NO872216L - PROGRESS FOR THE EXTRACTION OF INDIUM, GERMANIUM AND / OR GALLIUM. - Google Patents
PROGRESS FOR THE EXTRACTION OF INDIUM, GERMANIUM AND / OR GALLIUM.Info
- Publication number
- NO872216L NO872216L NO872216A NO872216A NO872216L NO 872216 L NO872216 L NO 872216L NO 872216 A NO872216 A NO 872216A NO 872216 A NO872216 A NO 872216A NO 872216 L NO872216 L NO 872216L
- Authority
- NO
- Norway
- Prior art keywords
- gallium
- solution
- metals
- germanium
- indium
- Prior art date
Links
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052733 gallium Inorganic materials 0.000 title claims description 45
- 229910052732 germanium Inorganic materials 0.000 title claims description 19
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052738 indium Inorganic materials 0.000 title claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000605 extraction Methods 0.000 title claims description 6
- 239000000243 solution Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000002739 metals Chemical class 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000010828 elution Methods 0.000 claims description 9
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 7
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical group NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002223 garnet Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000027455 binding Effects 0.000 description 8
- 238000009739 binding Methods 0.000 description 8
- 239000002609 medium Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- -1 arsenic cations Chemical class 0.000 description 3
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- PAXPHUUREDAUGV-UHFFFAOYSA-N OP(=O)OP(O)(O)=O Chemical group OP(=O)OP(O)(O)=O PAXPHUUREDAUGV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- SXZYCXMUPBBULW-FORAYFFESA-N (5r)-5-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxyoxolan-2-one Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)C1O SXZYCXMUPBBULW-FORAYFFESA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910017214 AsGa Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ISZIECUHZQGAPV-UHFFFAOYSA-N NP(O)(=O)OP(O)=O Chemical compound NP(O)(=O)OP(O)=O ISZIECUHZQGAPV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WWNZQFVHLBNMDJ-UHFFFAOYSA-N OP(OP(O)=O)=O.O Chemical compound OP(OP(O)=O)=O.O WWNZQFVHLBNMDJ-UHFFFAOYSA-N 0.000 description 1
- QPCMSEVGGYOTQK-UHFFFAOYSA-N P(=O)(O)OP(=O)O.OCO Chemical compound P(=O)(O)OP(=O)O.OCO QPCMSEVGGYOTQK-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- RHVWSRKGJFLDFG-UHFFFAOYSA-N [aminooxy(hydroxy)phosphoryl]methylphosphonic acid Chemical compound NOP(O)(=O)CP(O)(O)=O RHVWSRKGJFLDFG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Foreliggende oppfinnelse vedrører gjenvinning av metaller oppløst i en konsentrert sinksulfatoppløsning. Mere spesielt vedrører den gjennvinning av metaller omfattende indium, germanium og gallium. The present invention relates to the recovery of metals dissolved in a concentrated zinc sulphate solution. More particularly, it relates to the recycling of metals including indium, germanium and gallium.
I løpet av de siste 10 år har de såkalte "mindre metaller" så som indium, germanium og gallium funnet et stadig økende antall anvendelser, spesielt innen feltet elektronikk. Som følge derav har disse metaller nådd et relativt høyt pris-nivå og mange teknikker har derfor vært foreslått for deres gjenvinning fra forskjellige media. During the last 10 years, the so-called "minor metals" such as indium, germanium and gallium have found an ever-increasing number of applications, especially in the field of electronics. As a result, these metals have reached a relatively high price level and many techniques have therefore been proposed for their recovery from different media.
Noen av disse metaller er tilstede i sinkmalmer, mere spesielt i sinkblend. Av denne grunn har hovedandelen av de foreslåtte prosesser stammet fra sinkmetalurgien. Some of these metals are present in zinc ores, more particularly in zinc alloy. For this reason, the majority of the proposed processes have originated from zinc metallurgy.
Med hensyn til indium og germanium er to tilfredssstillende teknikker: for germanium, en hvor det anvendes en væske-væskeekstraksjon under anvendelse av 8-hydroksykinolin derivater, slik som beskrevet i europeisk patent nr. 0,046,437 og for indium, en hvor det anvendes ekstraksjon med en harpiks innholdende en 02EHPA gruppe, slik som beskrevet i fransk patent nr. 2,435,533. With regard to indium and germanium, two satisfactory techniques are: for germanium, one where a liquid-liquid extraction using 8-hydroxyquinoline derivatives is used, as described in European Patent No. 0,046,437 and for indium, one where extraction with a resin containing an 02EHPA group, as described in French patent no. 2,435,533.
