NO883038L - PROCEDURE FOR SEPARATING RARE EARTH ELEMENTS. - Google Patents
PROCEDURE FOR SEPARATING RARE EARTH ELEMENTS.Info
- Publication number
- NO883038L NO883038L NO88883038A NO883038A NO883038L NO 883038 L NO883038 L NO 883038L NO 88883038 A NO88883038 A NO 88883038A NO 883038 A NO883038 A NO 883038A NO 883038 L NO883038 L NO 883038L
- Authority
- NO
- Norway
- Prior art keywords
- organic phase
- rare earth
- diluent
- acids
- extraction
- Prior art date
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 10
- 239000012074 organic phase Substances 0.000 claims description 29
- 239000003085 diluting agent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- -1 benzene hydrocarbons Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 125000005608 naphthenic acid group Chemical group 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 5
- DUENOCOQRLXLKT-UHFFFAOYSA-N 5,8-diethyldodecan-6-ylphosphonic acid Chemical compound CCCCC(CC)CC(P(O)(O)=O)C(CC)CCCC DUENOCOQRLXLKT-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 4
- 229940075613 gadolinium oxide Drugs 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical class CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 101150023663 flu gene Proteins 0.000 description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- DPOZWTRVXPUOQW-UHFFFAOYSA-N 1,2-dibromo-1,1-difluoroethane Chemical compound FC(F)(Br)CBr DPOZWTRVXPUOQW-UHFFFAOYSA-N 0.000 description 1
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 1
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical class CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AMAPNDXGVRNGMZ-UHFFFAOYSA-N bis(2,4,4-trimethylcyclohexa-1,5-dien-1-yl)phosphinic acid Chemical compound C1=CC(C)(C)CC(C)=C1P(O)(=O)C1=C(C)CC(C)(C)C=C1 AMAPNDXGVRNGMZ-UHFFFAOYSA-N 0.000 description 1
- KZIUWSQALWALJH-UHFFFAOYSA-N bis(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)CP(O)(=O)CC(CC)CCCC KZIUWSQALWALJH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000002592 cumenyl group Chemical class C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical class CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 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
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
-
- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
-
- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for separering av sjeldne jordartselementer ved væske-væskeekstraksjon. The present invention relates to a method for separating rare earth elements by liquid-liquid extraction.
Man vet at separeringen av sjeldne jordartselementer ved væske-væskeekstraksjon kan gjennomføres på meget effektiv måte ved hjelp av organofosfonsyrer og organofosfinsyrer. It is known that the separation of rare earth elements by liquid-liquid extraction can be carried out very efficiently using organophosphonic acids and organophosphinic acids.
Denne separering foretas ved å bringe en vandig oppløsning inneholdende de sjeldne jordartselementer i kontakt med en organisk fase inneholdende som ekstraksjonsmiddel en organofosfonsyre eller organofosfinsyre. Denne type syre er meget selektiv og man oppnår følgelig utmerkede separeringer ved å anvende et forholdsvis lite antall teoretiske ekstraksjonstrinn i motstrøm. This separation is carried out by bringing an aqueous solution containing the rare earth elements into contact with an organic phase containing as extractant an organophosphonic acid or organophosphinic acid. This type of acid is very selective and excellent separations are consequently achieved by using a relatively small number of theoretical extraction steps in countercurrent.
Imidlertid oppstår et problem ved reekstraksjonen av de ekstraherte sjeldne jordartselementer fra den organiske fase. Denne reekstraksjon foretas med sure oppløsninger som f.eks. saltsyre og salpetersyre. Organofosfonsyren eller organofosfinsyren er imidlertid ekstraksjonsmidler som har en ganske lav surhet og videre anvendes de i industrielle prosesser fortynnet i parafinhydrokarboner av typen kerosen. Under disse betingelser nødvendiggjør reekstraksjonen forbruk av større mengder konsentrerte syrer alt etter som den ønskede utvinning av de sjeldne jordartselementer skal økes. However, a problem arises in the re-extraction of the extracted rare earth elements from the organic phase. This re-extraction is carried out with acidic solutions such as hydrochloric acid and nitric acid. However, the organophosphonic acid or organophosphinic acid are extractants that have a fairly low acidity and are further used in industrial processes diluted in paraffin hydrocarbons of the kerosene type. Under these conditions, the re-extraction necessitates the consumption of larger amounts of concentrated acids, depending on how the desired recovery of the rare earth elements is to be increased.
