriergasführung in Form eines Fließschemas dargestellt.In the drawing, the hydrogenation gas guide according to the invention is shown in the form of a flow diagram.
Getrocknete Kohle wird mit Lösungsmittel in einer Anmaischung (1) angemaischt und unter Zugabe von Wasserstoff in einem Reaktor (2) hydriert. In dem dem Hydrierreaktor (2) nachgeschalteten Heißabscheider (3), wird eine Phasentrennung durchgeführt. Die Gase und Dämpfe werden über Kopf abgezogen. Aus dem Sumpf wird eine - die Feststoffe enthaltene Flüssigphase - in die Vakuumdestillation (5) abgeführt.Dried coal is mashed with solvent in a slurry (1) and hydrogenated in a reactor (2) with the addition of hydrogen. A phase separation is carried out in the hot separator (3) downstream of the hydrogenation reactor (2). The gases and vapors are drawn off overhead. A liquid phase, which contains the solids, is removed from the sump into the vacuum distillation (5).
Das Kopfprodukt des Heißabscheiders (3) wird nach Abkühlung in den Kaltabscheider (4) geleitet. Neben Kohleöl fällt hier Wasser an, das getrennt zur Wiedergewinnung von wertvollen Inhaltsstoffen (Ammoniak, Phenol) abgepumpt wird.After cooling, the top product of the hot separator (3) is passed into the cold separator (4). In addition to coal oil, water is produced here, which is pumped off separately to recover valuable ingredients (ammonia, phenol).
Das Kohleöl wird abgezogen und atmosphärisch unter Zugabe von Strippdampf in einer atm. Destillation (6) destilliert. Leicht- und Mittel öl der atm. Destillation werden jeweils getrennt Raffinationsstufen (21 und 22) zugeführt.The coal oil is drawn off and atmospheric with the addition of stripping steam in one atm. Distillation (6) distilled. Light and medium oil of atm. Distillation is fed to separate refining stages (21 and 22).
Die über Kopf aus dem Kaltabscheider abgehende Gasphase wird in einer Ölwäsche (7) in rückgeführtes Kreislauf- und Ausschleusgas aufgeteilt. Das Ausschleusgas wird in einer Gaswäsche (8) gereinigt und in einer Tieftemperaturzerlegungsanlage (9) in Wasserstoff, Heizgas, SNG und LPG zerlegt.The gas phase leaving the cold separator at the top is divided in an oil scrubber (7) into recycle gas and discharge gas. The discharge gas is cleaned in a gas scrubber (8) and broken down into hydrogen, heating gas, SNG and LPG in a low-temperature separation plant (9).
Die im Heißabscheider anfallende feststoffhaltige Flüssigphase wird in der Vakuumdestillation (5) getoppt. Das dabei gewonnene Schweröl wird zusammen mit Schwer- und Mittelöl aus der atm. Destillation als Lösungsmittel in die Anmaischung (1) zurückgefahren.The solid-containing liquid phase obtained in the hot separator is topped in vacuum distillation (5). The resulting heavy oil is extracted from the atm together with heavy and medium oil. Distillation as solvent in the slurry (1).
Aus dem Rückstand der Vakuumdestillation wird in einer Vergasungsstufe (10) Synthesegas (CO + H2) bzw. in einer Konvertierung und Gaswäsche (11) Hydrierwasserstoff gewonnen.Hydrogen hydrogen is obtained from the residue from the vacuum distillation in a gasification stage (10) synthesis gas (CO + H 2 ) or in a conversion and gas scrubbing (11).
Reicht der über Kreislaufgas, Tieftemperaturzerlegung (9), Rückstandsvergasung (10) rückgeführte Wasserstoff für die Hydrierung nicht aus, so wird über eine zusätzliche Kohlevergasung (12) mit nachgeschalteter Konvertierung und Gaswäsche (13) das Defizit abgedeckt.If the hydrogen recirculated via cycle gas, low-temperature decomposition (9), residue gasification (10) is not sufficient for the hydrogenation, the deficit is covered by an additional coal gasification (12) with downstream conversion and gas scrubbing (13).
Die teersäurehaltigen Abwässer des Kaltabscheiders der atm. Destillation (6) werden einer Ammoniakgewinnung (23) und einer Phenolgewinnung (24) zugeführt. Die Abwässer werden nach biologischer Aufbereitung (25) in das öffentliche Abwassernetz eingeleitet. Desgleichen erfolgt eine Ableitung der bei der Vergasung (12) anfallenden Abwässer sowie der aus der Rückstandsvergasung (10) anfallenden Abwässer nach Neutralisation (26) in das öffentliche Abwassernetz.The tar-containing wastewater of the atmospheric cold separator. Distillation (6) are fed to an ammonia recovery (23) and a phenol recovery (24). After biological treatment (25), the wastewater is discharged into the public wastewater network. Likewise, the wastewater from gasification (12) and the wastewater from residue gasification (10) are discharged into the public sewage network after neutralization (26).
