WO2013177729A1 - Procédé pour la séparation de terre rare par recyclage couplé de matières - Google Patents

Procédé pour la séparation de terre rare par recyclage couplé de matières Download PDF

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Publication number
WO2013177729A1
WO2013177729A1 PCT/CN2012/001294 CN2012001294W WO2013177729A1 WO 2013177729 A1 WO2013177729 A1 WO 2013177729A1 CN 2012001294 W CN2012001294 W CN 2012001294W WO 2013177729 A1 WO2013177729 A1 WO 2013177729A1
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Prior art keywords
rare earth
acid
oxalic acid
solution
extraction
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PCT/CN2012/001294
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English (en)
Chinese (zh)
Inventor
廖春生
刘艳
张玻
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五矿（北京）稀土研究院有限公司
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Publication of WO2013177729A1 publication Critical patent/WO2013177729A1/fr

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    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • C22B59/00—Obtaining rare earth metals
    • 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

Definitions

  • the invention belongs to the technical field of rare earth separation, and particularly relates to a rare earth separation method for material linkage recycling. Background technique
  • Rare earth is a general term for all fifteen lanthanides of lanthanum and cerium. Because of their similar chemical properties, they coexist in minerals. The excellent intrinsic properties of light, electricity, magnetism and catalysis of each element often require a single high-purity rare earth. Fully reflected. Therefore, separation and purification have become an important process in the rare earth material industry.
  • the separation and purification of rare earths is usually carried out by solvent extraction and separation. This method has the advantages of large processing capacity, fast reaction speed and good separation effect. It is the main production method for rare earth separation at home and abroad.
  • the extractant used for rare earth extraction and separation is mainly an acidic phosphorus extractant, such as: P204 (2-ethylhexylphosphoric acid), P507 (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) and Cyanex272 (two (2, 2, 4, 4-trimethylpentyl)phosphonic acid), P229 (bis(2-ethylhexyl)phosphonic acid), etc.).
  • the separation and purification process of rare earth extraction mainly includes separate processes such as dissolution, extraction and precipitation.
  • the dissolving process mainly refers to the process of dissolving rare earth oxides or carbonates with an acid, which can be expressed by the following formula:
  • the acidic phosphorus extractant needs to be saponified by ammonia or an alkaline substance such as sodium hydroxide or ammonium hydrogencarbonate, and the saponified organic phase is a rare earth soap.
  • the saponification reaction can be represented by the following equation (where HA represents an acidic extractant):
  • REA 3 + 3HC1 REC1 3 + 3HA ( washed, back extracted) (6) via a single rare earth oxalate precipitate (according to Equation (7)), the re-ignition of a rare earth oxide.
  • the solution step can also be carried out by directly dissolving the carbonate with an acidic organic extractant, and the hydrogen ions in the extractant are consumed by the carbonate to cause the rare earth to enter the organic extract.
  • a rare earth carbonate solvent extraction separation process application number: 200810155328.5, application date October 27, 2008, public day March 18, 2009
  • a method of pretreatment of organic extractant and Its application application number: 200710163930.9, application date October 11, 2007, publication date September 10, 2008
  • “Saponification method of an organic extractant” application number: 200610001858.5, application date January 2006
  • the public day is August 16th, 200th).
  • the above method uses an acid extractant to directly dissolve the rare earth, and prepares the organic phase loaded with the mixed rare earth to replace the aqueous phase liquid into the tank, and can utilize the acid in the organic phase to reduce the acid consumption of the raw material dissolved, but still needs to consume the acid and alkali for separation.
  • the oxalic acid precipitation wastewater contains oxalic acid and a large amount of inorganic acid, and the conventional treatment method is lime neutralization precipitation treatment.
  • the object of the present invention is to provide a rare earth separation method for the coordinated use of two materials, which can perform the acid separation of the rare earth separation process including the raw material dissolution, the extraction separation and the oxalic acid precipitation.