Dette medfører store omkostninger av reaksjonskomponenter som kan gjøre væske-væskeekstraksjon mindre interessant fra et økonomisk synspunkt. This entails large costs of reaction components which can make liquid-liquid extraction less interesting from an economic point of view.
Formålet for den foreliggende oppfinnelse er å tilveiebringe en sammensetning av løsningsmiddel og særlig et løsningsmiddel som kan lette reekstråksjonen. The purpose of the present invention is to provide a composition of solvent and in particular a solvent which can facilitate the re-extraction.
Dette formål oppnås ved fremgangsmåten i henhold til oppfinnelsen for separering av sjeldne jordartselementer ved væske-væskeekstraksjon hvor en initial vandig oppløsning med et innhold av i det minste ett sjeldent jordartselement bringes i kontakt med en initial organisk fase omfattende et ekstråksjonsmiddel valgt fra gruppen av organofosforsyre og organofosfinsyre og minst ett oppløsningsmiddel. En separering av den vandige og den organiske fase foretas og det oppnås en reekstraksjon av det eller de sjeldne jordartselementer fra den organiske fase ved å bringe denne i kontakt med en vandig sur oppløsning, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at man anvender minst ett halogenert fortynningsmiddel eller et slikt valgt fra gruppen av karboksylsyrer. This purpose is achieved by the method according to the invention for the separation of rare earth elements by liquid-liquid extraction where an initial aqueous solution containing at least one rare earth element is brought into contact with an initial organic phase comprising an extraction agent selected from the group of organophosphoric acid and organophosphinic acid and at least one solvent. A separation of the aqueous and the organic phase is carried out and a re-extraction of the rare earth element(s) from the organic phase is achieved by bringing this into contact with an aqueous acidic solution, and the distinctive feature of the method according to the invention is that it is used at least one halogenated diluent or one selected from the group of carboxylic acids.
Anvendelse av fortynningsmidlene i samsvar med oppfinnelsen nedsetter meget vesentlig forbruket av syre for reekstraksjonen eller tillater ved ellers like betingelser å øke utbyttet ved utvinningen av sjeldne jordartselementer. Use of the diluents in accordance with the invention very significantly reduces the consumption of acid for the re-extraction or allows, under otherwise equal conditions, to increase the yield in the extraction of rare earth elements.
Andre egenskaper og fordeler ved oppfinnelsen forstås lettere ved hjelp av den etterfølgende beskrivelse og utførelseseksemplene. Other properties and advantages of the invention are more easily understood with the help of the following description and the design examples.
Den initiale organiske fase i samsvar med oppfinnelsen omfatter først og fremst et ekstraksjonsmiddel som kan være valgt fra gruppen bestående av organofosfonsyrer, dvs. forbindelser med formel (R^O) R2PO(OH) hvori R]_ og R2er like eller forskjellige og står for alkylradikaler, alicykliske radikaler, alkenylradikaler, alkoksyalkylradikaler som kan være rettkjedet eller forgrenet, og aryl-, alkylaryl- og arylalkyl-radikaler. The initial organic phase in accordance with the invention primarily comprises an extractant which can be selected from the group consisting of organophosphonic acids, i.e. compounds of formula (R^O) R2PO(OH) in which R]_ and R2 are the same or different and stand for alkyl radicals, alicyclic radicals, alkenyl radicals, alkoxyalkyl radicals which may be straight chain or branched, and aryl, alkylaryl and arylalkyl radicals.
Man kan mer spesielt for R^og R2velge alkylradikaler og særlig 2-etylheksyl-2-etylheksyl-fosfonsyre. Alkyl radicals and especially 2-ethylhexyl-2-ethylhexyl-phosphonic acid can be chosen more particularly for R 1 and R 2 .