Imidlertid er det ikke tilgjengelig noen tilfredsstillende teknikk som muliggjør gjenvinning av gallium fra disse media, spesielt pga. den høye fortynning av gallium og de høye konsentrasjoner av forskjellige konkurrerende elementer, spesielt sink, aluminum og sjeldene jordarter (eks. gadolinium). En av hensiktene med foreliggende oppfinnelse er derfor å tilveiebringe fremgangsmåte for gjenvinning av gallium fra sulfatoppløsninger som er tynne med hensyn til gallium eller innholder forurensninger. However, no satisfactory technique is available which enables the recovery of gallium from these media, particularly due to the high dilution of gallium and the high concentrations of various competing elements, especially zinc, aluminum and rare earths (e.g. gadolinium). One of the purposes of the present invention is therefore to provide a method for recovering gallium from sulphate solutions which are thin with regard to gallium or contain impurities.
En annen hensikt med foreliggende oppfinnelse er å gjenvinne samtidig minst to av metallene omfattende indium, germanium og gallium. Another purpose of the present invention is to simultaneously recover at least two of the metals comprising indium, germanium and gallium.
En annen hensikt med foreliggende oppfinnelse er å tilveiebringe fremgangsmåte som muliggjør at de overfornevnte metaller kan gjenvinnes fra fortynnede oppløsninger, dvs. med konsentrasjoner mindre enn 500 mg/l og fortrinnsvis mindre enn 100 mg/l. Another purpose of the present invention is to provide a method which enables the above-mentioned metals to be recovered from dilute solutions, i.e. with concentrations less than 500 mg/l and preferably less than 100 mg/l.
En annen hensikt med oppfinnelsen er å tilveiebringe fremgangsmåte som muliggjør at konsentrasjonen av de nevnte elementer kan nedsettes til mindre enn 10 mg/l, fortrinnsvis mindre enn 5 mg/l og mere fordelaktig mindre enn 1 mg/l. Another purpose of the invention is to provide a method which enables the concentration of the mentioned elements to be reduced to less than 10 mg/l, preferably less than 5 mg/l and more advantageously less than 1 mg/l.
En annen hensikt med oppfinnelsen er å tilveiebringe fremgangsmåte som er selektiv mot konkurrerende metaller så som et metall eller ikke-metallkation som er istand til å være trivalent i det påtenkte medium så som jern (III) eller arsenikk-kationer. Another purpose of the invention is to provide a method which is selective against competing metals such as a metal or non-metal cation which is capable of being trivalent in the intended medium such as iron (III) or arsenic cations.
En annen hensikt med foreliggende oppfinnelse er å tilveiebringe en galliumanriket oppløsning som muliggjør en lett gjenvinning av gallium, eks. ved elektrolyse i et basisk medium. Disse hensikter og ytterligere som vil bli åpenbart senere oppnås ved en fremgangsmåte ved gjenvinning av metallene indium, germanium og gallium fra en sur oppløsning av disse metaller og er særpreget ved at den omfatter de følgende trinn: a) bringe oppløsningen i kontakt med en ionebyttefase innholdende minst en fosfongruppe, og b) eluere metallene bundet til ionebyttefasen. Fosfongruppen er fortrinnsvis en difosfonsyregruppe eller en Another purpose of the present invention is to provide a gallium-enriched solution which enables an easy recovery of gallium, e.g. by electrolysis in a basic medium. These purposes and further ones that will become apparent later are achieved by a method of recovering the metals indium, germanium and gallium from an acidic solution of these metals and is characterized by the fact that it includes the following steps: a) bringing the solution into contact with an ion exchange phase containing at least one phosphonic group, and b) elute the metals bound to the ion exchange phase. The phosphonic group is preferably a diphosphonic acid group or a
aminofosfonsyregruppe. Gruppene som gir de beste resultater er metylendifosfonsyre, aminometylen-difosfonsyre og fortrinnsvis hydroksy-difosfonsyregrupper. Kontaktfasen kan enten være en væske-væske fase hvori de lipid-oppløslige forbindelser beskrevet i en europeisk patentsøknad nr. aminophosphonic acid group. The groups which give the best results are methylene diphosphonic acid, amino methylene diphosphonic acid and preferably hydroxy diphosphonic acid groups. The contact phase can either be a liquid-liquid phase in which the lipid-soluble compounds described in a European patent application no.
