WO2014137238A1 - A method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals - Google Patents

A method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals Download PDF

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WO2014137238A1
WO2014137238A1 PCT/RU2013/000990 RU2013000990W WO2014137238A1 WO 2014137238 A1 WO2014137238 A1 WO 2014137238A1 RU 2013000990 W RU2013000990 W RU 2013000990W WO 2014137238 A1 WO2014137238 A1 WO 2014137238A1
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rem
extraction
phase
acid
rare
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Inventor
Mikhail Vladimirovich Genkin
Aleksey Vladimirovich EVTUSHENKO
Aleksey Aleksandrovich KOMKOV
Alfiya Minerovna SAFIULINA
Vasiliy Sergeevich SPIRIDONOV
Sergey Vladimirovich SHVETSOV
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Uralchem JSC
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Priority to EP13877069.8A priority Critical patent/EP2964794B1/en
Priority to US14/773,739 priority patent/US9896743B2/en
Priority to CN201380076320.9A priority patent/CN105164283B/en
Priority to MA38442A priority patent/MA38442B1/en
Publication of WO2014137238A1 publication Critical patent/WO2014137238A1/en
Priority to TN2015000374A priority patent/TN2015000374A1/en
Anticipated expiration legal-status Critical
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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
    • C22B59/00—Obtaining rare earth metals
    • 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
    • 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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • 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 present invention relates to technologies for liquid extraction, in particular, preparing concentrate of rare-earth metals (REM) in nonferrous and ferrous metallurgy, in the course of treatment of waste of the chemical and metallurgical industries, as well as for purification of mine water and industrial wastewater.
  • REM rare-earth metals
  • Liquid extraction processes are widely used for recovering and concentrating valuable components, in particular REM.
  • Isolation of REM concentrate from nitrate solutions using organic extractants based on neutral organophosphorous compounds (preferably tributylphospate - TBP) and isolation of REM concentrate from chloride solutions using organic extractants based on organophosphorous acids (preferably di-(2-ethylhexyl)phosphoric acid - DEHPA) is disclosed in the art (e.g. Chemistry and technology of rare and trace elements (rus). Part 2. Ed. Bolshakov .A., Moscow, High School, 1976, p. 360; Slavetsky A.I. etc. Extraction of REM by DEHPA and TBP. Radiochemistry (rus), 1989, No. 1 , p.
  • the method for extracting rare metals from mixtures thereof using countercurrent re- extraction with a mineral acid solution, in particular distilled water acidified to a concentration of 0.05 mol/L with HNO3 or acidified to a concentration of 1.0 mol/L with hydrochloric acid is also known (RU patent 2049133).
  • the disadvantage of this method is incomplete REM recovery and obtaining REM in form of a dilute solution of low concentration.
  • a method for processing phosphate rare earth concentrate comprising treatment of the concentrate by heating in the presence of an excess of oxalic acid to precipitate oxalates of REM is known (RU patent 2344079), but this method is limited due to use of expensive oxalic acid.
  • REM re-extraction is usually carried out with concentrated acids, water (in particular, at an elevated temperature), carbonate or alkaline solutions.
  • Liquid phase re- extraction with concentrated acids is suitable for processes with organic extracts having a high content of REM. If the REM concentration in the organic phase is low, as often happens at the extraction of the target component from dilute salt solutions having a high content of impurities, acid re-extraction allows solutions of low concentration up to 10 g/L of REM to be obtained.
  • Re-extraction with carbonate or alkaline solutions allows one to obtain a concentrated precipitate of REM, however it is associated with losses of acid passed into the organic solution during the REM extraction step, significant consumption of re-extractant, the appearance of large volumes of solutions of alkali metal salts or ammonium salts, with increased losses of the organic extractant due to its increased solubility in an aqueous phase.
  • Water re-extraction possesses all these disadvantages, and re-extraction with oxalate solutions is limited due to the use of expensive oxalic acid.