Das aus der Ölwäsche (7) anfallende Kreislaufgas wird über einen Kreisgaskompressor (27) auf den notwendigen Betriebsdruck verdichtet. Zusätzlich zum Kreislaufgas und den aus der Tieftemperaturzerlegung (9) anfallenden Frischwasserstoff wird die Gesamtmenge der aus den Raffinationsstufen (21 + 22) austretenden wasserstoffreichen Gase wieder zugeführt. Die Raffinationsstufen haben die Aufgabe, aus dem Kohleöl die Heteroatome SNO durch Hydrierung zu entfernen, da sie in marktfähigen Produkten (Benzin/Heizöl) von Nachteil sind.The cycle gas obtained from the oil wash (7) is compressed to the necessary operating pressure by a cycle gas compressor (27). In addition to the cycle gas and the fresh hydrogen obtained from the low-temperature decomposition (9), the total amount of hydrogen-rich gases emerging from the refining stages (21 + 22) is fed in again. The refining stages have the task of removing the heteroatoms SNO from the coal oil by hydrogenation, since they are disadvantageous in marketable products (gasoline / heating oil).
Beispiel für den Mengenfluß einer erfindungsgemäßen HydriergasführungExample of the flow rate of a hydrogenation gas guide according to the invention
In der Kohleverflüssigungsanlage zur Hydrierung einer im Ruhrgebiet geförderten Gasflammkohle mit einem Durchsatz von 5 000 t(waf) Kohle/d, fallen entsprechend einer Stundenleistung von ca. 208 t/h in der atmosphärischen Destillation 31.833 kg/h Kohleleicht- und 64.006 kg/h Rohmittelöl an.In the coal liquefaction plant for the hydrogenation of a gas flame coal extracted in the Ruhr area with a throughput of 5,000 t (waf) coal / d, 31,833 kg / h of light coal and 64,006 kg / h fall in the atmospheric distillation, corresponding to an hourly output of approx. 208 t / h Crude oil.
Die Einheit t(waf) Kohle/d bezeichnet Tonne Kohle (wasser- und aschefrei) pro Tag.The unit t (waf) coal / d denotes ton of coal (water and ash free) per day.
Die Raffination des Kohleleichtöles erfolgt zweistufig unter Zugabe von 3.138 kg/h (Stufe I) und 2.587 kg/h (Stufe 11) Wasserstoff mit einer Reinheit von 98,5 Vol.-% bei 60 bar. In den Raffinationsreaktoren nachgeschalteten Abscheidern erfolgt eine Abtrennung der wasserstoffreichen Gasphase (Gesamtmenge 5.629 kg /h) vom Hydrierprodukt bei 55 bar. Diese Gasmenge wird dem Hydriergas direkt zugeführt.The light coal oil is refined in two stages with the addition of 3,138 kg / h (stage I) and 2,587 kg / h (stage 11) of hydrogen with a purity of 98.5% by volume at 60 bar. In the separators connected downstream of the refining reactors, the hydrogen-rich gas phase (total amount 5,629 kg / h) is separated from the hydrogenation product at 55 bar. This amount of gas is fed directly to the hydrogenation gas.
Die Raffination des Rohmittelöles erfolgt einstufig unter Zugabe von 9.873 kg/h Wasserstoff (98,5 Vol-%) ebenfalls bei 60 bar. Das im nachgeschalteten Abscheider anfallende Gas (9.565 kg/h wird wiederum der Kohlehydrierung direkt zugeführt.The crude oil is refined in one stage with the addition of 9,873 kg / h of hydrogen (98.5% by volume), also at 60 bar. The gas produced in the downstream separator (9,565 kg / h is in turn fed directly to the coal hydrogenation.
Durch Anreicherung an C, C4 - Kohlenwasserstoffgasanteilen sowie an CO-, C02 und H2S-Mengen sinkt der Wasserstoffgehalt des durch die Raffinationsstufen strömenden Hydriergases auf 98,0 Vol.-% im Falle des Leichtöles bzw. auf 97,5 Vol.-% beim Mittelöl.By enriching in C, C 4 - hydrocarbon gas fractions as well as in CO, C0 2 and H 2 S quantities, the hydrogen content of the hydrogenation gas flowing through the refining stages drops to 98.0 vol.% In the case of the light oil or to 97.5 vol .-% for middle oil.