81,400,633 er oppløst eller en stasjonær fase Innholdende aktive grupper. Hydroksy-difosfonsyreharpiksene beskrevet i den ovenfornevnte patentsøknad og aminodifosfonsyre-harpiksen så som solgt under handelsnavnet "E5 467 DIOLITE" kan spesielt nevnes. Denne kan også være stasjonær fase impreg-nert med hydrofobe molekyler innholdende disse aktive grupper. Oppløsningen innholdende de ovenfor angitte metaller bør fortrinnsvis ha en surhet mellom en pH er lik 5 og en hydrogenione-konsentrasjon tilsvarende en surhet på størrelsesorden 5 N. Et surhetsområde på IO-<2>og 2 N er spesielt foretrukket. 81,400,633 is dissolved or a stationary phase Containing active groups. The hydroxydiphosphonic acid resins described in the above-mentioned patent application and the aminodiphosphonic acid resin as sold under the trade name "E5 467 DIOLITE" may be particularly mentioned. This can also be a stationary phase impregnated with hydrophobic molecules containing these active groups. The solution containing the above mentioned metals should preferably have an acidity between a pH equal to 5 and a hydrogen ion concentration corresponding to an acidity of the order of magnitude 5 N. An acidity range of 10-<2> and 2 N is particularly preferred.
Anionene I oppløsningen er fortrinnsvis anioner av en sterk syre. Imidlertid er fremgangsmåten spesielt nyttig for syrer hvis anioner er ikke-kompleksdannende eller har lav kompleksdannende evne, så som salpetersyre, perklorsyre og svovelsyre. The anions in the solution are preferably anions of a strong acid. However, the method is particularly useful for acids whose anions are non-complexing or have low complexing ability, such as nitric acid, perchloric acid and sulfuric acid.
Undersøkelser som har ført til foreliggende oppfinnelse har vist at fosfonsyreharpikser er meget selektive mot forskjellige forurensninger som er tilstede i oppløsninger som stammer fra utvinning av sink under anvendelse av svovel-syreprosessen, og spesielt i oppløsninger som stammer fra kupolovnoksyder og de som stammer fra prosessen betegnet som "varm, sterk utlutning". Investigations which have led to the present invention have shown that phosphonic acid resins are highly selective against various contaminants present in solutions originating from the extraction of zinc using the sulfuric acid process, and particularly in solutions originating from cupola furnace oxides and those originating from the process designated as "hot, strong leaching".
Imidlertid må konsentrasjonsnivået for visse urenheter holdes innen visse grenser for å forøke innholdet i den org-aniske fase. Blandt disse kationer kan jern (III) og arsen (III) nevnes. However, the concentration level of certain impurities must be kept within certain limits in order to increase the content of the organic phase. Among these cations, iron (III) and arsenic (III) can be mentioned.
Konsentrasjonen av jern (III) må fortrinnsvis holdes under 1 g/l og fortrinnsvis under 500 mg/l. Ekstraksjonen av jern (III) kan utføres ved reduksjon, spesielt ved hjelp av sinkblend, svoveldioksyd og dets derivater og et hvilket som helst reduseringsmiddel som har et passende redokspotensial i den aktuelle oppløsning. The concentration of iron (III) must preferably be kept below 1 g/l and preferably below 500 mg/l. The extraction of iron (III) can be carried out by reduction, in particular by means of zinc blende, sulfur dioxide and its derivatives and any reducing agent having a suitable redox potential in the solution in question.
Med hensyn til arsen bør den maksimale konsentrasjon av det tilstedeværende arsen (III) ioner fortrinnsvis være mindre enn 3 g/l og mere fordelaktig mindre enn 1 g/l. With respect to arsenic, the maximum concentration of the arsenic (III) ions present should preferably be less than 3 g/l and more advantageously less than 1 g/l.
Arsen (III) kan fjernes ved oksydasjon til arsen (V). Arsen kan også fjernes ved i for seg kjente metoder. Arsenic (III) can be removed by oxidation to arsenic (V). Arsenic can also be removed by methods known per se.
Det kan sees at for å fjerne disse to interfererende elementer må to motsatte forholdsregler taes: reduksjon for den ene og oksydasjon for den andre. En løsning ligger i en total oksydasjon av arsen (III) til arsen (V). Denne oksydasjon muliggjør at jern kan utfelles i form av jernarsenat så snart pH for utfelling av denne forbindelse nåes. I et andre trinn kan gjenværende jern reduseres til jern (II). Oksydasjons/reduksjons reaksjonene av arsen er tilstrekkelig langsom til at nyomdannelse av arsen (V) til arsen (III) ikke er noe vesentlig problem. It can be seen that to remove these two interfering elements two opposite precautions must be taken: reduction for one and oxidation for the other. A solution lies in a total oxidation of arsenic (III) to arsenic (V). This oxidation enables iron to be precipitated in the form of iron arsenate as soon as the pH for precipitation of this compound is reached. In a second step, the remaining iron can be reduced to iron (II). The oxidation/reduction reactions of arsenic are sufficiently slow that re-formation of arsenic (V) to arsenic (III) is not a significant problem.
