NO852826L - PROCEDURE FOR WASTE-WASTE EXTRACTION OF GALLIUM FROM BASIC, Aqueous SOLUTIONS USING AN ORGANIC EXTRACTIVE AGENT - Google Patents
PROCEDURE FOR WASTE-WASTE EXTRACTION OF GALLIUM FROM BASIC, Aqueous SOLUTIONS USING AN ORGANIC EXTRACTIVE AGENTInfo
- Publication number
- NO852826L NO852826L NO852826A NO852826A NO852826L NO 852826 L NO852826 L NO 852826L NO 852826 A NO852826 A NO 852826A NO 852826 A NO852826 A NO 852826A NO 852826 L NO852826 L NO 852826L
- Authority
- NO
- Norway
- Prior art keywords
- gallium
- organic
- waste
- extractant
- basic
- Prior art date
Links
- 229910052733 gallium Inorganic materials 0.000 title claims description 38
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 11
- 239000007864 aqueous solution Substances 0.000 title claims description 3
- 238000000605 extraction Methods 0.000 title description 13
- 239000002699 waste material Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004131 Bayer process Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- 150000004325 8-hydroxyquinolines Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229960003540 oxyquinoline Drugs 0.000 claims description 4
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims 3
- 150000007513 acids Chemical class 0.000 claims 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims 2
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical group S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 claims 2
- 101100305864 Alteromonas mediterranea (strain DSM 17117 / CIP 110805 / LMG 28347 / Deep ecotype) rph2 gene Proteins 0.000 claims 1
- 101100135363 Yarrowia lipolytica (strain CLIB 122 / E 150) RIM101 gene Proteins 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000004645 aluminates Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 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
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 phosphine compound Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
- C01F7/47—Purification of aluminium oxide, aluminium hydroxide or aluminates of aluminates, e.g. removal of compounds of Si, Fe, Ga or of organic compounds from Bayer process liquors
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- 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)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Description
Oppfinnelsen angår en fremgangsmåte ved væske-væske-ekstraksjon av gallium fra basiske, vandige oppløsninger, spesielt fra natriumaluminatluten fra aluminiumproduksjonen ved Bayer-prosessen, ved hjelp av et organisk ekstraksjonsmiddel som er sammensatt av et oppløsningsmiddel og et substituert 8-hydroxykinolin. The invention relates to a method for the liquid-liquid extraction of gallium from basic, aqueous solutions, in particular from the sodium aluminate liquor from aluminum production by the Bayer process, using an organic extractant which is composed of a solvent and a substituted 8-hydroxyquinoline.
Ved den kjente Bayer-prosess som tjener for fremstilling av aluminiumoxyd fra aluminiummineraler (bauxitter), blir de sistnevnte oppsluttet med natronlut ved forhøyet temperatur og forhøyet trykk. In the well-known Bayer process, which is used for the production of aluminum oxide from aluminum minerals (bauxites), the latter are digested with caustic soda at elevated temperature and elevated pressure.
Fra natriumaluminatluten kan aluminiumhydroxyd utfelles Aluminum hydroxide can be precipitated from the sodium aluminate liquor
som deretter brennes til A^O^(aluminiumoxyd) .which is then burned to A^O^(aluminium oxide) .
Størstedelen av galliumproduksjonen skjer i dag fra bauxitter som inneholder inntil 0,01% gallium, i forbindelse med Bayer-prosessen. Etter oppslutningen av malmen blir gallium som oftest elektrolytisk utvunnet fra aluminatluten. The majority of gallium production today takes place from bauxites containing up to 0.01% gallium, in connection with the Bayer process. After digestion of the ore, gallium is usually electrolytically extracted from the aluminate liquor.
Ved resirkulasjonen av luten blir gallium/aluminium-forholdet øket fra ca. 1:4000 i bauxitt til ca. 1:300 i aluminatluten . During the recirculation of the lye, the gallium/aluminium ratio is increased from approx. 1:4000 in bauxite to approx. 1:300 in the aluminate liquor.
