EP0100744B1 - Procédé d'extraction de l'uranium des acides phosphoriques par les acides alkylpyrophosphoriques - Google Patents
Procédé d'extraction de l'uranium des acides phosphoriques par les acides alkylpyrophosphoriques Download PDFInfo
- Publication number
- EP0100744B1 EP0100744B1 EP83420127A EP83420127A EP0100744B1 EP 0100744 B1 EP0100744 B1 EP 0100744B1 EP 83420127 A EP83420127 A EP 83420127A EP 83420127 A EP83420127 A EP 83420127A EP 0100744 B1 EP0100744 B1 EP 0100744B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- uranium
- process according
- extraction
- extraction process
- acid
- 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
- 229910052770 Uranium Inorganic materials 0.000 title claims description 68
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims description 67
- 235000011007 phosphoric acid Nutrition 0.000 title claims description 37
- 239000002253 acid Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 17
- 150000003016 phosphoric acids Chemical class 0.000 title claims description 7
- 150000007513 acids Chemical class 0.000 title description 12
- 238000000605 extraction Methods 0.000 claims description 73
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GQEUNBGUKAIROG-UHFFFAOYSA-N octyl phosphono hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(O)=O GQEUNBGUKAIROG-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- QFYOFKLVLQRRNE-UHFFFAOYSA-N ethyl hexyl phosphono phosphate Chemical compound CCCCCCOP(=O)(OCC)OP(O)(O)=O QFYOFKLVLQRRNE-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 150000001224 Uranium Chemical class 0.000 description 1
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- -1 pyrophosphoric acid diester Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940093635 tributyl phosphate Drugs 0.000 description 1
- 229910000439 uranium oxide Inorganic materials 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
Definitions
- the invention relates to an improved process for extracting by means of an agent, consisting of alkylpyrophosphoric acids, uranium present in phosphoric acid solutions, process which makes it possible to conserve over time the extraction power of said agent in limiting its degradation.
- alkylpyrophosphoric acids as uranium extraction agent, used in a form dissolved in an organic diluent, such as that petroleum cut, kerosene, etc., the most commonly used extraction agent being alkylpyrophosphoric acid obtained by reaction of P 2 0 5 with octanol 2.
- recovering the uranium contained in phosphoric acid at a rate of 90 to 200 milligrams of uranium oxide U 3 0 8 per liter consists first of all in contacting the solution of phosphoric acid with the extraction agent most commonly constituted by octylpyrophosphoric acid in solution in kerosene, the extraction of uranium being carried out against the current in a group of mixing and sedimentation tanks cascade.
- the organic phase containing in solution the octylpyrophosphoric acid loaded with uranium, separated from the phosphoric acid solution, is treated by contact using hydrofluoric acid, giving fluoride d uranium (UF 4 ) and desuranic octylpyrophosphoric acid.
- alkylpyrophosphoric acids as uranium extraction agent, and in particular octylpyrophosphoric acid, lies in the fact of their strong extracting power, even when they are used in organic solution very diluted, allowing them to extract, with a very good yield, the uranium present, even in very small quantity, in solutions of phosphoric acids.
- 2423545 describes a process for extracting uranium from phosphoric acid solutions, the extracting agent of which is a pyrophosphoric acid diester such as dicaproyl pyrophosphate or dioctyl pyrophosphate, a process according to which the hydrolysis of said extracting agent would be greatly reduced, while the re-extraction of the uranium present in the organic phase is carried out by means of an alkaline solution and no longer by l hydrofluoric acid.
- the extracting agent of which is a pyrophosphoric acid diester such as dicaproyl pyrophosphate or dioctyl pyrophosphate
- the licensee thanks to her research, found and developed an improved process for extracting uranium contained in solutions of phosphoric acids, means of an extraction agent chosen from the group of alkylpyrophosphoric acids which makes it possible to avoid their degradation by acid hydrolysis, while retaining their extracting power.
- the process according to the invention for the extraction of uranium contained in phosphoric acid solutions by means of an extraction agent consisting of an alkylpyrophosphoric acid, which consists in bringing the mineral phase of phosphoric acid and an organic phase containing the extraction agent by creating an emulsion is characterized in that, in an extraction unit comprising n stages in cascade with n> 1, for each extraction stage, the emulsion is produced during a first step by simultaneously subjecting the two phases for a time T, to an intense mechanical shearing action corresponding to a shear coefficient of at least 5000 s -1 in order to increase the contact surfaces between these two phases, then said emulsion during a second step is suddenly broken in a time T z , the total time required for the completion of the two steps being at most 20 minutes.