  • the goal of the present invention is developing a method for re-extraction of REM from organic solutions in the form of a solid phase concentrate without neutralization of the acid present in the organic phase by using commercially available cheap reagents.
  • REM is used to indicate lanthanides and yttrium.
  • Ln is used for these elements.
  • the hydrogen cations present in the re-extractant have high activity and displace the REM atoms from the organic complex. Due to poor solubility in the aqueous phase, REM sulfates precipitate, thus shifting the equilibrium towards re-extraction.
  • the REM extraction is usually carried out from nitrate or chloride solution, therefore the organic phase contains the corresponding acid. Re-extraction of this acid by a cation mechanism does not occur due to the high activity of sulfuric acid in the aqueous re-extracting phase. Further, exchange of nitrate and chloride ions for sulfate ions between the organic and aqueous re-extracting phases also does not occur.
  • Phosphine oxide in kerosene, tributylphosphate in kerosene, di-(2- ethylhexyl)phosphoric acid (DEHPA) and other extractants known in the art can be used as an organic extractant for REM compounds.
  • the preferable ratio between organic and aqueous phase is 500: 1 to 1 :2.
  • Recovery of REM into the concentrate according to the method of the present invention is up to 99% in the course of one stage of the re-extraction.
  • the extractant may contain sulphuric acid, sulphate anions. If extraction of REM is carried out from calcium solutions, phase contact during the organic phase recycling leads to formation of precipitate, which can clog the extraction equipment (for example, box type mixer-settlers). Therefore, before the return to the extraction stage, the extractant is washed with calcium salt solution, and the formed precipitate is separated.
  • a raffinate of REM extraction obtained after filtration of REM concentrate is preferably used for washing.
  • REM extract 100 volume parts of REM extract in undiluted tributyl phosphate (TBP) containing 1.5 g/L of Ln 2 0 3 and 120 g/L of HNO3 were treated with 10 parts of 60 wt.% sulphuric acid.
  • the acid (aqueous) phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried.
  • the concentrate contained 45% Ln 2 (3 ⁇ 4 (78% Ln 2 (S0 4 )3 in terms of sulphate).
  • the acid contained 2.2 g/L of Ln 2 0 3 and 0.2 g/L of nitrate anions.
  • the organic phase was treated again with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was ⁇ 0.01 g/L. Thus, the complete re-extraction was carried out in the course of one stage.
  • the organic extractant was treated with 100 parts of a solution containing 60 g/L HNO3 and 200 g/L Ca(N(3 ⁇ 4)2.
  • aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed.
  • the phases were separated.
  • the acid content in the organic extractant was 128 g/L, the acid content in aqueous solution was 64 g/L.
  • REM extract 100 volume parts of REM extract in undiluted tributyl phosphate (TBP) containing 1.5 g/L of Ln 2 C>3 and 120 g/L of HNO3 were treated with 50 parts of solution containing 30 wt.% sulphuric acid and 13 wt.% MgS0 4 .
  • the aqueous phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried.
  • the concentrate contained 42% Ln 2 (3 ⁇ 4 (73% Ln 2 (S0 4 )3 in terms of sulphate).
  • the aqueous phase contained 3.2 g/L of Ln 2 (3 ⁇ 4 and 0.15 g/L of nitrate anions.
  • the organic phase was treated with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was ⁇ 0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
  • the organic extractant was treated with 100 parts of a solution containing 60 g/L HNO3 and 200 g/L Ca(N0 3 ) 2 .
  • aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed.
  • the phases were separated.
  • the acid content in the organic extractant was 120 g/L, the acid content in aqueous solution was 61 g/L.
  • REM extract 100 volume parts of REM extract in undiluted triburyl phosphate (TBP) containing 1.5 g/L of Ln 2 0 3 and 120 g/L of HN0 3 were treated with 10 parts of solution containing 240 g/L HNO3 and 300 g/L K2SO4.
