GB2032408A - Creación de Inventos y Patentes con Inteligencia Artificial

GB2032408A – Recovery of gallium
– Google Patents

GB2032408A – Recovery of gallium
– Google Patents
Recovery of gallium

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Publication number
GB2032408A

GB2032408A
GB7934114A
GB7934114A
GB2032408A
GB 2032408 A
GB2032408 A
GB 2032408A
GB 7934114 A
GB7934114 A
GB 7934114A
GB 7934114 A
GB7934114 A
GB 7934114A
GB 2032408 A
GB2032408 A
GB 2032408A
Authority
GB
United Kingdom
Prior art keywords
gallium
solution
chloride
organic phase
ferric
Prior art date
1978-10-03
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.)

Granted

Application number
GB7934114A
Other versions

GB2032408B
(en

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Anaconda Co

Original Assignee
Anaconda Co
Priority date (The priority date 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 date listed.)
1978-10-03
Filing date
1979-10-02
Publication date
1980-05-08

1979-10-02
Application filed by Anaconda Co
filed
Critical
Anaconda Co

1980-05-08
Publication of GB2032408A
publication
Critical
patent/GB2032408A/en

1982-09-08
Application granted
granted
Critical

1982-09-08
Publication of GB2032408B
publication
Critical
patent/GB2032408B/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS

C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS

C22B58/00—Obtaining gallium or indium

C—CHEMISTRY; METALLURGY

C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS

C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS

C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes

C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching

C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds

C22B3/28—Amines

C22B3/282—Aliphatic amines

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P10/00—Technologies related to metal processing

Y02P10/20—Recycling

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S423/00—Chemistry of inorganic compounds