Ved forskjellige ytterligere anrikningsmetoder blir galliuminnholdet i luten ytterligere hevet, hvorved imidlertid aluminatluten får sin sammensetning forandret og ikke lenger kan tilbakesendes til Bayer-prosessen. With various additional enrichment methods, the gallium content in the liquor is further raised, whereby, however, the alumina liquor has its composition changed and can no longer be returned to the Bayer process.
To fremgangsmåter er blitt utviklet som ikke forandrer Two methods have been developed that do not change
aluminatluten.the aluminate liquor.
Den første fremgangsmåte er særpreget ved at galliumet The first method is characterized by the gallium
fra luten blir direkte utskilt på en kvikksølvkatode.from the lye is directly separated on a mercury cathode.
Ved en annen fremgangsmåte utvinnes galliumet ved semen-ter ing med et natriumamalgam (seUllmanns Enzyklopådie aer technischen Chemie). In another method, the gallium is extracted by cementing with a sodium amalgam (seUllmann's Enzyklopådie aer technischen Chemie).
Også disse to fremgangsmåter er imidlertid kostbare og innsatskrevende fordi store kvikksølvmengder må behandles i forhold til den lille mengde av utvunnet gallium. However, these two methods are also expensive and labor-intensive because large amounts of mercury must be processed in relation to the small amount of extracted gallium.
Også organiske materialer er kjente som er i stand tilOrganic materials are also known which are capable of
å ekstrahere gallium fra basiske oppløsninger som f.eks. behandles ved Bayer-prosessen. De første organiske ekstraksjonsmidler som ble bekjentgjort, var hydroxykinolin og acetyl-aceton, som disse f.eks. er nevnt i fransk patentskrift 952 976 hhv. i US patentskrift 3 887 681. Deres høye oppløse- to extract gallium from basic solutions such as processed by the Bayer process. The first organic extractants to be introduced were hydroxyquinoline and acetyl-acetone, which e.g. is mentioned in French patent document 952 976 or in US Patent 3,887,681. Their high dissoln.
lighet i den basiske lut og deres lave selektivitet virker imidlertid mot den industrielle anvendelse av disse. However, their similarity in the basic lye and their low selectivity work against their industrial application.
Utviklingen og inføringen av de kobberspesifikke ekstraksjonsmidler på hydroxykinolinbasis har først ført til omfangs-rike undersøkelser angående den industrielle anvendelse av disse substituerte 8-hydroxykinoliner for ekstraksjon av gallium fra lutene fra Bayer-prosessen, som nevnt f.eks. i fransk patentskrift 74 242 63. The development and introduction of the copper-specific extractants on a hydroxyquinoline basis has first led to extensive research regarding the industrial use of these substituted 8-hydroxyquinolines for the extraction of gallium from the lyes from the Bayer process, as mentioned e.g. in French patent document 74 242 63.
Det var en vesentlig ulempe ved disse ekstraksjonsmidler at ekstraksjonshastighetene for gallium var forholdsvis lave også ved forhøyet temperatur. En ytterligere temperatur-økning for å øke ekstraksjonshastigheten er imidertid ikke mulig på grunn av den tiltagende spaltning av ekstraksjonsmidlet. It was a significant disadvantage of these extraction agents that the extraction rates for gallium were relatively low even at elevated temperatures. A further increase in temperature in order to increase the extraction rate is however not possible due to the increasing decomposition of the extractant.
Det har imidlertid vist seg, som nevnt f.eks. i fransk patentskrift 77 377 85, at tilblanding av en organisk forbindelse med minst én carboxylsyregruppe til substituert 8-hydroxykinolin øker ekstraksjonshastigheten for gallium be-traktelig. Tilsetningen av en carboxylsyre byr imidlertid på to ulemper. However, it has been shown, as mentioned e.g. in French patent document 77 377 85, that the addition of an organic compound with at least one carboxylic acid group to substituted 8-hydroxyquinoline increases the extraction rate for gallium considerably. However, the addition of a carboxylic acid presents two disadvantages.