  • the material can be recycled and recycled to avoid the alkali saponification process of the extractant.
  • the inorganic acid can be recycled and washed, and stripped.
  • the rare earth separation and purification process does not consume alkali and inorganic acid, does not produce salty wastewater, and has low production cost and is environmentally friendly.
  • the technical solution adopted by the present invention is: Dilution of material linkage recycling
  • the soil separation method includes the following steps:
  • the ratio of 0.1-20:1 is fully mixed, and the rare earth saponification reaction is directly carried out to obtain a rare earth-loaded organic phase and an acid-containing rare earth solution;
  • step (in) mixing the raw material to be extracted obtained in the step (I) with the rare earth-loaded organic phase obtained in the step (( )) in a cascade extraction tank for the rare earth exchange purification reaction, after multiple washings and stripping the organic phase, respectively Single rare earth solution and blank extractant A, blank extractant A is returned to step (II) for reuse;
  • step (IV) mixing the single rare earth solution obtained in the step (III) with the oxalic acid solution or the solid oxalic acid to precipitate the rare earth ions, separating and washing the rare earth oxalate precipitate to obtain the oxalic acid precipitation wastewater containing the oxalic acid and the inorganic acid;
  • Step (V) of the inorganic acid-containing equilibrium aqueous phase is returned to step (I) to dissolve the rare earth carbonate or oxide, or return to step (III) to wash and strip the organic phase;
  • the volume ratio of the rare earth soap material to the blank extractant A diluted with the organic solvent is 1-5:1, and the extracting agent A is selected from the group consisting of 2-ethylhexylphosphoric acid (P204), 2 -ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507;), bis(2,4,4-tridecylpentyl)phosphonic acid (Cyanex272) and di(2-ethylhexyl)phosphonate ( One or more of P229), the organic solvent is selected from one or more of industrial kerosene, sulfonated kerosene, mineral spirit oil, isooctanol, and octanol, and the concentration of extractant A is 0.5-1.8.
  • the extracting agent A is selected from the group consisting of 2-ethylhexylphosphoric acid (P204), 2 -ethylhexylphosphonic acid mono-2-eth
  • the rare earth soap in the step ( ⁇ ) is a single rare earth solution or a rare earth solution obtained by extracting and grouping, and the rare earth content thereof is 0.1-2.5 mol/L in terms of REO.
  • the rare earth solution obtained by the extraction grouping is preferably a solution containing the intractable rare earth component obtained by the extraction grouping.
  • step (VII) when the rare earth soap in the step ( ⁇ ) is a single rare earth solution, in step (VII), the rare earth acid-containing solution obtained by the saponification of the rare earth is combined with the same single rare earth solution obtained in the step (III), and the step is adopted ( The method in IV) precipitates rare earth ions. Further, in the step (V), the volume ratio of the oxalic acid precipitation wastewater to the extractant B diluted with the organic solvent is 0.5-5:1, and the extractant B is tributyl phosphate (TBP) and/or bismuth subruthenium phosphate.
  • TBP tributyl phosphate
  • the heptyl ester (P350) the organic solvent is selected from one or more of industrial kerosene, sulfonated kerosene, mineral spirits, isooctyl alcohol, and octanol, and the concentration of the extractant B is 0.1-1.8 mol/L.
  • the oxalic acid-containing organic phase is back-extracted with water to obtain an oxalic acid solution, and the oxalic acid is returned to the step (IV) to precipitate the rare earth ions; or the rare earth solution is used to back-extract the organic phase supporting the oxalic acid to obtain the oxalic acid.
  • the aqueous phase containing the inorganic acid is returned to the step (I) before the use of the mineral acid-containing equilibrium aqueous phase and the organic solvent-diluted extractant C by volume ratio of 0.1-20:1
  • the ratio of the mixed extract is concentrated, and the concentrated inorganic acid is returned to the step (I), and the aqueous phase is used as the bottom water of the solution or the water of the oxalic acid solution or the oxalic acid rare earth precipitate is used for the water washing cycle.