Konsentrasjonen av sink kan være meget høy og kan nå oppløs-lighetsgrensen for dets salt. Imidlertid vil tilstedeværelse av denne forbindelse forhindre at pH forøkes forbi en verdi på 1,5-2, ved hvilken verdi utfelling begynner å finne sted. Selektiviteten med hensyn til sink er ganske bemerkelses-verdig. The concentration of zinc can be very high and can reach the solubility limit for its salt. However, the presence of this compound will prevent the pH from increasing beyond a value of 1.5-2, at which value precipitation begins to take place. The selectivity with respect to zinc is quite remarkable.
For tilfelle av indium kan elueringen utføres under anvendelse av en sterk syre så som saltsyre eller svovelsyre. Imidlertid må høye konsentrasjoner, større enn 5 N nåes for å oppnå en god eluering eller et alkalimetall- , jordalkalimetall- eller amoniumsaltoppløsning må anvendes. In the case of indium, the elution can be carried out using a strong acid such as hydrochloric or sulfuric acid. However, high concentrations greater than 5 N must be reached to obtain a good elution or an alkali metal, alkaline earth metal or ammonium salt solution must be used.
Elueringen av germanium må utføres ved basiske pH-nivåer større enn 5. Imidlertid må oppløsligheten av germanium i mediet taes i betraktning. Sluttligen kan gallium elueres under anvendelse av en sterk basisk soppoppløsning som muliggjør at gallium går over i galliatformen. Natriumhyd-roksydoppløsninger med den pH 13- 15,3 er tilfredsstillende. 1-5 N natriumhydroksyd eller kaliumhydroksydoppløsninger kan spesielt anvendes. Elueringen er tilstrekkelig kraftig, slik at etter en eventuell resirkulering er det mulig å oppnå galliumkonsentrasjoner større enn 1 g/l som er en konsentrasjon som tillater en tilfredstillende elektrolyse av gallium. The elution of germanium must be carried out at basic pH levels greater than 5. However, the solubility of germanium in the medium must be taken into account. Finally, the gallium can be eluted using a strong basic mushroom solution which enables the gallium to transition into the galliate form. Sodium hydroxide solutions with a pH of 13-15.3 are satisfactory. 1-5 N sodium hydroxide or potassium hydroxide solutions can especially be used. The elution is sufficiently powerful, so that after any recycling it is possible to achieve gallium concentrations greater than 1 g/l, which is a concentration that allows a satisfactory electrolysis of gallium.
En prosedyre for å implementere oppfinnelsen for å gjenvinne gallium omfatter å utføre de følgende trinn i rekkefølge: den galliuminnholdende oppløsning bringes i kontakt med en ionebyttefase, fortrinnsvis en hydroksyd-difosfonsyrehar-piks, ionebyttefasen vaskes to ganger, først med fortynnet svovelsyre og deretter med vann, elueringen utføres under anvendelse av en 2 N natriumhydroksyd-oppløsning og ionebyttefasen bringes tilbake til sur form ved tilsetting av en fortynnet sur oppløsning, eks. svovelsyre og fasen er på ny "klar for å bli underkastet en ny gallium-utvinningssyklus. A procedure for implementing the invention to recover gallium comprises performing the following steps in sequence: the gallium-containing solution is brought into contact with an ion exchange phase, preferably a hydroxide-diphosphonic acid resin, the ion exchange phase is washed twice, first with dilute sulfuric acid and then with water , the elution is carried out using a 2 N sodium hydroxide solution and the ion exchange phase is returned to acidic form by the addition of a dilute acidic solution, e.g. sulfuric acid and the phase is again "ready to be subjected to a new gallium extraction cycle.