Y10S423/09—Reaction techniques

Y10S423/14—Ion exchange; chelation or liquid/liquid ion extraction

Description

1
GB 2 032 408 A 1
SPECIFICATION
Process for Use in the Recovery of Gallium
The present invention relates to a process for recovering gallium by selectively extracting 5 gallium from a hydrochloric acid leach solution of calcined clay containing aluminium, ferric and gallium chlorides.
Because of its low melting point and lack of toxicity gallium has been used in many diverse 10 applications. For example, gallium has been used instead of mercury in dental alloys, and has been used as a heat transfer medium. Also gallium has found limited use as a thermometric fluid for high temperature thermometers. More recently high 1 5 purity gallium has been alloyed with phosphorus or arsenic to form gallium phosphide or gallium arsenide which have found extensive use in the electronics industry.
No ore is known presently which contains any 20 appreciable concentration of gallium. The element is very widely distributed, particularly in aluminous materials where the gallium content is roughly proportional to the aluminium content. Gallium is also found in small concentrations 25 most zinc blends, and in germanite where it appears with the mixed sulphides.
Because of the variety of minerals in which gallium occurs, may processes have been devoloped to concentrate the element. The 30 concentration of gallium form germanite, the richest natural source of gallium, involves the conversion of the germanium and gallium to the chloride, and the more volatile germanium tetrachloride is separated by distillation while the 35 gallium is recovered by electrolysis.
In one of the prior art industrial processes for the recovery of gallium, carbon dioxide gas is blown through a filtrate of sodium aluminate solution obtained as a by-product in the course of 40 the manufacture of alumina to precipitate crude hydroxide of gallium. Alternatively, the filtrate is electrolyzed by using a mercury cathode to produce a gallium amalgam.
In another process for the recovery of gallium, 45 a residue from an electrolytic process or pyrometallurgical process is utilized. The residue is subjected to an acid extraction to prepare a gallium-containing solution, which is then neutralized to precipitate a crude hydroxide of 50 gallium.
The gallium hydroxide is dissolved in a hydrochloric acid solution and thereafter subjected to a liquid-liquid extraction with isopropyl ether to recover the gallium. 55 Gallium may also be recovered from the alumina purification processes of the aluminium industry. In the Bayer process, aluminium trihydrate is crystallized from a solution of a sodium aluminate by cooling and seeding. In this 60 process, gallium accumulates in the liquor. After concentration of the liquor and an adjustment of the pH, the gallium may be separated by electrolysis. On the other hand, United States Patent No. 2,582,376 discloses a process for
65 removing gallium from alkaline solutions containing dissolved alkali metal aluminate and gallium by adding a soluble calcium compound which results in the precipitation of calcium aluminate while leaving the gallium in the 70 solution. The gallium can then be precipitated and the precipitate redissolved in a solvent to provide a concentrated solution of gallium. Metallic gallium can then be recovered by electrolysis.
The prior art techniques mentioned above have 75 many disadvantages. For example, the process which utilizes blowing of carbon dioxide or neutralization to prepare hydroxide of gallium is complicated in its operations because filtration of the solution is very difficult. In addition, where a 80 starting solution contains many kinds of elements, such as iron, copper and aluminium too many hydroxides are involved and the yield and selectivity of a desired metal becomes poor.
The electrolytic process utilizing a mercury 85 cathode has disadvantages because current efficiency is very low. The process employing isopropyl ether as an extraction solvent can separate gallium in high selectivity, but it requires a highly concentrated hydrochloric acid solution, 90 which has a high solubility for isopropyl ether, so that life of the solvent is relatively short.
It has now been found that gallium may be recovered from a leach solution rich in chloride values with the use of multiple selective 95 extraction steps which separate gallium from chloride solutions of aluminium and iron.
The present invention provides a process for use in the recovery of gallium from calcined clay which comprises leaching calcined clay with a 100 hydrochloric acid solution, separating the resulting hydrochloric acid solution from residuals, treating the separated hydrochloric acid solution containing aluminium chloride, ferric chloride, and gallium chloride in an amine ion 105 extraction unit so as to separately recover aluminium chloride raffinate solution and an organic phase containing ferric chloride and gallium chloride, stripping the organic phase to yield a first strip extract solution containing ferric 110 chloride and gallium chloride, reducing the ferric chloride in said first strip extract solution to ferrous chloride and incorporating sufficient hydrochloric acid in the reduced solution to convert the gallium therein to GaCI^ ions, then 115 treating the solution in a second amine ion extraction unit so as to separately recover a raffinate solution containing ferrous chloride and a second organic phase containing gallium, stripping the second organic phase to yield a 120 second strip extract solution containing gallium, and recovering the gallium-containing solution.
Thus the process of the present invention avoids at least some of the disadvantages of the previously known processes in a simple and 125 efficient manner.
The invention is described more fully in the following more detailed description of preferred embodiments illustrated with reference to the accompanying drawing in which
2
GB 2 032 408 A 2
Figure 1 is a flow diagram illustrating recovery of gallium in accordance with the present invention.
In the processing of alumina, calcined clay is 5 leached with hydrochloric acid. Undissolved solid residue is separated and discarded. The leach solution containing aluminium chloride, ferric chloride and gallium chloride is passed to an ion exchange treatment. Although concentrated 10 hydrochloric acid may be employed to leach the calcined clay, it is found that as a practical matter less concentrated solutions of hydrochloric acid may be satisfactorily employed. Thus, for example, a 20% (6 molar) hydrochloride acid 15 solution may be used.