I samsvar med oppfinnelsen kan ekstraksjonsmiddelet også velges fra gruppen av organofosfinsyrer, dvs. forbindelser med formel R3R4PO (OH) hvori R3og R4er like eller forskjellige og har samme betydning som radikalene Rj_ og R2definert i det foregående. In accordance with the invention, the extractant can also be selected from the group of organophosphinic acids, i.e. compounds of the formula R3R4PO (OH) in which R3 and R4 are the same or different and have the same meaning as the radicals Rj_ and R2 defined in the foregoing.
Man kan spesielt for R3og R4anvende alkylradikaler og særlig bis(2-etylheksyl)-fosfinsyre eller bis(2,4,4-trimetylfenyl)-fosfinsyre. Alkyl radicals and particularly bis(2-ethylhexyl)-phosphinic acid or bis(2,4,4-trimethylphenyl)-phosphinic acid can be used in particular for R3 and R4.
Ved et vesentlig trekk ved oppfinnelsen omfatter den organiske fase minst ett fortynningsmiddel som kan velges innenfor gruppen av karboksylsyrer eller innenfor halogenerte fortynningsmidler. In an essential feature of the invention, the organic phase comprises at least one diluent which can be selected from within the group of carboxylic acids or within halogenated diluents.
Med hensyn til karboksylsyrer kan man først og fremst anvende rettkjedede eller forgrenede syrer, særlig fettsyrer med antall karbonatomer på minst 5, særlig mellom 6 og 15. With regard to carboxylic acids, one can primarily use straight-chain or branched acids, especially fatty acids with a number of carbon atoms of at least 5, especially between 6 and 15.
Man kan som eksempel nevne 2-etylheksansyre, laurinsyre, og syntetiske karboksylsyrer oppnådd ved den såkalte oksoprosess og som er en isomer blanding av dekansyrer. Examples include 2-ethylhexanoic acid, lauric acid and synthetic carboxylic acids obtained by the so-called oxo process and which are an isomeric mixture of decanoic acids.
Man kan også som fortynningsmiddel velge naftensyrer.You can also choose naphthenic acids as a diluent.
En ytterligere klasse av fortynningsmidler som anvendes ved oppfinnelsen er halogenerte fortynningsmidler og særlig i form av halogenerte hydrokarboner. A further class of diluents used in the invention are halogenated diluents and particularly in the form of halogenated hydrocarbons.
Man kan særlig nevne halogenerte alifatiske, alicykliske, etylenumettede og benzen-hydrokarboner. Particular mention may be made of halogenated aliphatic, alicyclic, ethylenically unsaturated and benzene hydrocarbons.
Ved en spesiell utførelsesform av oppfinnelsen anvendes fluorerte fortynningsmidler. In a particular embodiment of the invention, fluorinated diluents are used.
Som eksempel kan nevnes karbontetraklorid, klorbenzen, diklortoluen, kloroksylen, dikloretylen, trikloretylen, tetrakloretylen og triklorpropan. Examples include carbon tetrachloride, chlorobenzene, dichlorotoluene, chloroxylene, dichloroethylene, trichlorethylene, tetrachloroethylene and trichloropropane.
For fluorerte forbindelser kan nevnes forbindelsene solgt under handelsnavnet "Flugene", særlig triklortrifluoretan og difluortetrakloretan "Flugene 112"). For fluorinated compounds, mention may be made of the compounds sold under the trade name "Flugene", in particular trichlorotrifluoroethane and difluorotetrachloroethane "Flugene 112").
Man kan også anvende dibromdifluoretan, fluorerte derivater av kumen, dietylbenzen og p-etyltoluen. Dibromodifluoroethane, fluorinated derivatives of cumene, diethylbenzene and p-ethyltoluene can also be used.
Selvfølgelig kan de beskrevne fortynningsmidler anvendes alene eller i blanding. Videre er mengden av fortynningsmidler i den organiske fase ved oppfinnelsen mellom omtrent 30 og 95 volum% av denne fase. Videre, i visse tilfeller for å bedre hydrodynamikken i systemet, kan det være interessant å tilsette et hydrokarbon av vanlig anvendt type. Man kan tilrå et innhold av hydrokarbon på opptil 30 % av den organiske fase uten å forstyrre virkningen av fortynningsmidlene i samsvar med oppfinnelsen. Of course, the diluents described can be used alone or in a mixture. Furthermore, the amount of diluents in the organic phase in the invention is between approximately 30 and 95% by volume of this phase. Furthermore, in certain cases to improve the hydrodynamics of the system, it may be interesting to add a hydrocarbon of a commonly used type. One can recommend a hydrocarbon content of up to 30% of the organic phase without interfering with the effect of the diluents in accordance with the invention.