- the extraction unit has a number of stages n of between 2 and 20.
- this shear coefficient is chosen in the interval 5000 s -1 to 50,000 s -1 , but preferably in the interval 10,000 s -1 to 25,000 s -1 .
- the total time required to carry out the two stages according to the invention is preferably at most equal to 10 minutes for an extraction stage.
- the times T, and T of execution of the two stages can vary within wide limits, their ratio T, / T 2 being able to be chosen within the limits 1/100 to 5/1 and preferably within limits 1 / 25 to 2/1.
- the emulsion between the two organic and mineral phases is produced by any means known to those skilled in the art, making it possible to quickly and vigorously obtain the finest emulsion possible, in order to multiply the surfaces of contact and obtain a very high extraction yield.
- the rapid separation of the organic and mineral phases can be obtained by physical means using any known means allowing rapid rupture of said emulsion.
- the extracting agent, entrained by the desuranic phosphoric acid can be recovered by a physical separation of centrifugation for example and joined to the recycled extraction agent after re-extraction of the uranium .
- the uranium extracting agent is chosen from the well-known group of alkylpyrophosphoric acids, the alkyl radical of which is a carbon chain corresponding to the C 7 to C 13 alcohols obtained by oxo synthesis , such as for example octanol 2, ethylhexanol, cancanol.
- the preparation of alkylpyrophosphoric acid can be carried out in a known manner by adding P 2 O 5 to the abovementioned alcohol, used alone or as a mixture with a hydrocarbon.
- the temperature for preparing alkylpyrophosphoric acid is generally between 30 ° C and 80 ° C, but preferably between 30 ° C and 40 ° C.
- the uranium extracting agent is generally dissolved in an aliphatic and / or aromatic hydrocarbon, such as kerosene for example.
- the mixture thus formed constitutes the organic phase of extraction of the uranium, which contains from 5 to 100 g / l but preferably from 20 to 50 g / l of alkylpyrophosphoric acid.
- the phosphoric acid solutions resulting from the attack on phosphate ores generally contain from 30 to 200 milligrams of uranium per liter, this uranium being partly in the form U IV and for the other in the form U VI.
- the uranium VI is then reduced to uranium IV by the treatment of phosphoric acid solutions with iron, in the form of powder when the reduction treatment is carried out in a reactor or also in the form of scrap metal when the reduction treatment takes place in a column.
- the phosphoric acid solutions containing suspended solids are subjected to a separation operation, before being brought into contact with the extractant in solution in an aliphatic hydrocarbon. and / or aromatic.
- the two mineral and organic phases to be extracted and extracting are then brought into intimate contact in the form of a fine emulsion which is quickly broken in order to separate the organic phase loaded with uranium from the mineral phase with deuranied acid.
- the organic phase loaded with uranium is then treated with an aqueous hydrofluoric acid solution, this solution containing 10 to 20%, but preferably 14 to 18% by weight of free HF.
- the temperature at which the uranium is re-extracted by hydrofluoric acid is between 0 ° C and 60 ° C but preferably between 10 ° C and 30 ° C, temperature at which the degradation of the alkylpyrophosphoric acid remains low (less than 2%).
- the uranium then precipitates in the form of UF 4 , which is separated from the liquid medium by any means chosen from those known to those skilled in the art.
- the desuranized alkylpyrophosphoric acid is then recycled directly to the extraction of the uranium contained in the solutions of phosphoric acids after possible recharging with new alkylpyrophosphoric acid, while the solutions of desuranic phosphoric acids are themselves subjected to centrifugation to recover the mechanically driven extractant.
- This example illustrates the method of extracting uranium according to the invention, using alkylpyrophosphoric acids compared to the extraction method most commonly used in the processes belonging to the prior art.
- This acid is reduced either by powdered iron in a stirred tank for tests 1 to 4, or in a column by plate iron for tests 5 and 6.
- the reduced phosphoric acid contains Fe II and Fe III in an Fe II / Fe III ratio between 5 and 5.3.
- the phosphoric acid is treated with the extracting agent in solution in kerosene at a rate of 30 g / l.