Anvendelse av fosfonsyreharpikser i henhold til foreliggende fremgangsmåte er også attraktiv for utvinning av gallium fra forskjellige kilder i den grad gallium og/eller indium og germanium foreligger i en sur oppløsning, fortrinnsvis av en syre hvis anioner er ikke-kompleksdannende, slik som beskrevet ovenfor. Slike oppløsninger erholdes ved rensning av galliumekstrakt fra natriumaluminat-oppløsninger (Bayer-væsker) og motstrømsekstrahert med en relativt fortynnet saltsyreoppløsning, med en svovelsyreoppløsning eller en blanding av disse to. I det tilfelle hvor bindingsgraden for gallium er høy, spesielt når konsentrasjonen av klorid-ioner ikke er meget høy (konsentrasjoner mindre enn 3 N, fortrinnsvis mindre enn 1 N og mest foretrukket mindre enn 0,1 N). Slike oppløsninger kan også oppstå når forskjellige galliuminnholdende forbindelser, så som galliuminnholdende III-V-forbindeIser (AsGa, GaP og lignende) eller forbindelser av garnett (gadolinium-galliumgarné eller GGG) bringes i oppløsning. Det bør bemerkes at under denne utløsning, som kan utføres på i for seg kjent måte, kan andre metaller, spesielt indium, germanium og gadolinium også utløses. Use of phosphonic acid resins according to the present method is also attractive for extracting gallium from various sources to the extent that gallium and/or indium and germanium are present in an acidic solution, preferably of an acid whose anions are non-complex-forming, as described above. Such solutions are obtained by purifying gallium extract from sodium aluminate solutions (Bayer liquids) and countercurrently extracted with a relatively dilute hydrochloric acid solution, with a sulfuric acid solution or a mixture of these two. In the case where the binding degree of gallium is high, especially when the concentration of chloride ions is not very high (concentrations less than 3 N, preferably less than 1 N and most preferably less than 0.1 N). Such solutions can also occur when various gallium-containing compounds, such as gallium-containing III-V compounds (AsGa, GaP and the like) or compounds of garnet (gadolinium-gallium garnet or GGG) are dissolved. It should be noted that during this triggering, which can be carried out in a manner known per se, other metals, especially indium, germanium and gadolinium can also be triggered.
Foreliggende fremgangsmåte muliggjør at gallium kan separe-res med gadolinium, spesielt ved eluering med en base, i hvilket tilfelle gallium lett danner anioner og oppløses i det basiske medium mens gadolinium danner disse former i meget mindre grad. The present method makes it possible for gallium to be separated from gadolinium, especially by elution with a base, in which case gallium easily forms anions and dissolves in the basic medium, while gadolinium forms these forms to a much lesser extent.
Når disse tre metaller (indium, germanium og gallium) er bundet er det mulig å elluere gallium og germanium sellek-tivt fra indium når dette forblir uoppløst på harpiksen i et basiskt medium, men kan elueres med konsentrert (større enn 2 N, fordelaktig større enn 5 N og mere fordelaktig i nærheten av 8 N) saltsyre. Saltsyren kan delvis erstattes med en blanding av sterke uorganiske syrer (HC1, H2CO4og lignende) og kloridionene kan føres i form av alkalimetall-, jordalkalimetall- eller tilsvarende salter (med ekvivalente salter menes sterkt disossierte klorider), forutsatt at konsentrasjonen av kloridionenene tilfredstiller begrensingen som representeres av saltsyren som angitt ovenfor og at sur-heten av elueringsmiddelet er minst lik 1 N, fortrinnsvis When these three metals (indium, germanium and gallium) are bound, it is possible to elute gallium and germanium cell-selectively from indium when this remains undissolved on the resin in a basic medium, but can be eluted with concentrated (greater than 2 N, advantageously greater than 5 N and more advantageously in the vicinity of 8 N) hydrochloric acid. The hydrochloric acid can be partially replaced with a mixture of strong inorganic acids (HC1, H2CO4 and the like) and the chloride ions can be supplied in the form of alkali metal, alkaline earth metal or equivalent salts (by equivalent salts is meant strongly dissociated chlorides), provided that the concentration of the chloride ions satisfies the limitation that is represented by the hydrochloric acid as stated above and that the acidity of the eluent is at least equal to 1 N, preferably
2 N. 2N.
Når gadolinium er tilstede i store mengder kan i for seg kjente teknikker for å felle ut blandete alkalimetallsul-fater av gadolinium anvendes for å senke dens konsentrasjon eller anvende en i for seg kjent utfelling ved anvendelse av oksalsyre eller dets salter. When gadolinium is present in large quantities, per se known techniques for precipitating mixed alkali metal sulphates of gadolinium can be used to lower its concentration or use a per se known precipitation using oxalic acid or its salts.
De etterfølgende eksempler tjener til å illustrere oppfinnelsen og er påtenkt for at fagmannen skal kunne bestemme arbeidsbetingelsene som er passende for anvendelse i hvert spesielt tilfelle. The following examples serve to illustrate the invention and are intended to enable the person skilled in the art to determine the working conditions that are suitable for use in each particular case.
Eksempel 1.Example 1.
Sammenlignende undersøkelser av binding av gallium innholdt i en industriell sinksulfatoppløsning, til forskjellige harpikser . Comparative investigations of the binding of gallium contained in an industrial zinc sulphate solution to different resins.