The hydrochloric acid leach solution is next treated with an amine ion exchanger which extracts the ferric and gallium values from the aluminium chloride in solution. Methods are well-20 known in the art for making this separation, such as that disclosed in United States Patent No. 3,082,062. This patent describes amine extraction using any of a large number of commercially available materials such as primary, 25 secondary and tertiary amines, with the secondary and tertiary amine being preferred because of their higher affinity for the chloro-ferrate complex. Useful amines which may be used include, by way of example, triisooctylamine, 30 dodecenyl t-dodecyl amine, n-dodecyl t-
dodecylamine, and the like. One commercially available triisooctylamine found to be effective for use herein is that sold by General Mills under the tradename Alamine 336. The amine is dissolved 35 in any suitable water-immiscible organic solvent such as kerosene (the preferred solvent) benzene, toluene, or the like, and the solution may with advantage also contain an alcohol such as decyl alcohol, tridecyl alcohol, or a mixture of lauryl and 40 myristyl alcohol.
The amine-containing organic solution is intimately contacted with the aqueous leach solution, and then these immiscible solutions are allowed to separate. After such mixing and 45 separating, the organic phase, which contains the iron and gallium, is separated from the aqueous phase (the raffinate), which contains the aluminium chloride. The latter is withdrawn from the process and may be treated by any desired 50 procedure, such as by the process of U.S. Patent 3,406,010, for recovery of its aluminium content and its chloride values.
The separated organic phase is then intimately contacted with water or weak acid to strip it of 55 the iron and gallium it contains. The resulting aqueous strip extract solution, containing ferric and gallium chloride, is passed to further treatment, and the stripped organic phase is recycled to treat a further quantity of leach 60 solution.
The first strip extract solution, containing iron (ferric) and gallium chlorides is processed by any one of the number of reactions which effect reduction of ferric (Fe+++) ions to ferrous (Fe++) 65 ions. For example, reduction may be accomplished by contacting the solution, preferably at an acidic pH, with iron or metallic aluminium, or alternatively by introducing hydrogen gas into the solution.
70 Sufficient hydrochloric acid then is added to the solution to insure that the gallium ions are converted to gallium tetrachloride (GaCI^) ions. The iron in the reduced ferrous condition does not form a stable chloroferrate complex. 75 The solution, now containing iron only in the ferrous form, is again subjected to amine ion exchange, using the same reagents and techniques described above. However, with the iron now in the uncomplexed ferrous form, only 80 the gallium is extracted by the amine reagent, and the ferrous iron remains in the aqueous raffinate phase after separation of the organic phase. This aqueous phase (raffinate) is withdrawn and may be treated by any desired procedure for recovery 85 of hydrochloric acid from the iron chloride.
The organic phase, after separation from the aqueous phase, may be stripped either with water or with weak (e.g. 0.5 molar) hydrochloric acid solution to produce a second strip extract solution 90 which contains the gallium substantially free of iron. This gallium-bearing solution, free of major contaminants and with sufficiently high gallium concentration for treatment by known gallium recovery methods, is the end product of the 95 process of the invention. The stripped organic phase is recycled to the extraction unit for continuous processing of additional iron-gallium chloride solution.
The following example illustrates practice of 100 the present invention in greater detail.
EXAMPLE
Calcined clay is leached continuously with 20% by weight solution of hydrochloric acid. The leach solution is separated from the undissolved 105 residue. Analysis of the leach solution shows aluminium, ferric, and gallium ions present. This solution is next passed to an amine ion exchange extractor and contacted countercurrently with a kerosene solution containing triisooctylamine 110 (commercial Alamine 336). A 0.10 molar solution of amine is used, and decyl alcohol is also present in an amount of 6% by weight of the kerosene. The extraction is continuously effected and the organic phase is passed to a stripper for 115 countercurrent stripping with water to produce a first strip extract solution containing ferric chloride and gallium chloride. The organic phase, stripped of its metal values, is then returned to the extractor for continuous processing. The aqueous 120 phase is removed from the extractor and is found to contain aluminium chloride values in solution, and is suitable for further processing by the method disclosed in United States Patent No. 3,406,010
125 The ferric iron (Fe+++) in the aqueous first strip extract solution is reduced by passing hydrogen into the solution, thereby converting the ferric ions to ferrous ions. The reduced solution is then acidified with hydrochloric acid sufficiently to
3
GB 2 032 408 A 3
convert substantially all the gallium in solution to GaCI^ ions. Then the reduced solution is again selectively extracted using triisooctylamine, kerosene and alcohol solution as previously 5 indicated.
In this second countercurrent extraction operation, the organic phase, after separation from the aqueous phase, is stripped using a weak (3 g/l) hydrochloric acid solution to recover a 10 second strip extract solution containing gallium. The organic phase is re-cycled back to the extraction unit for continuous processing. The separated aqueous phase contains ferrous chloride in a hydrochloride acid solution and is 15 suitable for treatment to recover hydrochloric acid. The recovered second strip extract solution contains gallium in sufficient concentration so that it may economically be processed to recover gallium metal values by process techniques well 20 known in the art.
From the foregoing it will be readily apparent to those skilled in the art that various modifications and changes may be effected herein without departing from practice of the 1 25 present invention.