  • the extracting agent C is selected from the group consisting of primary carbon primary amine (N1923), trialkyl decylamine, N-decadiene (trialkyl decyl) amine, and bis(1-isobutyl-3,5- Dimercaptohexyl)amine, bis(1-fluorenylheptyl)amine, hydrazine, hydrazine-bis(1-decylheptyl)acetamide, tri-n-octylamine, triisooctylamine, trioctyl tertiary amine ( ⁇ 235), one or more of trilaurylamine and tris(2-ethylhexylamine), the organic solvent being selected from the group consisting of industrial kerosene, sulfonated kerosene, mineral spirits, isooctyl alcohol, and octanol
  • the organic solvent being selected from the group consisting of industrial kerosene, s
  • Another rare earth separation method utilizing the material linkage recycling provided by the invention includes a solvent, Extraction separation, oxalic acid precipitation and washing process, the extraction and separation process comprises saponification loading rare earth and rare earth exchange purification step, and the inorganic acid solution or the rare earth solution containing inorganic acid produced by extraction separation, oxalic acid precipitation and washing process is diluted with organic solvent
  • the extracting agent C is thoroughly mixed according to the volume ratio of 0.1-20:1, and the concentrated inorganic acid is extracted and extracted, and the concentrated inorganic acid is returned to the dissolving step for recycling, and the rare earth-containing low acid aqueous phase is returned to the saponification supporting rare earth step, and the rare earth is not contained.
  • the low acid aqueous phase is used as a bottom water for the solution or a water rinse for the bottom water of the oxalic acid solution or the rare earth oxalate precipitate.
  • the "mineral acid solution or rare earth solution containing inorganic acid" referred to in the method means a solution containing no oxalic acid and containing an inorganic acid, and the inorganic acid is mainly hydrochloric acid and/or nitric acid and/or sulphuric acid.
  • the above “inorganic acid solution or rare earth solution containing inorganic acid” includes a rare earth acid-containing rare earth solution after saponification of rare earth generated by a rare earth saponification step, a rare earth solution containing inorganic acid generated in an excess of rare earth in the oxalic acid precipitation step, and a low concentration in the washing step.
  • the extracting agent C is selected from the group consisting of primary carbon primary amine (N1923), trialkyl decylamine, decane-dodecene (trialkyl decyl) amine, and bis(1-isobutyl-3,5-di Amidinoyl, bis(1-indenylheptyl)amine, hydrazine, hydrazine-bis(1-decylheptyl)acetamide, tri-n-octylamine, triisooctylamine, trioctylalkyl tertiary amine ⁇ 235 ), one or more of trilaurylamine and tris(2-ethylhexylamine), the concentration of extractant C is 0.1-1.8 mol/L, and the organic solvent is selected from the group consisting of industrial kerosene, sulphurized kerosene, One or more of solvent oil, isooctanol, and oc
  • the saponification loading rare earth step is carried out by directly mixing the rare earth soap material with the blank extractant A diluted with the organic solvent at a volume ratio of 1-20:1, and directly performing the rare earth saponification reaction;
  • the extracting agent A is selected from the group consisting of 2- Ethylhexylphosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, bis(2,4,4-tridecylpentyl)phosphonic acid and di(2-ethylhexyl)phosphonate
  • One or more of the extractant A has a concentration of 0.5 to 1.8 mol/L.
  • the rare earth soap material is a single rare earth solution or a rare earth solution obtained by extracting and grouping, and the rare earth content thereof is 0.1-2.5 mol/L in terms of REO.
  • the rare earth separation method utilizing the material linkage cycle provided by the invention enables the independent processes to be uniformly coordinated under the premise of fully meeting the process objectives.
  • the hydrochloric acid required for the dissolution of the rare earth raw material corresponds to the hydrochloric acid produced by the precipitation of rare earth oxalic acid (see reactions (1), (2) and reaction (7)); saponification, extraction step reaction (3) (4) (5) can be combined to directly carry out the rare earth saponification reaction (8); the acid extractant extracts the rare earth displaced hydrochloric acid to match the hydrochloric acid required for washing and stripping (see reactions (6), (8) ).