For det første er tapene av ekstraksjonsmidlet på grunn av dets økede oppløselighet i aluminatluten forholdsvis store, og for det annet er carboxylsyren kinetisk virksom først ved store konsentrasjoner av denne i ekstraksjonsmiddelblandingen. Dette innebærer at først da kan en tilstrekkelig høy ekstraksjonshastighet oppnås. Firstly, the losses of the extractant due to its increased solubility in the aluminate liquor are relatively large, and secondly, the carboxylic acid is kinetically active only at high concentrations of this in the extractant mixture. This means that only then can a sufficiently high extraction rate be achieved.
I forhold hertil ligger den oppgave til grunn for oppfinnelsen å tilveiebringe en organisk ekstraksjonsmiddelblanding som foruten en forholdsvis lav oppløselighet i den basiske oppløsning muliggjør høye ekstraksjonshastigheter. In relation to this, the task underlying the invention is to provide an organic extractant mixture which, in addition to a relatively low solubility in the basic solution, enables high extraction rates.
Denne oppgave blir nådd ved hjelp av de særtrekk somThis task is achieved with the help of the distinctive features which
er nevnt i krav l's karakteriserende del.is mentioned in claim 1's characterizing part.
F.eks. kan ekstraksjonsmiddelblandingen ifølge oppfinnelsen foruten oppløsningsmidlet (løsemiddel) og det ovennevnte substituerte 8-hydroxykinolin inneholde en substituert fosfin-forbindelse. E.g. can the extractant mixture according to the invention contain a substituted phosphine compound in addition to the solvent (solvent) and the above-mentioned substituted 8-hydroxyquinoline.
Som oppløsningsmiddel kan ethvert ønsket organisk opp-løsningsmiddel med høyt kokepunkt, som f.eks. kerosin, anvendes . As a solvent, any desired organic solvent with a high boiling point, such as e.g. kerosene is used.
Det ble imidlertid fastslått at et oppløsningsmiddel som overveiende inneholder aromatiske hydrocarboner, gene-relt bibringer blandingen bedre egenskaper. Således forløper f.eks. separeringen av de to faser (organisk ekstraksjonsmiddel og aluminatlut) etter materialutvekslingen bedre og hurtigere enn dersom et alifatisk oppløsningsmiddel var blitt anvendt. However, it was determined that a solvent which predominantly contains aromatic hydrocarbons generally imparts better properties to the mixture. Thus, e.g. the separation of the two phases (organic extractant and aluminate liquor) after the material exchange better and faster than if an aliphatic solvent had been used.
Etter galliumutvekslingen mellom den organiske ekstraksjonsmiddelblanding og aluminatluten fra Bayer-prosessen er den organiske fase delvis også belastet med aluminium og natrium. Dette forårsakes av de meget høye konsentrasjoner av disse to metaller i aluminatluten. Forholdet aluminium/ gallium i ekstraksjonsmidlet og også forholdet natrium/gallium er langt lavere enn i den vandige, basiske lut. After the gallium exchange between the organic extractant mixture and the aluminate liquor from the Bayer process, the organic phase is also partially loaded with aluminum and sodium. This is caused by the very high concentrations of these two metals in the aluminate liquor. The aluminum/gallium ratio in the extractant and also the sodium/gallium ratio is far lower than in the aqueous, basic lye.
Således er ved en typisk ekstraksjon forholdet aluminium/ gallium i luten f.eks. 4 00:1 og f.eks. bare 2,5:1 i den organiske fase som står i kjemisk likevekt med denne lut. På lig-nende måte forholder det seg med selektiviteten hva gjelder natrium: forholdet natrium/gallium i luten er 940:1 og i ekstraksjonsmidlet 15:1. Uttrykt i absolutte konsentrasjoner: aluminatluten inneholder 150 g/l natrium, 64 g/l aluminium og 0,16 g/l gallium og ekstraksjonsmidlet 6 g/l natrium, Thus, in a typical extraction, the aluminum/gallium ratio in the lye is e.g. 4 00:1 and e.g. only 2.5:1 in the organic phase which is in chemical equilibrium with this lye. The same applies to the selectivity of sodium: the sodium/gallium ratio in the lye is 940:1 and in the extractant 15:1. Expressed in absolute concentrations: the aluminate liquor contains 150 g/l sodium, 64 g/l aluminum and 0.16 g/l gallium and the extractant 6 g/l sodium,
1 g/l aluminium og 0,4 g/l gallium.1 g/l aluminum and 0.4 g/l gallium.