  • the aqueous phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried.
  • the concentrate contained 34,5% Ln 2 0 3 (82% KLn(S0 4 ) 2 *H 2 0 in terms of sulphate).
  • the aqueous phase contained 0.5 g/L of Ln 2 0 3 and 232 g/L of H 0 3 .
  • the organic phase contained 123 g/L of HNO3.
  • the organic phase was treated with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was ⁇ 0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
  • the organic phase was treated with 10 parts of 45 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was ⁇ 0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
  • the organic extractant was treated with 100 parts of a solution containing 60 g/L HN0 3 and 200 g/L Ca(N0 3 ) 2 .
  • aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed.
  • the phases were separated.
  • the acid content in the organic extractant was 30 g/L, the acid content in aqueous solution was 60 g/L.
  • Example 5 500 volume parts of REM extract in 30% solution of di-(2-ethylhexyl)phosphoric acid in de-aromatized kerosene containing 2.1 g/L of Ln 2 0 3 were treated with 1 part of 70 wt.% H2SO4. The acid (aqueous) phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried.
  • the concentrate contained 51% Ln 2 03 (88,5% Ln 2 (SC>4)3 in terms of sulphate).
  • the acid phase contained 3.5 g L of Ln 2 ( 1 ⁇ 2.
  • the organic phase was treated with 10 parts of 70 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was ⁇ 0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
  • the organic extractant was treated with 100 parts of a solution containing 50 g/L CaCl 2 .
  • a solution containing 50 g/L CaCl 2 was brought into contact, copious white precipitate of calcium sulfate was formed.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Geochemistry & Mineralogy (AREA)
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Abstract

The present invention relates to a method for recovery of rare earth metals (REM) from diluted aqueous acidic solutions comprising steps of liquid-phase extraction of REM into an organic phase and re-extraction of REM from the organic phase, wherein the re-extraction is carried out by precipitation of REM as a solid phase in the form of a poorly soluble salt of a strong acid (pKa<0). Recovery of REM into the concentrate is up to 99% in the course of one stage of the re-extraction.

Description

A METHOD FOR RE-EXTRACTION OF RARE-EARTH METALS FROM ORGANIC SOLUTIONS AND PREPARING CONCENTRATE OF RARE-EARTH METALS
Field of the invention
The present invention relates to technologies for liquid extraction, in particular, preparing concentrate of rare-earth metals (REM) in nonferrous and ferrous metallurgy, in the course of treatment of waste of the chemical and metallurgical industries, as well as for purification of mine water and industrial wastewater.
Background of the invention
Liquid extraction processes are widely used for recovering and concentrating valuable components, in particular REM.
Isolation of REM concentrate from nitrate solutions using organic extractants based on neutral organophosphorous compounds (preferably tributylphospate - TBP) and isolation of REM concentrate from chloride solutions using organic extractants based on organophosphorous acids (preferably di-(2-ethylhexyl)phosphoric acid - DEHPA) is disclosed in the art (e.g. Chemistry and technology of rare and trace elements (rus). Part 2. Ed. Bolshakov .A., Moscow, High School, 1976, p. 360; Slavetsky A.I. etc. Extraction of REM by DEHPA and TBP. Radiochemistry (rus), 1989, No. 1 , p. 25-31 ; Stryapkov A.V., Salnikova E.V. Influence of amine nature on REM extraction by a mixture of amines and alkylphosphorous extractants. Vestnik OGU (rus), 2004, No. 5, p. 121-124).
The researchers pay considerable attention to the transfer of certain compounds from aqueous solutions into organic (extraction processes) and substantially less attention to the reverse processes (re-extraction processes).