De undersøkte harpikser var:The investigated resins were:
En metylenhydroksydifosfonsyre-harpiks, i det etterfølgende betegnet HDP, A methylene hydroxide diphosphonic acid resin, hereinafter referred to as HDP,
En aminofosfonsyreharpiks solgt av DUOLITE under betegnelsen "ES 467", og An aminophosphonic acid resin sold by DUOLITE under the designation "ES 467", and
En tributylfosfatimpregnert-harpiks fremstilt av Bayer under navnet "OC 1023". A tributyl phosphate impregnated resin manufactured by Bayer under the name "OC 1023".
Sammensetningen av sinksulfatoppløsningen var:The composition of the zinc sulfate solution was:
ln : 100 g/lln: 100 g/l
Ge : 209 mg/lGe: 209 mg/l
Fe : 1.6 g/lFe : 1.6 g/l
As : S.3 g/lAs : S.3 g/l
Mn : 100 mg/lMn: 100 mg/l
Sb : 100 mg/lSb: 100 mg/l
Mg 10 g/ lMg 10 g/l
Ca : 0.5 g/l.Approx: 0.5 g/l.
Denne oppløsning ble tilsatt gallium slik at det ble oppnådd en konsentrasjon på 20,6 mg/l. Jern (III) ionene ble redusert under anvendelse av askorbinsyre i en mengde på 1,5 SQ (beregnet som den storkiometriske mengde nødvendig for å omdanne syren til dihydroaskorbinsyre). pH var 0,5. Kontak-ten mellom oppløsningene og de forskjellige harpikser ble utført i en skylletrakt med et harpiks: oppløsning volumforhold på 1:20. Omgivelsestemperatur. Under disse betingelser binder HDP-harpiksen gallium bedre enn de andre, men med lavere selektivitet ovenfor germanium. Resultatende er gitt samlet i den etterfølgende tabell: Gallium was added to this solution so that a concentration of 20.6 mg/l was obtained. The iron (III) ions were reduced using ascorbic acid in an amount of 1.5 SQ (calculated as the stoichiometric amount necessary to convert the acid to dihydroascorbic acid). pH was 0.5. The contact between the solutions and the different resins was carried out in a rinsing funnel with a resin:solution volume ratio of 1:20. Ambient temperature. Under these conditions, the HDP resin binds gallium better than the others, but with lower selectivity over germanium. The results are given together in the following table:
Harpikser med amidooksim-, ammonium- og aminoeddik-aktive grupper gir ingen sinifikante resultater for bindingen. Resins with amidoxime, ammonium and aminoacetic active groups give no significant results for the bond.
Resultatene vedrørende binding av TBP er heller ikke signifikante. The results regarding binding of TBP are not significant either.
Et forsøk ble utført med den samme oppløsning på et harpiks-sikt under anvendelse av et strømningshastighet på 4 bv/timer førte til binding av 1,7 g gallium/l og 1,2 g germanium/l. Når germanium utelates (redusert til en konsentrasjon på 0,6 mg/l) ble en kapasitet på 2 g/l oppnådd. An experiment carried out with the same solution on a resin screen using a flow rate of 4 bv/hr resulted in binding of 1.7 g gallium/l and 1.2 g germanium/l. When germanium is omitted (reduced to a concentration of 0.6 mg/l) a capacity of 2 g/l was achieved.
Eksempel 2.Example 2.
Effekten av Fe<3+>i nærvær av sink og germanium.The effect of Fe<3+> in the presence of zinc and germanium.
En syntetisk oppløsning med den følgende sammensetning:A synthetic solution with the following composition:
Zn = 100 g/lZn = 100 g/l
Ga =20mg/Ga = 20mg/
Ge = 200 mg/lGe = 200 mg/l
Total Fe = 1,5 g/lTotal Fe = 1.5 g/l
Fe<3+>= variabel.Fe<3+>= variable.
ble brakt i kontakt med en HDP-ioenbytteharpiks med et volumforhold mellom harpiksoppløsning på 1:20 under de samme betingelser som tidligere angitt. was contacted with an HDP ion exchange resin with a volume ratio of resin solution of 1:20 under the same conditions as previously stated.
Bindingene etter 1 time er gitt i den etterfølgende tabell: The bindings after 1 hour are given in the following table:
Eksempel 3. Example 3.
Eluering av gallium.Elution of gallium.
5 ml galliuminnholdende harpiks ble brakt i kontakt med 50 ml av en elueringsoppløsning I 1 time ved romtempratur. 5 ml of gallium-containing resin was contacted with 50 ml of an elution solution for 1 hour at room temperature.
Type elueringsmiddel og erholdte resultater er gitt samlet i den etterfølgende tabell: Type of eluent and results obtained are given together in the following table:
Eksempel 4. Example 4.