De tre metaller kan, hvilket også er kjent fra praksis innen metallekstraksjon, igjen fjernes fra den organiske fase med en mineralsyre, som f.eks. svovelsyre. Her kan en ennu bedre separering av gallium fra de andre to metaller (aluminium og natrium) oppnås fordi de tre metallkompleksers rela-tive stabilitet i ekstraksjonsmiddelblandingen er forskjellig høy. Således er galliumkomplekset mer stabilt sammenlignet med aluminium- og natriumkompleksene, og det er nødvendig med en sterkt konsentrert mineralsyre for å spalte dette galliumkompleks og derved igjen å utvinne galliumet. Metallene aluminium og natrium kan før strippingen av galliumet vaskes ut av ekstraksjonsmidlet med en fortynnet syre, hvorved galliumet forblir i ekstraksjonsmidlet. Dermed kan en ytterligere galliumrensning oppnåes. The three metals can, which is also known from practice in metal extraction, again be removed from the organic phase with a mineral acid, such as e.g. sulfuric acid. Here, an even better separation of gallium from the other two metals (aluminum and sodium) can be achieved because the relative stability of the three metal complexes in the extractant mixture is different. Thus, the gallium complex is more stable compared to the aluminum and sodium complexes, and a highly concentrated mineral acid is required to split this gallium complex and thereby extract the gallium again. Before stripping the gallium, the metals aluminum and sodium can be washed out of the extractant with a dilute acid, whereby the gallium remains in the extractant. Thus, a further gallium purification can be achieved.
TalleksempelNumerical example
Et organisk ekstraksjonsmiddel som var sammensatt av 10 mol% KELEX (varemerke tilhørende firmaet Schering GmbH), (R) 15 vol% isodecanol, 30 g/l Cyanex CNX w (varemerke til-hørende Cyanamid Company) i Solvesso 150 ^ (varemerke til-hørende ESSO Chem. Comp.) og belastet med 0,4 g/l gallium, 1 g/l aluminium, 6 g/l natrium, ble i to motstrømstrinn bragt i kontakt med en svovelsyreoppløsning som inneholdt 100 g/l H^ SO^ i vann. Etter separeringen oppviste fasene de følgende konsentrasjoner: An organic extractant that was composed of 10 mol% KELEX (trademark of Schering GmbH), (R) 15 vol% isodecanol, 30 g/l Cyanex CNX w (trademark of Cyanamid Company) in Solvesso 150 ^ (trademark of belonging to ESSO Chem. Comp.) and charged with 0.4 g/l gallium, 1 g/l aluminum, 6 g/l sodium, was brought into contact in two countercurrent stages with a sulfuric acid solution containing 100 g/l H^ SO^ in water. After separation, the phases showed the following concentrations:
1. fase1st phase
Deretter ble ekstråksjonsmiddelblandingen nok en gang 2. fase i to motstrømstrinn bragt i kontakt med en svovelsyreoppløs-ning som imidlertid denne gang hadde 300 g/l H2SO^inneholdt i vann. Etter separeringen var konsentrasjonene: Organisk ekstraksjonsmiddelblanding: The extractant mixture was then once again brought into contact with a sulfuric acid solution, which this time contained 300 g/l H2SO4 in water in the second phase in two countercurrent stages. After the separation, the concentrations were: Organic extractant mixture:
Den første vandige fase (fortynnet svovelsyre) som inneholder størstedelen av aluminium og natrium, kan fullstendig tilbakeføres til Bayer-prosessen hvor den kan viderebehandles uten ytterligere innsats. The first aqueous phase (dilute sulfuric acid) containing the majority of aluminum and sodium can be completely returned to the Bayer process where it can be further processed without further effort.
De eventuelle tap av aluminium og natrium er forholdsvis ubetydelige og neglisjerbart små. Fra den annen vandige fase (konsentrert svovelsyre) som inneholder størstedelen av det ekstraherte gallium, kan f.eks. med en lut et gallium-hydroxyd utfelles som kan anvendes for videre bearbeidelse til rent gallium. Any losses of aluminum and sodium are relatively insignificant and negligibly small. From the second aqueous phase (concentrated sulfuric acid) which contains the majority of the extracted gallium, e.g. with a lye a gallium hydroxide is precipitated which can be used for further processing into pure gallium.