The method for extracting rare-earth elements from phosphogypsum by treatment with nitric acid and subsequent extraction of rare earth elements (REE) by phosphine oxide is known (Martynova I.N. et al. Research of distribution of REE in the course of extraction from acidic nitrate-phosphate solutions. Collected articles "Processing and physico-chemical properties of compounds of rare elements. Apatity, 1984, pp. 6-8 (Rus)). The disadvantage of this method is the need for expensive trialkyl phosphine oxide and the impossibility of complete liquid-phase removal of REE from the organic phase. Furthermore, because of the high loss of trialkyl phosphine oxide with the aqueous phase, this method is uneconomical and requires additional facilities for trialkyl phosphine oxide utilization.
The method for extracting rare metals from mixtures thereof using countercurrent re- extraction with a mineral acid solution, in particular distilled water acidified to a concentration of 0.05 mol/L with HNO3 or acidified to a concentration of 1.0 mol/L with hydrochloric acid is also known (RU patent 2049133). The disadvantage of this method is incomplete REM recovery and obtaining REM in form of a dilute solution of low concentration.
A method for processing phosphate rare earth concentrate comprising treatment of the concentrate by heating in the presence of an excess of oxalic acid to precipitate oxalates of REM is known (RU patent 2344079), but this method is limited due to use of expensive oxalic acid.
Thus, REM re-extraction is usually carried out with concentrated acids, water (in particular, at an elevated temperature), carbonate or alkaline solutions. Liquid phase re- extraction with concentrated acids is suitable for processes with organic extracts having a high content of REM. If the REM concentration in the organic phase is low, as often happens at the extraction of the target component from dilute salt solutions having a high content of impurities, acid re-extraction allows solutions of low concentration up to 10 g/L of REM to be obtained.
Re-extraction with carbonate or alkaline solutions allows one to obtain a concentrated precipitate of REM, however it is associated with losses of acid passed into the organic solution during the REM extraction step, significant consumption of re-extractant, the appearance of large volumes of solutions of alkali metal salts or ammonium salts, with increased losses of the organic extractant due to its increased solubility in an aqueous phase. Water re-extraction possesses all these disadvantages, and re-extraction with oxalate solutions is limited due to the use of expensive oxalic acid.
The goal of the present invention is developing a method for re-extraction of REM from organic solutions in the form of a solid phase concentrate without neutralization of the acid present in the organic phase by using commercially available cheap reagents. In the present invention, the term "REM" is used to indicate lanthanides and yttrium. Also, the symbol "Ln" is used for these elements.
The problem is solved by use of strong mineral acid (pKa<0), which forms a poorly soluble salt of REM, as an re-extractant. Use of sulphuric acid at concentration 30-70 wt.% is preferable. Use of solutions of sodium sulphate, potassium sulphate, ammonium sulphate or magnesium sulphate in sulfuric, hydrochloric or nitric acid, as well as solutions of sulphates of lanthanides in these acids, is also possible. The process is described by the following equations, where M is Na or :
2Ln3+(organic) + 3H2SO4 (aqua) Ln2(SC>4)3 | + 6H+(organic)
Ln3+(organic) + M+(aqua) + 2H2S04 (aqUa) ^ MLn(S04)2 | + 4H+(organic)
The hydrogen cations present in the re-extractant have high activity and displace the REM atoms from the organic complex. Due to poor solubility in the aqueous phase, REM sulfates precipitate, thus shifting the equilibrium towards re-extraction.
The REM extraction is usually carried out from nitrate or chloride solution, therefore the organic phase contains the corresponding acid. Re-extraction of this acid by a cation mechanism does not occur due to the high activity of sulfuric acid in the aqueous re-extracting phase. Further, exchange of nitrate and chloride ions for sulfate ions between the organic and aqueous re-extracting phases also does not occur.
Thus, acid is not washed out from the organic extractant in the course of re-extraction by sulphuric acid, the process proceeds virtually without loss of acid in an organic extractant and REM precipitate to the solid phase at a concentration of 95% (in terms of the corresponding poorly soluble salt).