  • the direct rare earth saponification process (see reaction (8)) is used, and the produced inorganic acid is recycled;
  • the acid in the oxalic acid precipitation mother liquor that needs to be neutralized and discharged in the current process should be properly treated and reused. It should meet the acid demand of the raw material dissolution and extraction separation process, and the raw material can be dissolved and extracted.
  • the intermediate materials in the process of rare earth precipitation washing are used in the whole process, so that the whole process of rare earth separation is equivalent to equation (9), and only equivalent equivalent of oxalic acid is consumed:
  • the material linkage separation method in the process of the overall material linkage recycling, the method of directly preparing the rare earth loaded organic phase, and recycling all the acid separated in the saponification and precipitation mother liquor for the rare earth
  • the chemical reagent consumed in the whole process of rare earth separation including raw material dissolution, extraction separation and oxalic acid precipitation is only oxalic acid
  • the hydrogen ion is used for dissolving the raw material
  • the oxalate is used for precipitating rare earth ions.
  • waste acid generated by the saponification of rare earth is extracted and recovered and used in the production process.
  • the entire rare earth separation process does not require additional inorganic acid from the dissolution to the extraction and stripping.
  • the alkali added for neutralizing the acidic wastewater is omitted, and the reagent cost in production is greatly reduced.
  • the oxalic acid precipitation wastewater, the saponification wastewater, and the extraction washing water are recycled after the extraction of oxalic acid and/or inorganic acid to improve the water utilization rate and reduce the unit water consumption in the production process.
  • FIG. 1 is a flow chart of a rare earth separation method utilizing the material linkage recycling provided by the present invention. detailed description
  • the bismuth carbonate dissolved in hydrochloric acid (La, Ce molar ratio is 60:40), the solution obtained by dissolution is used as the raw material to be extracted, and P204 is used as the extracting agent, and La/Ce separation is carried out in a 60-stage 30 L main extraction tank.
  • the organic phase flow rate was 6 L/min and the concentration was 1.5 mol/L (diluted with a mixed organic solvent of 30% octanol + 70% sulfonated kerosene).
  • Another 10 grade 30L sub-extraction tank was used for acid extraction and recovery.
  • Trialkyl decylamine was used as the extractant at a flow rate of 5 L/min and a concentration of 1.0 mol/L (diluted with sulfonated kerosene).
  • the organic phases of the two extraction tanks flow from front to back.
  • the concentration of (LaCe)Cl 3 in the main extraction tank is 1 mol/L, and is added from the 30th stage at a flow rate of 1.5 L/min, and the 3.0 mol/L washing acid is added from the 50th stage at 0.4 L/min, 3.0 mol.
  • the /L stripping acid was added from the 60th stage at 0.7 L/min.
  • the easy-to-extract component Ce enters the organic phase, and is purified by multiple extractions and acid washing. After stripping acid stripping, a total of 0.7 L / min cerium chloride solution is discharged from the 51st stage, and the rare earth concentration is about 0.89 mol/L.
  • the process of extracting and concentrating the inorganic acid by the acid-containing rare earth solution after saponification is as follows: In the first 10 stages of the main extraction tank and the auxiliary extraction tank, the 0.9 L/min ruthenium chloride solution is firstly contacted with the trialkyl decylamine of the 10th stage of the auxiliary extraction tank for extraction, and then with the main extraction tank.
  • the P204 of the 10th stage is contacted for extraction, and the cerium chloride solution flowing out from the 10th stage of the main extraction tank is sequentially followed by the secondary extraction tank.
  • the tertiary tridecylamine of the ninth stage and the P204 of the ninth stage of the main extraction tank are contacted for extraction, and so on, until the first stage of the autonomous extraction tank outputs 0.9 L/min of an aqueous solution substantially free of rare earth and having a pH of about 4. recycle and re-use.