Således er ved det ovenfor beskrevne talleksempel ved hjelp av oppfinnelsen en galliumutvinningsprosess blitt reali-sert som uten noen forandring av Bayer-prosessen kan til-knyttes ethvert Bayer-aluminiumoxydanlegg. Ved denne prosess behandles en forholdsvis liten del av aluminatluten, og bort-sett fra et noe nedsatt metallinnhold (aluminium og natrium) Thus, in the numerical example described above, with the aid of the invention, a gallium extraction process has been realized which can be connected to any Bayer aluminum oxide plant without any change to the Bayer process. In this process, a relatively small part of the aluminate liquor is treated, and apart from a somewhat reduced metal content (aluminium and sodium)
gir den denne lut uforandret igjen tilbake til prosessen for aluminiumoxydutvinning.Tapene av aluminium og natrium er forsvinnende små, og også forbruket av driftsmaterialer for galliumanlegget er lite sammenlignet med produktets verdi (gallium). it returns this lye unchanged to the aluminum oxide extraction process. The losses of aluminum and sodium are vanishingly small, and the consumption of operating materials for the gallium plant is also small compared to the value of the product (gallium).
Det følgende diagram viser en sammenligning mellom gal-liumekstraksjonshastighetene for to ekstraksjonsmiddelblandinger. The following chart shows a comparison between gallium extraction rates for two extractant mixtures.
Ekstraksjonsmiddelblanding I ifølge oppfinnelsen:Extractant mixture I according to the invention:
10 vol% KELEX, 30 g/l Cyanex CNX<®>,10 vol% KELEX, 30 g/l Cyanex CNX<®>,
(S) (S)
15 vol% isodecanol i Solvesso 150 15 vol% isodecanol in Solvesso 150
Ekstraksjonsmiddelblanding II med carboxylsyre:Extractant mixture II with carboxylic acid:
10 vol% KELEX, 5 vol% Versatic 10<®>(varemerke til-hørende Shell Comp.), 15 vol% isodecanol i Solvesso 150 ®. 10 vol% KELEX, 5 vol% Versatic 10<®> (trademark belonging to Shell Comp.), 15 vol% isodecanol in Solvesso 150 ®.
Begge blandinger ble på samme art og måte bragt i kontakt med en industriell aluminatlut ved et faseforhold W/O = Both mixtures were similarly brought into contact with an industrial aluminate liquor at a phase ratio W/O =
8/1 ved 50°C. Luten inneholder 150 g/l natrium, 64 g/l aluminium og 0,16 g/l gallium. Alle metallanalyser ble utført med at atomabsorpsjonsspektrofotometer. 8/1 at 50°C. The lye contains 150 g/l sodium, 64 g/l aluminum and 0.16 g/l gallium. All metal analyzes were performed with an atomic absorption spectrophotometer.