Phosphine oxide in kerosene, tributylphosphate in kerosene, di-(2- ethylhexyl)phosphoric acid (DEHPA) and other extractants known in the art can be used as an organic extractant for REM compounds.
The preferable ratio between organic and aqueous phase is 500: 1 to 1 :2. Recovery of REM into the concentrate according to the method of the present invention is up to 99% in the course of one stage of the re-extraction.
After re-extraction of lanthanides, the extractant may contain sulphuric acid, sulphate anions. If extraction of REM is carried out from calcium solutions, phase contact during the organic phase recycling leads to formation of precipitate, which can clog the extraction equipment (for example, box type mixer-settlers). Therefore, before the return to the extraction stage, the extractant is washed with calcium salt solution, and the formed precipitate is separated. A raffinate of REM extraction obtained after filtration of REM concentrate is preferably used for washing. The present invention is explained in more detail below using exemplary embodiments, serving solely for illustrative purposes and not intended to limit the scope of the present invention defined by the appended claims.
Example 1.
100 volume parts of REM extract in undiluted tributyl phosphate (TBP) containing 1.5 g/L of Ln203 and 120 g/L of HNO3 were treated with 10 parts of 60 wt.% sulphuric acid. The acid (aqueous) phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried. The concentrate contained 45% Ln2(¾ (78% Ln2(S04)3 in terms of sulphate). The acid contained 2.2 g/L of Ln203 and 0.2 g/L of nitrate anions.
The organic phase was treated again with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was <0.01 g/L. Thus, the complete re-extraction was carried out in the course of one stage.
The organic extractant was treated with 100 parts of a solution containing 60 g/L HNO3 and 200 g/L Ca(N(¾)2. When the aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed. The phases were separated. The acid content in the organic extractant was 128 g/L, the acid content in aqueous solution was 64 g/L.
Example 2.
100 volume parts of REM extract in undiluted tributyl phosphate (TBP) containing 1.5 g/L of Ln2C>3 and 120 g/L of HNO3 were treated with 50 parts of solution containing 30 wt.% sulphuric acid and 13 wt.% MgS04. The aqueous phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried. The concentrate contained 42% Ln2(¾ (73% Ln2(S04)3 in terms of sulphate). The aqueous phase contained 3.2 g/L of Ln2(¾ and 0.15 g/L of nitrate anions.
The organic phase was treated with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was <0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
The organic extractant was treated with 100 parts of a solution containing 60 g/L HNO3 and 200 g/L Ca(N03)2. When the aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed. The phases were separated. The acid content in the organic extractant was 120 g/L, the acid content in aqueous solution was 61 g/L.
Example 3.
100 volume parts of REM extract in undiluted triburyl phosphate (TBP) containing 1.5 g/L of Ln203 and 120 g/L of HN03 were treated with 10 parts of solution containing 240 g/L HNO3 and 300 g/L K2SO4. The aqueous phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried. The concentrate contained 34,5% Ln203 (82% KLn(S04)2*H20 in terms of sulphate). The aqueous phase contained 0.5 g/L of Ln203 and 232 g/L of H 03. The organic phase contained 123 g/L of HNO3.
The organic phase was treated with 10 parts of 60 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was <0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
Example 4.
200 volume parts of REM extract in 20% solution of trialkylphosphine oxide in de- aromatized kerosene containing 2.1 g/L of Ln203 and 30 g/L of HNO3 were treated with 1 part of 45 wt.% H2S04. The acid (aqueous) phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried. The concentrate contained 57% Ln203 (98% Ln2(S04)3 in terms of sulphate). The acid phase contained 2.4 g L of Ln203 and 0.1 g/L of nitrate anions.
The organic phase was treated with 10 parts of 45 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was <0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
The organic extractant was treated with 100 parts of a solution containing 60 g/L HN03 and 200 g/L Ca(N03)2. When the aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed. The phases were separated. The acid content in the organic extractant was 30 g/L, the acid content in aqueous solution was 60 g/L.