Den initiale vandige oppløsning kan være av en hvilken som helst art og omfatter ett eller flere sjeldne jordartselementer generelt i form av klorider eller nitrater. The initial aqueous solution can be of any kind and includes one or more rare earth elements generally in the form of chlorides or nitrates.
Med hensyn til å bringe fasen i kontakt med hverandre er dette ikke noe kritisk trekk ved oppfinnelsen og det nevnes bare at kontakten kan foretas i apparatur av typen blandings-avsetningsapparatur eller kolonneapparatur, foretrukket gjennomført kontinuerlig og i motstrøm i flere trinn. With regard to bringing the phases into contact with each other, this is not a critical feature of the invention and it is only mentioned that the contact can be made in apparatus of the type mixing-deposition apparatus or column apparatus, preferably carried out continuously and in countercurrent in several stages.
Temperaturen ved denne separasjon er ikke kritisk og er generelt i området fra romtemperatur til omtrent 80°C. The temperature for this separation is not critical and is generally in the range from room temperature to about 80°C.
Reekstraksjonen foretas på kjent måte i apparatur av samme type som nevnt i det foregående. The re-extraction is carried out in a known manner in apparatus of the same type as mentioned above.
Man anvender for reekstraksjonen av de sjeldne jordartselementer en vandig sur løsning som ved fremgangsmåten i henhold til oppfinnelsen kan være vesentlig mindre konsentrert. An aqueous acidic solution is used for the re-extraction of the rare earth elements, which in the method according to the invention can be significantly less concentrated.
De følgende eksempler illustrerer oppfinnelsen:The following examples illustrate the invention:
Eksempel 1 ( sammenligning)Example 1 (comparison)
En vandig oppløsning av neodymklorid med konsentrasjon 93,2 g oksyd pr. liter bringes i kontakt med en organisk fase som utgjøres av 2-etylheksyl-2-etylheksyl-fosfonsyre i oppløsning i mengde 1 mol pr. liter i kerosen, idet volumforholdet mellom fasene er 1:1. An aqueous solution of neodymium chloride with a concentration of 93.2 g of oxide per liter is brought into contact with an organic phase consisting of 2-ethylhexyl-2-ethylhexyl-phosphonic acid in solution in an amount of 1 mol per liter in the kerosene, the volume ratio between the phases being 1:1.
Ekstråksjonen gjennomføres ved vanlig temperatur.The extraction is carried out at normal temperature.
Man oppnår en organisk fase inneholdende 5,54 g/l neodymoksyd. An organic phase containing 5.54 g/l neodymium oxide is obtained.
Man gjennomfører en ny kontakt mellom den organiske fase og en vandig saltsyreløsning med konsentrasjon 0,1 mol pr. liter, idet volumforholdet mellom fasene er 1:1 og man oppnår en vandig fase inneholdende 2,09 g/l neodymoksyd, hvilket betyr et utbytte ved gjenvinningen fra den organiske fase på bare 37,7 %. A new contact is made between the organic phase and an aqueous hydrochloric acid solution with a concentration of 0.1 mol per litres, as the volume ratio between the phases is 1:1 and an aqueous phase containing 2.09 g/l neodymium oxide is obtained, which means a yield from the recovery from the organic phase of only 37.7%.
Eksempel 2Example 2
Den vandige neodymoppløsning fra eksempel 1 bringes i kontakt under de samme betingelser som i det foregående eksempel med en organisk fase som utgjøres av 2-etylheksyl-2-etylheksyl-fosfonsyre i oppløsning 1 M/l i et fortynningsmiddel som utgjøres av kerosen (20 volum% av den organiske fase) og 2-etylheksansyre (50 volum% av den organiske fase). The aqueous neodymium solution from example 1 is brought into contact under the same conditions as in the preceding example with an organic phase consisting of 2-ethylhexyl-2-ethylhexyl-phosphonic acid in a solution of 1 M/l in a diluent consisting of kerosene (20% by volume of the organic phase) and 2-ethylhexanoic acid (50% by volume of the organic phase).