Et svovelsyre surt-eluat som stammet fra utløsning av et oppløsningsmiddel innholdende 8-hydroksykinolln aktive grupper hvor oppløsningsmiddelet var "ladet" ved kontakt me( en industriell Bayer natrium-aluminatoppløsning ble perkol-ert med den hastighet på 15 bv/h Igjennom aminofosfonsyreharpiksen solgt under handelsnavnet "ES 467". A sulfuric acid eluate resulting from dissolution of a solvent containing 8-hydroxyquinol active groups where the solvent was "charged" by contact with an industrial Bayer sodium aluminate solution was percolated at the rate of 15 bv/h through the aminophosphonic acid resin sold under trade name "ES 467".
Dette eluat med den surhet tilsvarende 3 N innholdt gallium (475 mg/l) og aluminium (535 mg/l) som hovedelementer og mindre urenheter som er felles for denne type eluat. This eluate with the acidity corresponding to 3 N contained gallium (475 mg/l) and aluminum (535 mg/l) as main elements and minor impurities common to this type of eluate.
Analyse av oppløsningen som forlot kolonnen ble utført med like intervaller hvorfra det er mulig å beregne mengden av bundet gallium som diferanse. Disse analyser er summarisk angitt i den etterfølgende tabell: Analysis of the solution leaving the column was carried out at equal intervals from which it is possible to calculate the amount of bound gallium as a difference. These analyzes are summarized in the following table:
Disse resultater viser en høy grad av selektivitet for gallium i forhold til aluminium fordi alluminium bindes kun i de initiale trinn av syklusen og når meget raskt et metningspunkt. Ytterligere er det trolig at aluminum i det minste delvis frigjøres ved fortrengning til fordel for gallium, selv om man ikke kan trekke konklusjonen fra analysen. These results show a high degree of selectivity for gallium in relation to aluminum because aluminum is bound only in the initial stages of the cycle and very quickly reaches a saturation point. Furthermore, it is likely that aluminum is at least partially released by displacement in favor of gallium, although one cannot draw the conclusion from the analysis.
Eksempel 5.Example 5.
Syntetiske oppløsninger av gallium og gadolinium i forskjellige vandige media ble fremstilt og brakt i kontakt med aminofosfonsyreharpiksen solgt under handelsnavnet "ES 467" i separasjonstrakter under omrøring. Synthetic solutions of gallium and gadolinium in various aqueous media were prepared and contacted with the aminophosphonic acid resin sold under the trade name "ES 467" in separatory funnels with stirring.
Binding som funksjon av tiden og resultatene av forsøkene er summarisk angitt i den etterfølgende tabell: Binding as a function of time and the results of the experiments are summarized in the following table:
Resultatende viser at binding av gallium og gadolinium er relativt nær hverandre i hvert medium. Disse relativt høye The results show that binding of gallium and gadolinium is relatively close to each other in each medium. These relatively high
bindinger tiltross for den sterke surhet i det 8 N saltsyre-medium synes å være relatert til binding av anion til amino-posisjonen i aminofosfonsyreharpiksen, spesielt for tilfelle av gallium. bonds despite the strong acidity of the 8 N hydrochloric acid medium appear to be related to binding of the anion to the amino position of the aminophosphonic acid resin, especially in the case of gallium.