Example 5 500 volume parts of REM extract in 30% solution of di-(2-ethylhexyl)phosphoric acid in de-aromatized kerosene containing 2.1 g/L of Ln203 were treated with 1 part of 70 wt.% H2SO4. The acid (aqueous) phase and precipitate were separated, the precipitate was washed with acetone until a neutral reaction was achieved and dried. The concentrate contained 51% Ln203 (88,5% Ln2(SC>4)3 in terms of sulphate). The acid phase contained 3.5 g L of Ln2 (½.
The organic phase was treated with 10 parts of 70 wt.% sulphuric acid. Precipitation was not observed, the content of REM in inorganic phase was <0.01 g/L. Thus, the complete re- extraction was carried out in the course of one stage.
The organic extractant was treated with 100 parts of a solution containing 50 g/L CaCl2. When the aqueous and organic phases were brought into contact, copious white precipitate of calcium sulfate was formed.
While the present invention is described in detail above, one skilled in the art will recognize that modifications and equivalent substitutions can be made, and such modifications and substitutions are within the scope of the present invention defined by the appended claims.

Claims

What is claimed:
1. A method for recovery of rare earth metals (REM) from diluted aqueous acidic solution comprising steps of liquid-phase extraction of REM into an organic phase and re-extraction of REM from the organic phase, wherein the re-extraction is carried out by precipitation of REM as a solid phase in the form of a poorly soluble salt of a strong acid (pKa<0).
2. The method of claim 1, wherein an extractant used as the organic phase is chosen from a group consisting of phosphine oxide in kerosene, tributylphosphate in kerosene, di-(2- ethylhexyl)phosphoric acid (DEHPA).
3. The method of claim 1, wherein the poorly soluble salt of REM is REM sulphates.
4. The method of claim 1, wherein the re-extraction of REM compounds is carried out with sulphuric acid, a mixture of H2SO4 with HC1 or HNO3, a mixture of M(HSC>4)n with H2SO4 and HC1 or HN03j where M is Na, , Mg or REM atom.
5. The method of claim 4, wherein 30-70% aqueous solution of sulphuric acid is used for the re-extraction.
6. The method of claim 1, wherein the ratio between organic phase and aqueous phase is 500: 1 to 1 :2.
7. The method of claim 2, wherein the extractant after REM re-extraction is washed with calcium salt solution, preferably with raffinate of REM extraction.
PCT/RU2013/000990 2013-03-05 2013-11-08 A method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals Ceased WO2014137238A1 (en)

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EP13877069.8A EP2964794B1 (en) 2013-03-05 2013-11-08 A method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals
US14/773,739 US9896743B2 (en) 2013-03-05 2013-11-08 Method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals
CN201380076320.9A CN105164283B (en) 2013-03-05 2013-11-08 Rare earth metal and the method for preparing rare earth metal concentrate are stripped from organic solution
MA38442A MA38442B1 (en) 2013-03-05 2013-11-08 Process for stripping rare earth metals from organic solutions and preparation of rare earth metal concentrate
TN2015000374A TN2015000374A1 (en) 2013-03-05 2015-08-31 A method for re-extraction of rare-earth metals from organic solutions and preparing concentrate of rare-earth metals

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RU2013109742/05A RU2538863C2 (en) 2013-03-05 2013-03-05 Re-extraction method of rare-earth metals from organic solutions and obtainment of concentrate from rare-earth metals
RU2013109742 2013-03-05

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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RU2538863C2 (en) 2013-03-05 2015-01-10 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Re-extraction method of rare-earth metals from organic solutions and obtainment of concentrate from rare-earth metals
