BE815951A - Zinc extraction from dross - by cation exchange in an organic phase - Google Patents
Zinc extraction from dross - by cation exchange in an organic phaseInfo
- Publication number
- BE815951A BE815951A BE145106A BE145106A BE815951A BE 815951 A BE815951 A BE 815951A BE 145106 A BE145106 A BE 145106A BE 145106 A BE145106 A BE 145106A BE 815951 A BE815951 A BE 815951A
- Authority
- BE
- Belgium
- Prior art keywords
- zinc
- organic phase
- dross
- waste
- emi
- Prior art date
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 40
- 239000011701 zinc Substances 0.000 title claims abstract description 40
- 239000012074 organic phase Substances 0.000 title claims abstract description 20
- 238000005341 cation exchange Methods 0.000 title 1
- 238000000605 extraction Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 3
- 239000011707 mineral Substances 0.000 claims abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 239000002699 waste material Substances 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 239000010814 metallic waste Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 copper and nickel Chemical class 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1683—Leaching with organo-metallic compounds
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Method of extracting zinc and other metals from zinc dross contg. free zinc as well as zinc in the form of chloride, other halides, nitrate, phosphate etc., comprises leaching with an org. liq. contg. a cation exchanger, e.g. a carboxylic acid or an alkylphosphoric acid to form an organometallic complex soluble in the organic phase while the halogens and other impurities are washed away with water or alkaline soln. The org. phase is then treated with a mineral acid (H2SO4) to remove the zinc and other metals in aq. soln., so that the zinc can be isolated by known methods.
Description
Procédé d'isolement du zinc et d'autres métaux de déchets contena
des anions gênants .
Un fondant contenant du chlore est utilisé pour l'appli-
<EMI ID=1.1>
protection contre la corrosion. Ces procédés conduisent à des
déchets contenant du chlore et se présentant sous la forme de
crasses de zinc séparées par écumage.
Ces déchets contiennent d'habitude aussi une certaine
quantité de zinc métallique. On connaît toutefois un procédé qui
permet de séparer la fraction métallique des crasses de zinc jusqu'au degré utile pour la poursuite du traitement des crasses de
zinc.
Ces déchets sont d'habitude tellement contaminés par le chlore qu'il est impossible, par exemple, de les amener directe-
<EMI ID=2.1>
tion dans l'acide sulfurique. Par conséquent, les déchets contenant du chlore sont .utilisés principalement par vole thermique suivant les procédés déjà connus.
Le brevet norvégien n[deg.] 126.852 décrit un procédé pour traiter des déchets de zinc contenant du chlore afin de l�s utiliser comme matière première dans la production du zinc au départ d'une solution de sulfate de zinc. Le procédé de ce brevet est basé sur la dissolution du zinc par lixiviation des déchets dans l'acide sulfurique et sur la purification ultérieure qui sépare le chlore de la solution résultante de sulfate de zinc contenant du chlore au cours d'une extraction liquide-liquide.
La présente invention a pour objet un procédé pour isoler le zinc et d'autres métaux des crasses de zinc et d'autres déchets métallifères contenant du chlore et/ou d'autres halogènes et d'autres anions formant des sels métalliques gênants, par exemple des nitrates et phosphates, qui est caractérisé en ce qu'on soumet les déchets métallifères à une lixiviation au moyen d'une phase organique liquide contenant un échangeur de cations, par exemple un
<EMI ID=3.1>
ou un acide alkylphosphorique tel que l'acide di(2-étbylhexyl)-, phosphorique.pour la formation d'un complexe organique métallique qui est soluble dans la phase organique,tandis'que les halogènes et autres impuretés de la phase organique sont éliminés par lavage de cette phase organique au moyen d'eau ou au moyen d'une solution aqueuse alcaline, après quoi la phase organique est mise en contact avec un acide minéral de sorte que le zinc et les autres. métaux sont extraits dans la phase aqueuse sous la forme de sels métalliques purs on d'une solution de sels métalliques purs dont le zinc peut être isolé suivant les procédés connus.
L'avantage du procédé de l'invention sur les procédés
<EMI ID=4.1>
L'invention a pour objet un procédé basé sur le traitement. direct des déchets de zinc contenant du chlore au moyen d'une phase organique contenant un échangeur de cations liquide du
type d'usage général pour la séparation et l'isolement des ions métalliques des solutions aqueuses de sels métalliques par extraction liquide-liquide. Des exemples de ces échangeurs de cations sont certains acides gras acides naphténiques et autres acides
<EMI ID=5.1>
la société Shell, outre certains acides alkylphosphoriques,comme l'acide di(2-éthylhexyl)phosphorique. Les échangeurs de cations organiques sont de préférence présentés sous la forme acide et dissous dans un solvant organique approprié qui est peu soluble dans la phase aqueuse.