  • the organic phase of P204 was loaded with La
  • the organic phase of the trialkylguanamine was loaded with 0.54 mol/L of hydrochloric acid.
  • the 11th grade of the main extraction tank produces an additional 1.OL/min ruthenium chloride solution (ie, another portion of the acid-containing rare earth solution produced by the saponification loading rare earth step shown in Figure 1) precipitated with solid oxalic acid, oxalic acid precipitated wastewater and 1.5 mol/L tributyl phosphate (diluted with sec-octanol) was mixed with 20:1, and a small amount of oxalic acid was extracted and extracted to obtain an aqueous solution of 1.0 OL/min acidity of 3.0 mol/L, of which 0.4 L/ Min is returned to the main extraction tank as acid washing, and the remaining 0.6 L/min of hydrochloric acid is dissolved in cesium carbonate together with hydrochloric acid extracted by trialkylguanamine in the auxiliary extraction tank to obtain a cerium chloride solution to be extracted and separated, and the specific operation is carried out.
  • the process is shown in Figure 1.
  • the addition of stripping acid, acid addition and La, Ce liquid solution and rare earth saponification process are the same as in Example 1.
  • the cerium chloride soap material is mixed with the blank P204/P507 mixed extractant for saponification reaction, and the P204/P507 organic phase is loaded.
  • the organic phase of La, ⁇ , ⁇ -bis(1-decylheptyl)acetamide is loaded with hydrochloric acid.
  • the oxalic acid precipitation wastewater is mixed with 0.5 mol/L didecyl heptyl phosphate (diluted with isooctyl alcohol) according to 1:1, and a small amount of oxalic acid is extracted and recovered.
  • the niobium oxide is dissolved in nitric acid (La, Ce molar ratio is 60:40), and the obtained solution is used as the raw material to be extracted, and P507 is used as the extracting agent, and the concentration of the extracting agent is 1.8 mol/L (using 20% No. 200 solvent oil + 40) % industrial kerosene + 40% octanol diluted), La/Ce separation in a 60-stage 30L main extraction tank with an organic flow rate of 6 L/min. Another 10 grade 30L sub-extraction tank was used for acid extraction and recovery, using trilaurylamine as extractant, flow rate 5L/min, concentration 1.5mol/L (diluted with 20% solvent oil + 80% kerosene kerosene). The organic phases of both extraction tanks flow from front to back.
  • the 1.9L/min lanthanum nitrate solution was discharged, and 1.5L/min was taken as the rare earth soap material to carry out the saponification reaction with the blank organic phase.
  • the process of extracting and concentrating the inorganic acid from the acid-containing rare earth solution after saponification was carried out. .
  • the specific operation is as follows: in the first 10 stages of the main extraction tank and the auxiliary extraction tank, the 1.5 L/min lanthanum nitrate solution is firstly extracted in the 10th stage of the auxiliary extraction tank by trilaurylamine, and 10 times in the main extraction tank. The phase is contacted with P507 for extraction.
  • the cerium nitrate solution flowing out of the 10th stage of the autonomous extraction tank is sequentially contacted with the secondary phase tank of the secondary extraction tank and the 9th organic phase of the main extraction tank for extraction, and so on. Finally, the P507 organic phase is loaded with 0.135 mol/ The lanthanum of L, the laurylamine organic phase was loaded with 0.53 mol/L of nitric acid. From the first stage of the main extraction tank, 1.5 L/min of saponified acid-containing rare earth solution, wherein cerium nitrate is 0.36 mol/L, and S history is 0.15 mol/L.
  • the acid-containing rare earth solution is precipitated with oxalic acid, and after the oxalic acid in the oxalic acid precipitation wastewater is recovered by using tributyl phosphate, the aqueous phase is 1.5 L/min of nitric acid at a concentration of 1.23 mol/L.