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RU2747574C2 (en) * 2019-05-21 2021-05-07 Общество С Ограниченной Ответственностью "Минералс Ресайклинг" Method of separation of heavy rem (yttrium, ytterbium, erbium and dysprosium) during extraction thereof from phosphatic solutions
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026132A1 (en) * 1979-09-21 1981-04-01 Rhone-Poulenc Chimie De Base Process for global recovery of uranium, rare earth metals, thorium and yttrium from an acid solution
SU1370076A1 (en) * 1986-01-20 1988-01-30 Донецкий государственный университет Method of extracting rare-earth elements from sulfate solutions
US5011665A (en) 1989-03-03 1991-04-30 Rhone-Poulenc Chimie Nonpolluting recovery of rare earth values from rare earth minerals/ores
US5030424A (en) * 1989-04-03 1991-07-09 Alcan International Limited Recovery of rare earth elements from Bayer process red mud
RU2047562C1 (en) * 1991-08-02 1995-11-10 Научно-производственное объединение "Радиевый институт им.В.Г.Хлопина" Method for extracting rare-earth and actinide elements from liquid high active wastes
RU2049133C1 (en) 1992-11-19 1995-11-27 Науменко Николай Александрович Method of extraction of rare-earth metals from their mixtures
RU2172719C1 (en) * 2000-07-17 2001-08-27 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН Method for isolation of rare-earth minerals from acidic solutions
RU2293781C1 (en) * 2005-07-04 2007-02-20 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method of recovering rare-earth elements from phosphogypsum
RU2337881C1 (en) 2007-02-26 2008-11-10 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method for extracting lanthanides from phosphoric acid
RU2344079C1 (en) 2007-04-25 2009-01-20 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Phosphate rare-earth concentrate processing method
RU2349652C2 (en) * 2007-04-17 2009-03-20 Российский химико-технологический университет им. Д.И. Менделеева Method of metal recovery from solid-phase raw-materials

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783125A (en) 1949-07-21 1957-02-26 Produits Chim Terres Rares Soc Treatment of monazite
FR2391953A1 (en) 1976-11-02 1978-12-22 Ugine Kuhlmann NITRIC EFFLUENT TREATMENT PROCESS
SU950684A1 (en) 1980-08-01 1982-08-15 Кингисеппское Ордена Трудового Красного Знамени Производственное Объединение "Фосфорит" Method for purifying fluorinaceous effluents from phosphorous production
EP0265547A1 (en) 1986-10-30 1988-05-04 URAPHOS CHEMIE GmbH Method of recovering rare earths, and in a given case, uranium and thorium from heavy phosphate minerals
PL155815B1 (en) 1988-05-16 1992-01-31 Politechnika Krakowska Method of recovering lanthanides from phospogypsum wastes
RU2031842C1 (en) 1991-07-01 1995-03-27 Юрий Георгиевич Горный Method of rare-earth elements extraction from phosphate ore
RU2118613C1 (en) 1997-06-04 1998-09-10 Александр Васильевич Вальков Method of rare-earth elements extraction
RU2225892C1 (en) 2002-07-23 2004-03-20 Институт химии и технологии редких элементов и минерального сырья им. И.В.Тананаева Кольского научного центра РАН Method of recovering rare-earth minerals from phosphogypsum
CZ20041156A3 (en) 2004-11-30 2006-07-12 Ústav chemickych procesu AV CR Method of extracting europium and yttrium ions from luminophore dust or sludge concentrates
CN1317086C (en) * 2005-02-21 2007-05-23 华南师范大学 Method for recycling mixed waste batteries
RU2293134C1 (en) * 2005-05-26 2007-02-10 Институт химии и химической технологии СО РАН (ИХХТ СО РАН) Process for extracting rare-earth metals and yttrium from coals and ash-slag waste material of coal burning
RU2288171C1 (en) * 2005-06-16 2006-11-27 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method of recovering rare-earth elements from eudialyte concentrate solution subjected to hydrochloric acid decomposition
CN101597688A (en) 2008-06-03 2009-12-09 贵州光大能源发展有限公司 From phosphogypsum, reclaim a kind of method of rare earth