Claims (6)

Claims

1. A process for use in the recovery of gallium from calcined clay which comprises leaching calcined clay with a hydrochloric acid solution, 30 separating the resulting hydrochloric acid solution from residuals, treating the separated hydrochloric acid solution containing aluminium chloride, ferric chloride, and gallium chloride in an amine ion extraction unit so as to separately
35 recover aluminium chloride raffinate solution and an organic phase containing ferric chloride and gallium chloride, stripping the organic phase to yield a first strip extract solution containing ferric chloride and gallium chloride, reducing the ferric 40 chloride in said first strip extract solution to ferrous chloride and incorporating sufficient hydrochloride acid in the reduced solution to convert the gallium therein to GaCI^ ions, then treating the solution in a second amine ion 45 extraction unit so as to separately recover a raffinate solution containing ferrous chloride and a second organic phase containing gallium, stripping the second organic phase to yield a second strip extract solution containing gallium, 50 and recovering the gallium-containing solution.

2. A process as claimed in Claim 1 wherein is used as an extraction medium in each amine ion extraction unit, triisooctylamine dissolved in kerosene.
55

3. A process as claimed in Claim 1 or Claim 2 wherein the ferric chloride is reduced by metallic iron.

4. A process as claimed in Claim 1 or Claim 2 wherein the ferric chloride is reduced by hydrogen
60 gas.

5. A process for use in the recovery of gallium from calcined clay according to Claim 1, substantially as described hereinbefore with particular reference to the Example and/or Figure
65 1.

6. A process according to any one of the claims which includes the further step of recovering gallium metal from said gallium-containing solution.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.

GB7934114A
1978-10-03
1979-10-02
Recovery of gallium

Expired

GB2032408B
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

US05/948,296

US4193968A
(en)

1978-10-03
1978-10-03
Process for recovering gallium

Publications (2)

Publication Number
Publication Date

GB2032408A
true

GB2032408A
(en)

1980-05-08

GB2032408B

GB2032408B
(en)

1982-09-08

Family
ID=25487614
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

GB7934114A
Expired

GB2032408B
(en)

1978-10-03
1979-10-02
Recovery of gallium

Country Status (5)

Country
Link

US
(1)

US4193968A
(en)

CA
(1)

CA1132802A
(en)

DE
(1)

DE2939911A1
(en)

FR
(1)

FR2438096A1
(en)

GB
(1)

GB2032408B
(en)

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Title

US4298380A
(en)

1980-02-14
1981-11-03
Bochkarev Ellin P
Process for purifying low-melting metals from impurities

FR2495600A1
(en)

1980-12-05
1982-06-11
Rhone Poulenc Ind

PROCESS FOR PURIFYING A GALLIUM SOLUTION BY LIQUID-LIQUID EXTRACTION USING QUATERNARY AMMONIUM SALTS

EP0053971B1
(en)

1980-12-05
1984-08-15
Rhone-Poulenc Specialites Chimiques
Process for purifying a gallium solution by liquid-liquid extraction

FR2495601A1
(en)

1980-12-05
1982-06-11
Rhone Poulenc Ind

PROCESS FOR PURIFYING GALLIUM SOLUTIONS

FR2495599A1
(en)

1980-12-05
1982-06-11
Rhone Poulenc Ind

PROCESS FOR PURIFYING A GALLIUM SOLUTION BY LIQUID-LIQUID EXTRACTION USING ALCOHOLS

US4442073A
(en)

1982-05-21
1984-04-10
University Patents, Inc.
Separation and recovery of metal alloys from superalloy scrap

JPS59186686A
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1983-04-07
1984-10-23
Dowa Mining Co Ltd
Process for selectively separating and concentrating gallium or indium from liquid containing many kinds of metallic ion at high concentration