- the reduced phosphoric acid flow rate was 200 l / h while that of the extractant solution was 20 l / h.
- the desuranized solvent was recycled to extraction after adding a fraction of an hour of the extractant.
- Test No. 1 which illustrates the prior art, was carried out in an industrial installation whose extraction unit consisted of a battery of 4 mixer-settlers - extraction unit in which the cumulative times T 1 and T 2 for 4 stages as defined in the method according to the invention, is equal to 14 hours.
- Test No. 2 illustrating the invention was carried out in an industrial installation, the extraction unit of which consisted of a 4-stage multi-stage centrifugal extractor, rotating at the speed of 2800 rpm, a unit in which the accumulation residence times T, and T z for 4 stages was less than two minutes.
- Test No. 3 illustrating the prior art, differs from test No. 1 in the nature of the extractant which in this case was a solution of ethylhexylpyrophosphoric acid.
- Test No. 4 illustrating the invention, differs from test No. 2 in the nature of the extractant which was ethylhexylpyrophosphoric acid.
- Test No. 5 illustrating the prior art, differs from test No. 1 only in the mode of reduction of phosphoric acid (on platelets in column).
- Test N ° 6 illustrating the invention, differs from test N ° 2 by the mode of reduction of phosphoric acid and by the constitution of the extraction unit which included four single stage centrifugal extractors in battery - unit in which the cumulative residence times T, and T 2 was less than two minutes.
- This example illustrates the method of extracting uranium according to the invention, using alkylpyrophosphoric acids, compared to the extraction method most commonly used in methods belonging to the prior art.
- the phosphoric acid treated had the following composition:
- Test No. 7 which illustrates the prior art, was carried out like test 1, in a battery of 4 mixer-settlers.
- Test No. 8 which illustrates the invention, was carried out like test 2, but using a battery comprising 3 single-stage centrifugal extractors.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8213820 | 1982-07-30 | ||
| FR8213820A FR2531102B1 (fr) | 1982-07-30 | 1982-07-30 | Procede d'extraction de l'uranium des acides phosphoriques par les acides alkylpyrophosphoriques |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0100744A1 EP0100744A1 (fr) | 1984-02-15 |
| EP0100744B1 true EP0100744B1 (fr) | 1985-12-18 |
Family
ID=9276723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83420127A Expired EP0100744B1 (fr) | 1982-07-30 | 1983-07-20 | Procédé d'extraction de l'uranium des acides phosphoriques par les acides alkylpyrophosphoriques |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4510122A (es) |
| EP (1) | EP0100744B1 (es) |
| KR (1) | KR870002187B1 (es) |
| BR (1) | BR8304067A (es) |
| CA (1) | CA1209808A (es) |
| ES (1) | ES8404419A1 (es) |
| FI (1) | FI832749A (es) |
| FR (1) | FR2531102B1 (es) |
| GR (1) | GR78860B (es) |
| IL (1) | IL69342A (es) |
| JO (1) | JO1260B1 (es) |
| MA (1) | MA19852A1 (es) |
| OA (1) | OA07505A (es) |
| PH (1) | PH19136A (es) |
| PT (1) | PT77136B (es) |
| YU (1) | YU157783A (es) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2573415B1 (fr) * | 1984-11-16 | 1986-12-12 | Pechiney Uranium | Procede de recuperation sous forme de fluorure tetravalent de l'uranium extrait de solutions phosphatees |
| US5463177A (en) * | 1994-08-23 | 1995-10-31 | General Electric Company | Solvent extraction process |
| KR100675919B1 (ko) * | 2005-11-08 | 2007-06-04 | 정영기 | 원심분리기를 이용한 우라늄 동위원소 분리방법 |
| US8883096B2 (en) | 2008-07-31 | 2014-11-11 | Urtek, Llc | Extraction of uranium from wet-process phosphoric acid |