Man oppnår en organisk fase etter kontakt og som inneholderAn organic phase is obtained after contact and which contains
3,69 g/l neodymoksyd.3.69 g/l neodymium oxide.
Man gjennomfører en ny kontakt mellom den organiske fase og en saltsyreoppløsning ved 0,1 mol pr. liter, idet volumforholdet mellom fasene er 1:1 og man oppnår en vandig fase inneholdende 3,07 g/l neodymoksyd som er et utbytte ved gjenvinningen på 83,5 %. A new contact is made between the organic phase and a hydrochloric acid solution at 0.1 mol per litres, the volume ratio between the phases being 1:1 and an aqueous phase containing 3.07 g/l neodymium oxide is obtained, which is a recovery yield of 83.5%.
Eksempel 3Example 3
Den vandige oppløsning av neodym som i eksempel 1 bringes i kontakt med en organisk fase som utgjøres av 2-etylheksyl-2-etylheksyl-fosfonsyre i oppløsning med 1 mol pr. liter i tetrakloretylen. The aqueous solution of neodymium which in example 1 is brought into contact with an organic phase consisting of 2-ethylhexyl-2-ethylhexyl-phosphonic acid in solution with 1 mol per liters in tetrachloroethylene.
Man oppnår under de samme betingelser som i eksempel 1 en organisk fase inneholdende 4,03 g/l neodymoksyd. An organic phase containing 4.03 g/l neodymium oxide is obtained under the same conditions as in example 1.
Man gjennomfører en ny kontakt mellom den organiske fase og en 0,1 mol pr. liter saltsyreoppløsning under betingelsene i . eksempel 1 og man oppnår en vandig fase inneholdende 3,1 g/l neodymoksyd som er et gjenvinningsutbytte på 77 %. A new contact is made between the organic phase and a 0.1 mol per liters of hydrochloric acid solution under the conditions in . example 1 and an aqueous phase containing 3.1 g/l neodymium oxide is obtained, which is a recovery yield of 77%.
Eksempel 4 ( sammenligning)Example 4 (comparison)
En vandig oppløsning av gadoliniumnitrat med 90 g oksyd pr. liter bringes i kontakt ved vanlig temperatur med den organiske fase fra eksempel 1 i volumforhold mellom fasene på 1:1. An aqueous solution of gadolinium nitrate with 90 g of oxide per liter is brought into contact at ordinary temperature with the organic phase from example 1 in a volume ratio between the phases of 1:1.
Man oppnår en organisk fase inneholdende 16,1 g/l gadoliniumoksyd. An organic phase containing 16.1 g/l gadolinium oxide is obtained.
Man gjennomfører en ny kontakt med et volumforhold mellom fasene på 1:1 med en vandig 0,5 mol/liter salpetersyreoppløsning og man oppnår en vandig fase inneholdende 6,2 g/l gadoliniumoksyd med et gjenvinningsutbytte på 38 %. A new contact is carried out with a volume ratio between the phases of 1:1 with an aqueous 0.5 mol/litre nitric acid solution and an aqueous phase containing 6.2 g/l gadolinium oxide is obtained with a recovery yield of 38%.
Eksempel 5Example 5
Den vandige oppløsning av gadoliniumnitrat fra eksempel 4 bringes i kontakt med den organiske fase i eksempel 2 og man oppnår en organisk fase inneholdende 8,5 g/l gadoliniumoksyd. The aqueous solution of gadolinium nitrate from example 4 is brought into contact with the organic phase in example 2 and an organic phase containing 8.5 g/l gadolinium oxide is obtained.