US5030427A
(en)

1986-12-04
1991-07-09
Monsanto Company
Gallium purification

EP0285055B1
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1987-04-03
1992-06-24
Sumitomo Chemical Company, Limited
Process for recovery of gallium by chelate resin

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1989-08-01
1990-10-23
Henkel Corporation
Process of extraction of gallium from aqueous solutions thereof

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2002-07-16
2005-10-04
Inco Limited
Method for removing impurities from solvent extraction solutions

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2005-09-02
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Sachem, Inc.
Removal of metal ions from onium hydroxides and onium salt solutions

CN101842504B
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2007-05-21
2012-11-14
奥贝特铝业有限公司
Processes for extracting aluminum from aluminous ores

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2011-03-18
2012-09-27
Orbite Aluminae Inc.
Processes for recovering rare earth elements from aluminum-bearing materials

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2011-05-04
2017-03-15
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Processes for recovering rare earth elements from various ores

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2011-06-03
2014-11-25
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Methods for preparing hematite

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2011-09-16
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Alumina and various other product preparation processes

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2012-01-10
2017-07-04
Orbite Aluminae Inc

processes for treating red mud

CN104603303A
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2012-03-19
2015-05-06
奥佰特氧化铝有限公司
Processes for recovering rare earth elements and rare metals

AU2013203808B2
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2012-03-29
2016-07-28
Orbite Aluminae Inc.
Processes for treating fly ashes

MY175471A
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2012-07-12
2020-06-29
Orbite Tech Inc
Processes for preparing titanium oxide and various other products

WO2014047728A1
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2012-09-26
2014-04-03
Orbite Aluminae Inc.
Processes for preparing alumina and magnesium chloride by hc1 leaching of various materials

CA2891427C
(en)

2012-11-14
2016-09-20
Orbite Aluminae Inc.
Methods for purifying aluminium ions

CN103805794B
(en)

2013-12-30
2015-04-08
中国神华能源股份有限公司
Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash

CN109234541B
(en)

2018-11-16
2021-04-13
攀枝花学院
Method for extracting gallium from vanadium extraction tailings by alkaline roasting

CN111961867B
(en)

2020-09-15
2022-05-20
神华准格尔能源有限责任公司
Method for extracting gallium from iron-removing waste liquid generated in process of preparing alumina from fly ash

EP4279619A1
(en)

2022-05-19
2023-11-22
Helmholtz-Zentrum Dresden – Rossendorf e.V.
Method for the separation of indium, germanium, and/or gallium from iron

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1958-11-18
1963-03-19
Rohm & Haas
Removal of ferric chloride from ironaluminum chloride solutions

FR1297623A
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Alumina purification process

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Process for purifying alumina and recovering a gallium concentrate

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Process for the recovery of gallium

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Gallium recovery process

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Process for recovering pure aqueous solution of ferric chloride and aqueous solution of metal chlorides free of ferric chloride from ferrous metal material

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1974-07-12
1976-02-06
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Gallium prodn from sodium aluminate solns – using liq.-liq. extn with organic phase contg a substd hydroxy-quinoline

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1974-10-18
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Solvent extraction of In and/or Ga

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METHOD FOR PRODUCING PURE ALUMINUM OXIDE

1978

1978-10-03
US
US05/948,296
patent/US4193968A/en
not_active
Expired – Lifetime

1979

1979-09-24
CA
CA336,193A
patent/CA1132802A/en
not_active
Expired

1979-10-02
DE
DE19792939911
patent/DE2939911A1/en
not_active
Withdrawn

1979-10-02
FR
FR7924524A
patent/FR2438096A1/en
not_active
Withdrawn

1979-10-02
GB
GB7934114A
patent/GB2032408B/en
not_active
Expired

Also Published As

Publication number
Publication date

GB2032408B
(en)

1982-09-08

CA1132802A
(en)

1982-10-05

US4193968A
(en)

1980-03-18

DE2939911A1
(en)

1980-04-24

FR2438096A1
(en)

1980-04-30

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