Diagrammet viser at ekstraksjonsmiddelblandingen I ifølge oppfinnelsen ekstraherer gallium vesentlig hurtigere enn den kjente, ovenfor beskrevne ekstraksjonsmiddelblanding II. The diagram shows that the extractant mixture I according to the invention extracts gallium significantly faster than the known, above-described extractant mixture II.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6369/83A CH656643A5 (en) | 1983-11-29 | 1983-11-29 | METHOD FOR THE LIQUID-LIQUID EXTRACTION OF GALLIUM FROM BASIC, AQUEOUS SOLUTIONS BY MEANS OF AN ORGANIC EXTRACTION AGENT. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO852826L true NO852826L (en) | 1985-07-15 |
Family
ID=4308499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO852826A NO852826L (en) | 1983-11-29 | 1985-07-15 | PROCEDURE FOR WASTE-WASTE EXTRACTION OF GALLIUM FROM BASIC, Aqueous SOLUTIONS USING AN ORGANIC EXTRACTIVE AGENT |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0143749A1 (en) |
| AU (1) | AU3613584A (en) |
| BR (1) | BR8405943A (en) |
| CH (1) | CH656643A5 (en) |
| NO (1) | NO852826L (en) |
| WO (1) | WO1985002390A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3508041A1 (en) * | 1985-03-07 | 1986-09-11 | Preussag Ag Metall, 3380 Goslar | METHOD FOR LIQUID-LIQUID EXTRACTION OF GALLIUM, GERMANIUM OR INDIUM FROM AQUEOUS SOLUTIONS |
| BE1002453A3 (en) * | 1989-04-28 | 1991-02-12 | Acec Union Miniere | METHOD FOR WINNING GERMANIUM. |
| FR2660645B1 (en) * | 1990-04-04 | 1992-12-11 | Rhone Poulenc Chimie | PROCESS FOR SEPARATING YTTRIUM. |
| BRPI0709451A2 (en) * | 2006-03-31 | 2011-07-12 | Alcoa Australia | method for the control of alumina precipitation from bayer and organic solvent solutions |
| CN103451428B (en) * | 2012-05-28 | 2015-03-11 | 中国原子能科学研究院 | Ruthenium purifying technology in plutonium purification cycle of Purex process |
| CN107460329A (en) * | 2017-08-08 | 2017-12-12 | 中条山有色金属集团有限公司 | A kind of method that indium metal is reclaimed from Bellamya aeruginosa |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR952976A (en) * | 1947-08-25 | 1949-11-28 | Alais & Froges & Camarque Cie | Process for extracting gallin from aluminous products |
| AU448131B2 (en) * | 1969-06-27 | 1974-04-24 | Ashland Oil Inc | Solvent extraction of metal values using oil-soluble 8-hydroxy quinolines |
| FR2277897A1 (en) * | 1974-07-12 | 1976-02-06 | Rhone Poulenc Ind | Gallium prodn from sodium aluminate solns - using liq.-liq. extn with organic phase contg a substd hydroxy-quinoline |
| CA1069316A (en) * | 1975-04-01 | 1980-01-08 | Metallurgie Hoboken-Overpelt | Treatment of ores or metallurgical by-products containing arsenic and antimony |
| US4039404A (en) * | 1975-05-19 | 1977-08-02 | Kennecott Copper Corporation | Cyclic process using A.C. for selective recovery of metals from materials containing same |
| FR2365641A2 (en) * | 1976-09-27 | 1978-04-21 | Rhone Poulenc Ind | PROCESS FOR RECOVERING GALLIUM FROM VERY BASIC SOLUTIONS BY LIQUID / LIQUID EXTRACTION |
| FR2397464A2 (en) * | 1977-07-13 | 1979-02-09 | Rhone Poulenc Ind | PROCESS FOR RECOVERING GALLIUM FROM VERY BASIC SOLUTIONS BY LIQUID / LIQUID EXTRACTION |
| FR2411894A1 (en) * | 1977-12-15 | 1979-07-13 | Rhone Poulenc Ind | GALLIUM EXTRACTION PROCESS |
| FR2532296B1 (en) * | 1982-08-26 | 1985-06-07 | Rhone Poulenc Spec Chim | PROCESS FOR THE EXTRACTION OF GALLIUM USING SUBSTITUTED HYDROXYQUINOLEINS AND ORGANOPHOSPHORUS COMPOUNDS |
-
1983
- 1983-11-29 CH CH6369/83A patent/CH656643A5/en not_active IP Right Cessation
-
1984
- 1984-11-20 WO PCT/CH1984/000184 patent/WO1985002390A1/en not_active Ceased
- 1984-11-20 EP EP84810566A patent/EP0143749A1/en not_active Withdrawn
- 1984-11-20 AU AU36135/84A patent/AU3613584A/en not_active Abandoned
- 1984-11-22 BR BR8405943A patent/BR8405943A/en unknown
-
1985
- 1985-07-15 NO NO852826A patent/NO852826L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU3613584A (en) | 1985-06-13 |
| WO1985002390A1 (en) | 1985-06-06 |
| CH656643A5 (en) | 1986-07-15 |
| BR8405943A (en) | 1985-09-17 |
| EP0143749A1 (en) | 1985-06-05 |
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