Denne organiske fase bringes deretter i kontakt med en 0,5 N salpetersyreløsning og man oppnår en vandig løsning inneholdende 8,13 g/l gadoliniumoksyd med et utbytte på 95,5 %. This organic phase is then brought into contact with a 0.5 N nitric acid solution and an aqueous solution containing 8.13 g/l gadolinium oxide is obtained with a yield of 95.5%.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8709796A FR2617829A1 (en) | 1987-07-10 | 1987-07-10 | PROCESS FOR SEPARATING RARE EARTHS BY LIQUID-LIQUID EXTRACTION USING HALOGENIC DILUENTS OR CARBOXYLIC ACID TYPE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO883038D0 NO883038D0 (en) | 1988-07-07 |
| NO883038L true NO883038L (en) | 1989-01-11 |
Family
ID=9353053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO88883038A NO883038L (en) | 1987-07-10 | 1988-07-07 | PROCEDURE FOR SEPARATING RARE EARTH ELEMENTS. |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0298843A1 (en) |
| JP (1) | JPH0193418A (en) |
| KR (1) | KR890001613A (en) |
| AU (1) | AU1887188A (en) |
| BR (1) | BR8803441A (en) |
| FR (1) | FR2617829A1 (en) |
| NO (1) | NO883038L (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2668763A1 (en) * | 1990-11-07 | 1992-05-07 | Rhone Poulenc Chimie | METHOD FOR SEPARATING RARE EARTHS |
| CN110373543A (en) * | 2019-08-26 | 2019-10-25 | 贵州省材料技术创新基地 | The technique of alkyl phosphinic acid extraction phosphorus ore rare earth element under a kind of acid system |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2859092A (en) * | 1953-02-05 | 1958-11-04 | Richard H Bailes | Solvent extraction process for the recovery of metals from phosphoric acid |
| US3230036A (en) * | 1963-09-18 | 1966-01-18 | Frederick A Kappelmann | Method for separating americium and curium from the lanthanide rare earths and yttrium |
| US3378352A (en) * | 1965-12-15 | 1968-04-16 | Dow Chemical Co | Process for extracting thorium and rare earths |
| GB1180921A (en) * | 1966-02-04 | 1970-02-11 | Thorium Ltd | Improvements in Separation Procedures. |
| US3554693A (en) * | 1969-01-07 | 1971-01-12 | Atomic Energy Commission | Separation of scandium from rare earth elements |
| DE2843574A1 (en) * | 1977-10-11 | 1979-04-19 | Mitsubishi Chem Ind | METHOD FOR SEPARATING YTTRIUM IONS |
| FR2460275B1 (en) * | 1979-06-29 | 1985-03-22 | Daihachi Chem Ind | PROCESS FOR SEPARATING RARE EARTH METALS BY SOLVENT EXTRACTION |
| FR2460276A1 (en) * | 1979-07-03 | 1981-01-23 | Rhone Poulenc Ind | PROCESS FOR TREATING RARE EARTH OXIDES AND GALLIUM MIXTURES |
| FR2562059B1 (en) * | 1984-04-02 | 1989-12-01 | Rhone Poulenc Spec Chim | PROCESS FOR SEPARATING RARE EARTH BY LIQUID-LIQUID EXTRACTION |
| FR2580273B1 (en) * | 1985-03-25 | 1990-01-05 | Rhone Poulenc Spec Chim | PROCESS FOR SEPARATING CERIUM AND RARE EARTH |
| FR2594429A1 (en) * | 1986-02-14 | 1987-08-21 | Rhone Poulenc Chimie | METHOD FOR REMOVING LEAD FROM RARE EARTHS |
-
1987
- 1987-07-10 FR FR8709796A patent/FR2617829A1/en not_active Withdrawn
-
1988
- 1988-07-01 EP EP88401703A patent/EP0298843A1/en not_active Withdrawn
- 1988-07-07 NO NO88883038A patent/NO883038L/en unknown
- 1988-07-08 JP JP63169132A patent/JPH0193418A/en active Pending
- 1988-07-08 BR BR8803441A patent/BR8803441A/en unknown
- 1988-07-08 AU AU18871/88A patent/AU1887188A/en not_active Abandoned
- 1988-07-09 KR KR1019880008535A patent/KR890001613A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0193418A (en) | 1989-04-12 |
| NO883038D0 (en) | 1988-07-07 |
| FR2617829A1 (en) | 1989-01-13 |
| EP0298843A1 (en) | 1989-01-11 |
| BR8803441A (en) | 1989-01-31 |
| AU1887188A (en) | 1989-01-12 |
| KR890001613A (en) | 1989-03-28 |
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