  • This nitric acid is combined with the nitric acid extracted with trilaurylamine to dissolve the cerium oxide to obtain a cerium nitrate solution to be extracted.
  • the other 0.4L/min cerium nitrate solution produced in the 11th stage of the main extraction tank is precipitated with solid oxalic acid, and the oxalic acid precipitation wastewater is mixed with 1.0 mol/L tributyl phosphate in a ratio of 10:1, and a small amount of oxalic acid is extracted and recovered.
  • An aqueous solution having an acidity of 3.0 mol/L of 0.4 L/min was obtained, and the acid was fed back to the main extraction tank.
  • the rare earth soap material is a difficult-to-extract component obtained by the extraction and separation of the rare earth leaching solution obtained by roasting sulfuric acid and water leaching of the Baotou mixed rare earth ore.
  • the REO content is 15g/L
  • the pH is 3, and the main component is La.
  • the rare earth soap material was mixed with P204 blank organic phase to carry out rare earth saponification reaction, and the concentration of P204 was 1.2 mol/L (diluted with solvent oil No. 200).
  • the rare earth saponification process uses 8-stage extraction tank in series countercurrent extraction. The volume ratio of water phase to oil phase is 2:1. In this process, the hydrogen ions in the organic phase are exchanged into the water phase by rare earth, and most of the rare earth in the water enters the organic phase.
  • the rare earth-containing rare earth solution obtained by saponification of rare earth contains H+0.27mol/L and REO 0.5g/L, and the organic phase flowing out is the rare earth-loaded organic phase, and enters the rare earth extraction separation tank for subsequent linkage extraction separation.
  • an oxalic acid solution is added to precipitate rare earth ions, and an excess of oxalic acid is controlled at the end of the precipitation, filtered, and washed to obtain an oxalic acid precipitation wastewater containing H+ 0.08 mol/L of rock-filled acid and 0.01 mol/L of oxalic acid.
  • the oxalic acid precipitation wastewater and the decyl heptyl phosphate extractant were mixed to extract oxalic acid in a ratio of 10:1 by volume, and the concentration of dinonyl heptyl phosphate was 0.5 mol/L (diluted with solvent oil No. 260).
  • the equilibrium organic phase loaded with oxalic acid was back extracted with Imol/L NaOH solution to obtain sodium oxalate solution, and the equilibrium aqueous phase was dilute acid solution.
  • the separated dilute acid solution is mixed with 1.8 mol/L primary amine N1923 (diluted with deuterated kerosene) in a volume ratio of 20:1, and subjected to a second-stage countercurrent extraction, and the sulfuric acid is extracted into the organic phase by the amine extractant, water
  • the regeneration cycle can be used as the water immersion liquid of the sulfuric acid roasting ore; the extracted and concentrated sulfuric acid is used to dissolve 40% of the Baotou ore mixed rare earth carbonate to obtain 30 g/L of mixed rare earth sulfate. Liquid.
  • the 1.5 mol/L SmCl 3 solution obtained after extraction and separation was mixed with the blank organic phase with P507 as extractant to carry out rare earth saponification reaction.
  • the concentration of P507 was 0.5 mol/L (using 10% isooctanol + 90% deuterated kerosene)
  • the mixed organic solvent is diluted).
  • the rare earth saponification process uses a 4-stage extraction tank in series countercurrent extraction.
  • the volume ratio of the aqueous phase to the oil phase is 20:1.
  • the hydrogen ions in the organic phase are exchanged into the aqueous phase by the rare earth, and the aqueous phase flowing out contains H + 0.01 mol. /L of the acid-containing rare earth solution, the organic phase flowing out is the rare earth-loaded organic phase, and enters the rare earth extraction separation tank for subsequent linkage extraction separation.
  • the rare earth acid-containing solution obtained by saponifying the rare earth is mixed with a 1.8 mol/L trioctyl tertiary amine extractant (diluted with kerosene) in a volume ratio of 20:1, and subjected to a second-stage countercurrent extraction, and the hydrochloric acid is extracted with an amine extractant.