L'oxyde de zinc des déchets de zinc contenant du-chlore réagit directement avec l'acide organique ou échangeur de cations pour donner un complexe organique de zinc qui est soluble dans
la phase organique.
Au cours de cette réaction, le chlore contenu dans les :déchets peut intervenir dans la formation du complexe, par exemple sous forme d'acide chlorhydrique ou d'autres composés chlorés,qui se dissolvent dès lors dans la phase organique. Lors du con-
<EMI ID=6.1>
tuellement en présence d'un alcali, tel que l'hydroxyde de sodium, les composés du chlore éventuellement contenus dans la phase organique la quittent par lavage. Après le lavage au moyen d'une phas aqueuse neutre ou alcaline, la phase organique est exempte de chlor et ne contient que le complexe organique de métal.
Au cours d'un contact ultérieur de la phase organique avec de l'acide sulfurique, le métal est séparé et entraîné dans la phase aqueuse pour donner une solution de sulfate de zinc qui se prête à la production hydrométallurgique/électrolytique du zinc de la manière classique. Il est possible aussi de précipite:
le sulfate de zinc directement de la solution si l'opération appa rait favorable.
L'échangeur de cations organique, après le contact avec l'acide sulfurique, se retrouve sous la forme acide et est renvoyé à la réaction avec les déchets de zinc contenant du chlore.
L'invention n'est pas applicable uniquement aux déchets contenant du zinc et se prête de manière générale à l'isolement de métaux, tels que le cuivre et le nickel, de déchets métallifères au moyen de la réaction décrite entre les composés métallique et l'agent de lixiviation organique liquide, par exemple l'un des échangeurs de cations décrits. L'avantage du procédé sur la dissolution directe des déchets métalliques dans les acides inorga- <EMI ID=7.1> aqueuse pour éviter la présence d'anions gênants, comme les ions chlorure, bromure, fluorure etc. dans la solution résultante de sels métalliques.
<EMI ID=8.1>
On souset des déchets de zinc de qualité industrielle
(crasses de zinc) collecté lors de la fusion du métal pour la <EMI ID=9.1>
poursuit. les expériences sur le produit de criblage.
On soumet les déchets de zinc d'abord à un examen par
<EMI ID=10.1>
sente l'aspect du sable. Les déchets de zinc contiennent 3% de cet insoluble.
La poursuite de l'analyse des déchets de zinc indique
<EMI ID=11.1>
Le criblage mécanique préliminaire laisse subsister du zinc métallique très finement divisé dans les crasses de zinc.
Ce zinc métallique forme environ 30% de ces crasses. Le reste du zinc (à peu près 50%) est formé surtout par des oxydes, chlorures et oxychlorures.
On met 100 g de; déchets de zinc en contact avec 1 litre
<EMI ID=12.1>
on sépare le solide de la phase liquide. On dissout ainsi 66 g de crasses de zinc dans la phase organique. A l'analyse, la pha organique se révèle contenir,par litre, 52,7 g de zinc et 0,61 g de chlore.
On met la phase organique alors en contact avec un égal volume d'eau et on agite le tout pendant 10 minutes à 20[deg.]C. Cet unique lavage fait baisser la teneur en chlorure de la phase org;
nique de 0,61 à 0,01 g/litre.
<EMI ID=13.1>
forme de sulfate de zinc dans la phase aqueuse acide.
A process for isolating zinc and other metals from waste contena
troublesome anions.
A flux containing chlorine is used for the application.
<EMI ID = 1.1>
corrosion protection. These processes lead to
wastes containing chlorine and in the form of
zinc dross separated by skimming.
These wastes usually also contain some
amount of metallic zinc. However, a process is known which
allows the metal fraction to be separated from the zinc dross to the extent useful for the further treatment of the zinc dross
zinc.
These wastes are usually so contaminated with chlorine that it is impossible, for example, to bring them directly
<EMI ID = 2.1>
tion in sulfuric acid. Therefore, waste containing chlorine is used mainly by thermal stealing according to already known methods.
Norwegian Patent No. 126,852 describes a process for treating waste zinc containing chlorine for use as a raw material in the production of zinc from a zinc sulphate solution. The process of this patent is based on the dissolution of zinc by leaching the waste in sulfuric acid and on the subsequent purification which separates the chlorine from the resulting solution of zinc sulfate containing chlorine during liquid-liquid extraction. .