Diese H2-Partialdrücke liegen wesentlich über dem des Hydriergases der Kohlehydrierung (216.252 kg/h, 85 Vol.-%), so daß eine Zuspeisung unproblematisch möglich ist.These H2 partial pressures are substantially higher than that of the hydrogenation gas from the coal hydrogenation (216,252 kg / h, 85% by volume), so that feeding is possible without any problems.
Claims (1)
- Hydrogenation gas distribution in coal liquefaction plants, wherein the coal oils coming from the hydrogenation are cleansed of heteroatoms S, N, 0 by hydrogenation in a refining unit, characterized in that the fresh hydrogen is supplied directly to the refining and the hydrogen partly exhausted in the refining is thereafter fed to the hydrogenation reactor, the quantity of hydrogen additionally necessary being supplied as fresh hydrogen directly to the hydrogenation reactor in known manner.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3401650 | 1984-01-19 | ||
| DE19843401650 DE3401650A1 (en) | 1983-12-10 | 1984-01-19 | Hydrogenation gas arrangement in coal liquefaction plants |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0151399A2 EP0151399A2 (en) | 1985-08-14 |
| EP0151399A3 EP0151399A3 (en) | 1987-05-13 |
| EP0151399B1 true EP0151399B1 (en) | 1989-08-02 |
Family
ID=6225291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85100277A Expired EP0151399B1 (en) | 1984-01-19 | 1985-01-12 | Hydrogen gas distribution in coal liquefaction plants |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0151399B1 (en) |
| JP (1) | JPS60161483A (en) |
| AU (1) | AU582133B2 (en) |
| BR (1) | BR8500578A (en) |
| CA (1) | CA1239366A (en) |
| DD (1) | DD236340A5 (en) |
| DE (1) | DE3572001D1 (en) |
| PL (1) | PL141658B1 (en) |
| SU (1) | SU1473714A3 (en) |
| ZA (1) | ZA85428B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3519830A1 (en) * | 1985-06-03 | 1986-12-18 | Ruhrkohle Ag, 4300 Essen | METAL OF COAL HYDRATION WITH INTEGRATED REFINING STAGES |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4179352A (en) * | 1975-08-07 | 1979-12-18 | Exxon Research & Engineering Co. | Coal liquefaction process |
| JPS5681390A (en) * | 1979-12-07 | 1981-07-03 | Chiyoda Chem Eng & Constr Co Ltd | Multistage hydrogenation treatment of coal |
| US4400263A (en) * | 1981-02-09 | 1983-08-23 | Hri, Inc. | H-Coal process and plant design |
| CA1199293A (en) * | 1982-06-17 | 1986-01-14 | Chevron Research And Technology Company | Two-stage hydroprocessing of heavy oils with recycle of residua |
-
1985
- 1985-01-12 DE DE8585100277T patent/DE3572001D1/en not_active Expired
- 1985-01-12 EP EP85100277A patent/EP0151399B1/en not_active Expired
- 1985-01-16 AU AU37720/85A patent/AU582133B2/en not_active Ceased
- 1985-01-16 JP JP60004178A patent/JPS60161483A/en active Pending
- 1985-01-17 PL PL1985251583A patent/PL141658B1/en unknown
- 1985-01-18 ZA ZA85428A patent/ZA85428B/en unknown
- 1985-01-18 CA CA000472170A patent/CA1239366A/en not_active Expired
- 1985-01-18 DD DD85272651A patent/DD236340A5/en unknown
- 1985-01-18 SU SU853837677A patent/SU1473714A3/en active
- 1985-02-08 BR BR8500578A patent/BR8500578A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU582133B2 (en) | 1989-03-16 |
| EP0151399A2 (en) | 1985-08-14 |
| SU1473714A3 (en) | 1989-04-15 |
| BR8500578A (en) | 1985-09-24 |
| PL141658B1 (en) | 1987-08-31 |
| ZA85428B (en) | 1986-04-30 |
| DD236340A5 (en) | 1986-06-04 |
| EP0151399A3 (en) | 1987-05-13 |
| AU3772085A (en) | 1985-07-25 |
| CA1239366A (en) | 1988-07-19 |
| PL251583A1 (en) | 1985-11-05 |
| JPS60161483A (en) | 1985-08-23 |
| DE3572001D1 (en) | 1989-09-07 |
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