| US8226910B2 (en) * | 2008-07-31 | 2012-07-24 | Urtek, Llc | Extraction of uranium from wet-process phosphoric acid |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2847275A (en) * | 1955-01-04 | 1958-08-12 | James H Yeager | Uranium recovery process |
| GB860428A (en) * | 1958-01-29 | 1961-02-08 | Ca Atomic Energy Ltd | Liquid-liquid contact extractor |
| US3416320A (en) * | 1967-07-14 | 1968-12-17 | Exxon Research Engineering Co | Turbo-jet propulsion method using emulsified fuels and demulsification |
| GB1596410A (en) * | 1976-12-27 | 1981-08-26 | Exxon Research Engineering Co | Liquid membranes and process for uranium recovery therewith |
| FR2376688A1 (fr) * | 1977-01-10 | 1978-08-04 | Anglian Water Authority | Procede et appareil pour former une dispersion aqueuse stable de produits a base de silicate |
| US4180545A (en) * | 1977-03-25 | 1979-12-25 | Tennessee Valley Authority | Uranium recovery from wet-process phosphoric acid |
| US4154698A (en) * | 1977-06-08 | 1979-05-15 | Nalco Chemical Company | Resolution of oil-in-water emulsions containing uranium |
| FR2423545A1 (fr) * | 1977-08-25 | 1979-11-16 | Minemet Rech Sa | Procede pour la recuperation de l'uranium contenu dans des solutions phosphatees |
| US4243637A (en) * | 1977-10-11 | 1981-01-06 | Occidental Petroleum Company | Uranium recovery from pre-treated phosphoric acid |
| US4311676A (en) * | 1978-09-08 | 1982-01-19 | Minemet Recherche | Process for the recovery of uranium contained in phosphated compounds |
| US4293529A (en) * | 1978-10-27 | 1981-10-06 | Uranium Recovery Corporation | Process for recovering uranium from wet-process phosphoric acid using alkyl pyrophosphoric acid extractants |
| US4292278A (en) * | 1979-02-21 | 1981-09-29 | Wyoming Mineral Corp. | Purification of wet process phosphoric acid as a pretreatment step in the recovery of uranium |
| US4287071A (en) * | 1979-10-10 | 1981-09-01 | Occidental Research Corporation | Simultaneous extraction of more than one ion by liquid membrane process |
-
1982
- 1982-07-30 FR FR8213820A patent/FR2531102B1/fr not_active Expired
-
1983
- 1983-07-07 US US06/511,478 patent/US4510122A/en not_active Expired - Fee Related
- 1983-07-08 PH PH29192A patent/PH19136A/en unknown
- 1983-07-20 EP EP83420127A patent/EP0100744B1/fr not_active Expired
- 1983-07-22 KR KR1019830003380A patent/KR870002187B1/ko active IP Right Grant
- 1983-07-25 YU YU01577/83A patent/YU157783A/xx unknown
- 1983-07-25 MA MA20073A patent/MA19852A1/fr unknown
- 1983-07-26 IL IL69342A patent/IL69342A/xx unknown
- 1983-07-26 GR GR72027A patent/GR78860B/el unknown
- 1983-07-27 OA OA58072A patent/OA07505A/xx unknown
- 1983-07-29 CA CA000433538A patent/CA1209808A/fr not_active Expired
- 1983-07-29 PT PT77136A patent/PT77136B/pt unknown
- 1983-07-29 FI FI832749A patent/FI832749A/fi not_active Application Discontinuation
- 1983-07-29 BR BR8304067A patent/BR8304067A/pt unknown
- 1983-07-29 ES ES524587A patent/ES8404419A1/es not_active Expired
- 1983-07-30 JO JO19831260A patent/JO1260B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| ES524587A0 (es) | 1984-05-01 |
| KR840005414A (ko) | 1984-11-12 |
| BR8304067A (pt) | 1984-03-07 |
| PT77136A (fr) | 1983-08-01 |
| PH19136A (en) | 1986-01-10 |
| FR2531102A1 (fr) | 1984-02-03 |
| FR2531102B1 (fr) | 1986-08-14 |
| EP0100744A1 (fr) | 1984-02-15 |
| FI832749A0 (fi) | 1983-07-29 |
| IL69342A (en) | 1986-07-31 |
| US4510122A (en) | 1985-04-09 |
| JO1260B1 (en) | 1985-04-20 |
| GR78860B (es) | 1984-10-02 |
| PT77136B (fr) | 1986-01-24 |
| YU157783A (en) | 1986-04-30 |
| ES8404419A1 (es) | 1984-05-01 |
| KR870002187B1 (ko) | 1987-12-28 |
| FI832749A (fi) | 1984-01-31 |
| MA19852A1 (fr) | 1984-04-01 |
| OA07505A (fr) | 1985-03-31 |
| CA1209808A (fr) | 1986-08-19 |
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