  • the solution is extracted into an organic phase, and the aqueous phase is a SmCl 3 solution having a pH of 4, which is recycled as a rare earth soap material for preparing a rare earth soap.
  • the concentrated hydrochloric acid extracted by the trioctyl tertiary amine extractant is used to dissolve the southern ore mixed oxidized rare earth (REO content 92%), and the rare earth is dissolved to obtain a mixed rare earth liquid of 64 g/L.
  • the oxalic acid precipitation wastewater was mixed with 0.3 mol/L bis(1-isobutyl-3,5-didecylhexyl)amine extractant (diluted with octanol) in a volume ratio of 0.5:1, and subjected to a 2-stage countercurrent extraction.
  • the nitric acid is extracted into the organic phase by an amine extractant, and the aqueous phase is a Dy(N0 3 ) 3 solution having a pH of 4, which is recycled to the oxalic acid precipitation step.
  • the concentrated nitric acid is extracted by di(1-isobutyl-3,5-dimercaptohexyl)amine extractant to dissolve the rare earth carbonate (REO content of 30%), and the rare earth is dissolved to obtain a mixture of 20g/L. Rare earth liquid.

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Abstract

L'invention porte sur un procédé pour la séparation d'un terre rare par recyclage couplé de matières. Le procédé comprend : l'utilisation d'une phase organique préparée par mélange d'un agent d'extraction et d'une pâte de neutralisation de terre rare et chargée du terre rare pour une séparation par extraction couplée subséquente et la réutilisation de celle-ci dans la dissolution de matières premières après extraction et concentration de l'acide inorganique dans la phase aqueuse restante ou le recyclage de celle-ci après précipitation du terre rare dans celle-ci avec de l'acide oxalique ; l'extraction de la solution de terre rare après purification par séparation, à l'aide d'acide oxalique pour faire précipiter le terre rare, l'extraction de la solution mère précipitée contenant l'acide oxalique et l'acide inorganique, la réutilisation de l'acide oxalique extrait pour faire précipiter le terre rare et l'utilisation de l'acide inorganique restant directement pour le lavage, pour un processus d'extraction inverse ou pour la dissolution de matières premières après extraction et concentration. Le procédé permet de recycler les matières intermédiaires produites pendant la séparation du terre rare entre des sections du procédé, il permet d'éviter la saponification alcaline de l'agent d'extraction et il permet de mettre en œuvre des processus tels qu'une dissolution, un lavage et une extraction inverse des matières premières en n'utilisant que l'acide inorganique recyclé.
PCT/CN2012/001294 2012-05-28 2012-09-21 Procédé pour la séparation de terre rare par recyclage couplé de matières WO2013177729A1 (fr)

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CN201210170171XA CN102676853B (zh) 2012-05-28 2012-05-28 物料联动循环利用的稀土分离方法

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CN107828961A (zh) * 2017-11-02 2018-03-23 中国科学院过程工程研究所 一种稀土元素离子的萃取方法及得到的稀土富集液
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CN110560018A (zh) * 2019-09-09 2019-12-13 中国科学院城市环境研究所 一种P2O4复合UiO-66材料的合成及其用于吸附分离液晶面板中铟的方法
CN111874936A (zh) * 2020-07-03 2020-11-03 福建省长汀金龙稀土有限公司 一种用于制备纳米稀土氧化物的原料的制备方法
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CN113651352A (zh) * 2021-09-02 2021-11-16 甘肃稀土新材料股份有限公司 一种从高钙氯化镧铈溶液中制备低钙碳酸镧铈的方法
CN115652113A (zh) * 2022-10-28 2023-01-31 广东省科学院资源利用与稀土开发研究所 一种从海洋稀土硫酸浸出液中萃取分离稀土的方法
CN115652113B (zh) * 2022-10-28 2023-10-10 广东省科学院资源利用与稀土开发研究所 一种从海洋稀土硫酸浸出液中萃取分离稀土的方法
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