RU2374260C1 (en) * 2008-06-30 2009-11-27 Учреждение Российской академии наук Институт органической и физической химии им. А.Е. Арбузов Казанского научного центра РАН Method of producing dialkyl(aryl)-1,1-dimethyl-3-oxobut-1-ylphosphine oxides
CN101823750A (en) 2010-04-30 2010-09-08 汪晋强 Method for producing calcium chloride dihydrate and gypsum by using phosphogypsum
RU2471011C1 (en) 2011-11-16 2012-12-27 Общество с ограниченной ответственностью "Научно-производственное предприятие Уралхим" Extraction method of rare-earth metals from phosphogypsum
JP2013209689A (en) * 2012-03-30 2013-10-10 Sumitomo Heavy Ind Ltd Method for recovering rare-earth element
RU2546739C2 (en) 2013-03-05 2015-04-10 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Method of purifying working leaching solutions from phosphates and fluorides
RU2538863C2 (en) 2013-03-05 2015-01-10 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Re-extraction method of rare-earth metals from organic solutions and obtainment of concentrate from rare-earth metals
RU2528573C1 (en) 2013-03-05 2014-09-20 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Method of extracting rare-earth metals and producing gypsum plaster from phosphogypsum hemihydrate
RU2528576C1 (en) 2013-03-05 2014-09-20 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Method of extracting rare-earth metals and producing gypsum plaster from phosphogypsum hemihydrate
RU2543160C2 (en) 2013-03-18 2015-02-27 Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" Method of sulphuric acid decomposition of rem-containing phosphate raw material

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026132A1 (en) * 1979-09-21 1981-04-01 Rhone-Poulenc Chimie De Base Process for global recovery of uranium, rare earth metals, thorium and yttrium from an acid solution
SU1370076A1 (en) * 1986-01-20 1988-01-30 Донецкий государственный университет Method of extracting rare-earth elements from sulfate solutions
US5011665A (en) 1989-03-03 1991-04-30 Rhone-Poulenc Chimie Nonpolluting recovery of rare earth values from rare earth minerals/ores
US5030424A (en) * 1989-04-03 1991-07-09 Alcan International Limited Recovery of rare earth elements from Bayer process red mud
RU2047562C1 (en) * 1991-08-02 1995-11-10 Научно-производственное объединение "Радиевый институт им.В.Г.Хлопина" Method for extracting rare-earth and actinide elements from liquid high active wastes
RU2049133C1 (en) 1992-11-19 1995-11-27 Науменко Николай Александрович Method of extraction of rare-earth metals from their mixtures
RU2172719C1 (en) * 2000-07-17 2001-08-27 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН Method for isolation of rare-earth minerals from acidic solutions
RU2293781C1 (en) * 2005-07-04 2007-02-20 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method of recovering rare-earth elements from phosphogypsum
RU2337881C1 (en) 2007-02-26 2008-11-10 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method for extracting lanthanides from phosphoric acid
RU2349652C2 (en) * 2007-04-17 2009-03-20 Российский химико-технологический университет им. Д.И. Менделеева Method of metal recovery from solid-phase raw-materials
RU2344079C1 (en) 2007-04-25 2009-01-20 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Phosphate rare-earth concentrate processing method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. BENEDICT ET AL.: "Nuclear Chemical Engineering", 1981, MCGRAW-HILL, pages: 304 - 306
See also references of EP2964794A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104561614A (en) * 2015-01-29 2015-04-29 赣州稀土矿业有限公司 Process for recycling rare earth from south ion adsorption type rare earth ore leaching mother liquor
RU2852695C1 (en) * 2024-07-26 2025-12-12 Федеральное государственное бюджетное научное учреждение "Федеральный исследовательский центр "Красноярский научный центр Сибирского отделения Российской академии наук" (ФИЦ КНЦ СО РАН, КНЦ СО РАН) Method for extracting scandium from sulphuric acid solutions with di(2-ethylhexyl)phosphoric acid

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