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8607525A FR2599271A1 (en) | 1986-05-27 | 1986-05-27 | PROCESS FOR RECOVERING INDIUM, GERMANIUM AND / OR GALLIUM USING PHASES EXCHANGING IONS WITH PHOSPHONIC GROUP. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO872216D0 NO872216D0 (en) | 1987-05-26 |
| NO872216L true NO872216L (en) | 1987-11-30 |
Family
ID=9335654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO872216A NO872216L (en) | 1986-05-27 | 1987-05-26 | PROGRESS FOR THE EXTRACTION OF INDIUM, GERMANIUM AND / OR GALLIUM. |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0249520A1 (en) |
| JP (1) | JPS6324025A (en) |
| AU (1) | AU7327587A (en) |
| FI (1) | FI872310A (en) |
| FR (1) | FR2599271A1 (en) |
| NO (1) | NO872216L (en) |
| ZA (1) | ZA873768B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU590023B2 (en) * | 1985-11-21 | 1989-10-26 | Sumitomo Chemical Company, Limited | Process for recovery of rare metals |
| BE1002453A3 (en) * | 1989-04-28 | 1991-02-12 | Acec Union Miniere | METHOD FOR WINNING GERMANIUM. |
| CN107746965B (en) * | 2017-09-20 | 2019-09-10 | 郴州丰越环保科技有限公司 | A kind of method of germanium vacuum distillation slag recovery indium germanium |
| CN112877550B (en) * | 2021-01-11 | 2022-12-13 | 北京高能时代环境技术股份有限公司 | Indium-germanium combined leaching and extraction process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2435533A1 (en) * | 1978-09-11 | 1980-04-04 | Penarroya Miniere Metall | INDIUM RECOVERY PROCESS |
| DE3065878D1 (en) * | 1979-07-09 | 1984-01-19 | Elf Aquitaine | Diphosphonic and triphosphonic acid esters, their preparation and applications |
| FR2489711A1 (en) * | 1980-04-21 | 1982-03-12 | Minemet Rech Sa | EXCHANGE COMPOSITIONS OF METAL CATIONS |
| DE3235136A1 (en) * | 1982-09-23 | 1984-03-29 | Hoechst Ag, 6230 Frankfurt | METHOD FOR SEPARATING GALLIUM AND INDIUM FROM AQUEOUS SOLUTIONS |
| JPS60145913A (en) * | 1984-01-05 | 1985-08-01 | Sumitomo Chem Co Ltd | Elution of indium absorbed to chelate resin |
-
1986
- 1986-05-27 FR FR8607525A patent/FR2599271A1/en not_active Withdrawn
-
1987
- 1987-05-21 AU AU73275/87A patent/AU7327587A/en not_active Abandoned
- 1987-05-25 FI FI872310A patent/FI872310A/en not_active IP Right Cessation
- 1987-05-25 EP EP87401179A patent/EP0249520A1/en not_active Withdrawn
- 1987-05-26 JP JP62129590A patent/JPS6324025A/en active Pending
- 1987-05-26 ZA ZA873768A patent/ZA873768B/en unknown
- 1987-05-26 NO NO872216A patent/NO872216L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI872310A (en) | 1987-11-28 |
| AU7327587A (en) | 1987-12-03 |
| JPS6324025A (en) | 1988-02-01 |
| ZA873768B (en) | 1987-11-20 |
| FR2599271A1 (en) | 1987-12-04 |
| EP0249520A1 (en) | 1987-12-16 |
| NO872216D0 (en) | 1987-05-26 |
| FI872310A0 (en) | 1987-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wassink et al. | Solvent extraction separation of zinc and cadmium from nickel and cobalt using Aliquat 336, a strong base anion exchanger, in the chloride and thiocyanate forms | |
| US5011665A (en) | Nonpolluting recovery of rare earth values from rare earth minerals/ores | |
| US3211521A (en) | Process for removing iron from acidic aluminum-containing solutions | |
| EP1071828B1 (en) | Processing route for direct production of mixed rare earth metal oxides by selective extraction | |
| US4968504A (en) | Recovery of scandium and uranium | |
| US3751553A (en) | Process for separating yttrium values from the lanthanides | |
| US4012481A (en) | Process for the separation of platinum group metals | |
| JPH0556288B2 (en) | ||
| US4241027A (en) | Reductive stripping process for the recovery of either or both uranium and vanadium | |
| De Schepper | Liquid-liquid extraction of germanium by LIX 63 | |
| US3923976A (en) | Process for recovery of zinc from solutions that contain it as a result of extraction with solvents for their adaptation to electrolysis | |
| CA1218529A (en) | Method of selective separation and concentration of gallium and/or indium from solutions containing low levels of them and high levels of other metal ions | |
| CA2104736A1 (en) | Process for high extraction of zinc from zinc ferrites | |
| JP3369855B2 (en) | Method for producing high purity nickel aqueous solution | |
| Crouse et al. | The amex process for extracting thorium ores with alkyl amines | |
| JPS5928614B2 (en) | Method for separating and purifying platinum and/or palladium | |
| NO307995B1 (en) | Procedure for extraction and recovery of thallium | |
| NO872216L (en) | PROGRESS FOR THE EXTRACTION OF INDIUM, GERMANIUM AND / OR GALLIUM. | |
| Orive et al. | THE RECOVERY OF COBALT AND NICKEL FROM ACIDIC SULPHATE SOLUTIONS IN THE PRESENCE OF ALUMINUM. | |
| US2863717A (en) | Recovery of uranium values from copper-bearing solutions | |
| CA2040541C (en) | Method for stripping metals in solvent extraction | |
| EA024748B1 (en) | Process for extracting uranium | |
| AU621833B2 (en) | Procedure for recovering gallium by liquid-liquid extraction | |
| De Schepper | Liquid-liquid extraction of gallium by tri-n-butyl phosphate | |
| Kyuchoukov et al. | Extraction of copper (II) and zinc (II) from chloride media with mixed extractants |