The present invention relates to a process for isolating zinc and other metals from zinc dross and other metal-bearing wastes containing chlorine and / or other halogens and other anions forming troublesome metal salts, for example nitrates and phosphates, which is characterized in that the metalliferous waste is subjected to leaching by means of a liquid organic phase containing a cation exchanger, for example a
<EMI ID = 3.1>
or an alkylphosphoric acid such as di (2-ethylhexyl) - phosphoric acid for the formation of an organic metal complex which is soluble in the organic phase, while halogens and other impurities in the organic phase are removed. by washing this organic phase with water or with an aqueous alkaline solution, after which the organic phase is contacted with a mineral acid so that zinc and the like. metals are extracted in the aqueous phase in the form of pure metal salts or a solution of pure metal salts from which the zinc can be isolated according to known methods.
The advantage of the method of the invention over the methods
<EMI ID = 4.1>
The object of the invention is a method based on the treatment. direct from waste zinc containing chlorine by means of an organic phase containing a liquid cation exchanger of the
General purpose type for the separation and isolation of metal ions from aqueous solutions of metal salts by liquid-liquid extraction. Examples of these cation exchangers are certain fatty acids naphthenic acids and other acids
<EMI ID = 5.1>
the company Shell, in addition to certain alkylphosphoric acids, such as di (2-ethylhexyl) phosphoric acid. The organic cation exchangers are preferably presented in the acid form and dissolved in a suitable organic solvent which is sparingly soluble in the aqueous phase.
Zinc oxide from chlorine-containing zinc waste reacts directly with the organic acid or cation exchanger to give an organic zinc complex which is soluble in
the organic phase.
During this reaction, the chlorine contained in the: waste can intervene in the formation of the complex, for example in the form of hydrochloric acid or other chlorinated compounds, which therefore dissolve in the organic phase. When con-
<EMI ID = 6.1>
ually in the presence of an alkali, such as sodium hydroxide, the chlorine compounds possibly contained in the organic phase leave it by washing. After washing by means of a neutral or alkaline aqueous phase, the organic phase is free from chlorine and contains only the organic metal complex.
During a subsequent contact of the organic phase with sulfuric acid, the metal is separated and entrained in the aqueous phase to give a solution of zinc sulfate which lends itself to the hydrometallurgical / electrolytic production of zinc in the manner classic. It is also possible to precipitate:
zinc sulphate directly from the solution if the operation appears favorable.
The organic cation exchanger, after contact with sulfuric acid, returns to the acid form and is returned to the reaction with the waste zinc containing chlorine.
The invention is not applicable only to zinc-containing wastes and generally lends itself to the isolation of metals, such as copper and nickel, from metal-bearing wastes by means of the reaction described between the metallic compounds and the metal. liquid organic leaching agent, for example one of the cation exchangers described. The advantage of the process on the direct dissolution of metal waste in inorganic acids - <EMI ID = 7.1> aqueous to avoid the presence of troublesome anions, such as chloride, bromide, fluoride ions etc. in the resulting solution of metal salts.
<EMI ID = 8.1>
We supply industrial grade zinc waste
(zinc dross) collected during metal melting for <EMI ID = 9.1>
continues. the experiments on the screening product.
The zinc waste is first subjected to an examination by
<EMI ID = 10.1>
feel the appearance of sand. Zinc waste contains 3% of this insoluble matter.
Continued analysis of zinc waste indicates
<EMI ID = 11.1>
The preliminary mechanical screening leaves very finely divided metallic zinc in the zinc dross.
This metallic zinc forms about 30% of this dross. The remainder of the zinc (approximately 50%) is formed mainly by oxides, chlorides and oxychlorides.
100 g of; zinc waste in contact with 1 liter
<EMI ID = 12.1>
the solid is separated from the liquid phase. 66 g of zinc dross are thus dissolved in the organic phase. On analysis, the organic pha is found to contain, per liter, 52.7 g of zinc and 0.61 g of chlorine.
The organic phase is then brought into contact with an equal volume of water and the whole is stirred for 10 minutes at 20 [deg.] C. This single washing lowers the chloride content of the org phase;
from 0.61 to 0.01 g / liter.
<EMI ID = 13.1>
form of zinc sulfate in the acidic aqueous phase.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE145106A BE815951A (en) | 1974-06-05 | 1974-06-05 | Zinc extraction from dross - by cation exchange in an organic phase |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE815951 | 1974-06-05 | ||
| BE145106A BE815951A (en) | 1974-06-05 | 1974-06-05 | Zinc extraction from dross - by cation exchange in an organic phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE815951A true BE815951A (en) | 1974-09-30 |
Family
ID=25647923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE145106A BE815951A (en) | 1974-06-05 | 1974-06-05 | Zinc extraction from dross - by cation exchange in an organic phase |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE815951A (en) |
-
1974
- 1974-06-05 BE BE145106A patent/BE815951A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RE | Patent lapsed |
Owner name: THORSEN G. Effective date: 19870630 |