WO2014148945A1 - A method for concentrating rare-earth metals in phosphogypsum - Google Patents

A method for concentrating rare-earth metals in phosphogypsum Download PDF

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Publication number
WO2014148945A1
WO2014148945A1 PCT/RU2013/000988 RU2013000988W WO2014148945A1 WO 2014148945 A1 WO2014148945 A1 WO 2014148945A1 RU 2013000988 W RU2013000988 W RU 2013000988W WO 2014148945 A1 WO2014148945 A1 WO 2014148945A1
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Prior art keywords
rem
phosphogypsum
terms
rare
apatite
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PCT/RU2013/000988
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French (fr)
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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Uralchem JSC
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Priority to US14/775,241 priority Critical patent/US10011891B2/en
Priority to CN201380074771.9A priority patent/CN105051224B/en
Priority to EP13879034.0A priority patent/EP2989222B1/en
Priority to MA38444A priority patent/MA38444B1/en
Publication of WO2014148945A1 publication Critical patent/WO2014148945A1/en
Priority to TN2015000372A priority patent/TN2015000372A1/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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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 producing rare-earth metal (REM) compounds during complex processing of apatite, in particular to a method for concentrating rare-earth metals in phosphogypsum and purification of wet process phosphoric acid from REM.
  • REM rare-earth metal
  • phosphorus-containing minerals such as apatite, rock phosphate, etc.
  • the processing is carried out by treating these natural materials with concentrated nitric or sulphuric acid.
  • sulphuric acid apatite is decomposed with precipitation of calcium sulphate and formation of phosphoric acid solution.
  • 65%-85% of REM are precipitated with phosphogypsum, and the rest of REM are dissolved in the wet process phosphoric acid.
  • apatite of the Kola Peninsula contains up to 1 % of rare-earth metals, 70 to 80 % of which are precipitated with calcium sulphate in the course of the hemihydrate processing at apatite with sulphuric acid. All REM which remain in phosphoric acid further goes to fertilizers produced therefrom.
  • a method comprising treatment for 20-25 minutes with 22-30% sulfuric acid solution is carried out to provide extraction of rare earth elements and compounds of phosphorus in solution followed by separation of insoluble residue in the form of gypsum which contains a considerable amount of sulfuric and phosphoric acid is well-known (RU patent No. 2337897).
  • the extraction solution also contains double sulfates of rare earth metals with sodium or potassium.
  • the resulting crystalline gypsum is treated with Ca(OH) 2 or CaO or CaC0 3 to neutralize residual sulfuric and phosphoric acid to reach pH>5.
  • the content of phosphorus impurities in the mother liquor shall be monitored.
  • the mother liquor is directed to the extraction step or subjected to purification treatment by adding T1OSO4 * H 2 0 to reach an acceptable level of P2O5.
  • This method allows the recovery of up to 82.1 % REM in the extraction solution with subsequent isolation thereof by crystallization in the form of concentrate with a degree of recovery up to 68.5%.
  • the disadvantages of this method include obtaining crystalline gypsum with a pH which does not meet the standard requirements for construction and has a high content of P2O5. Isolation of the lanthanides from the oversaturated extraction solution requires a significant period of time (2 hours).
  • the method of recovering rare-earth elements from phosphogypsum disclosed in RU patent No. 2293781 seems to be the closest analog of the present invention.
  • the method comprises treatment of phosphogypsum with sulphuric acid solution to recover rare-earth elements into solution, separation of gypsum precipitate, increasing the oversaturation rate of the solution in terms of rare-earth elements to crystalize rare-earth metal concentrate, and separation of the concentrate from mother liquor followed by concentrate processing.
  • Phosphogypsum is treated with 22-30%) sulphuric acid solution at liquids-to-solids ratio 1.8-2.2 during 20-30 min to prevent spontaneous crystallization of rare-earth element concentrate in solution before insoluble precipitate is separated.
  • Concentrating REM from solutions in solid phase is required not only after its recovery from phosphogypsum into the target solution, but also, for example, during REM extraction from wet process phosphoric acid in the course of apatite processing with sulphuric acid.
  • a method for extracting REM from the wet process phosphoric acid and concentrating REM on the solid sorbent using the acid retention method applying the effect of isothermal saturation in adsorbing layers is cited below ( hamizov R.H., rachak A.N., Gruzdeva A.N., Bolotokov A.A., Khamizov S.H., Smirnov A.A., Zhiguleva T.I.
  • REM salt and some other components poorly soluble in such conditions form a precipitate at the column outlet.
  • Salts soluble in such conditions for example calcium and manganese compounds, are even concentrated and can be detected in outgoing fractions of solution, corresponding to phosphorus output. Part of REM remained in the solution is also detected in these fractions.
  • the main disadvantage of this method is its relatively low productivity limited by capacity of the ion-exchange resins and, therefore, high price thereof.
  • the present invention addresses the problem of concentrating REM in phosphogypsum in the course of processing apatite with sulphuric acid and removing REM from wet process phosphoric acid.
  • REM is used to indicate lanthanides and yttrium.
  • Ln is used for these elements.
  • the problem is solved by adding a sodium salt in the amount of 0.25-5.0 kg in terms of Na 2 0 or a potassium salts in the amount of 0.25-5.0 kg in terms of K 2 0 or a mixture thereof in the amount of 0.25-5 kg in terms of Na 2 0 and K 0 to 1 kg of REM (in terms of Ln 2 03 present in raw phosphate material) to a process of decomposition of the REM containing raw phosphate material with sulphuric acid.
  • the technical effect is an increase in the degree of transfer of REM into phosphogypsum up to 98%.
  • Sulphates, chlorides, nitrates of sodium or potassium or mixtures thereof can be used. Use of sodium or potassium sulphates is preferable.
  • solubility of double sulphates MLn(S04) 2 is much lower than solubility of sulfate Ln 2 (S0 4 ) 3 .
  • the addition of sodium or potassium salts to apatite reduces the solubility of REM in the wet process phosphoric acid and promotes their precipitation in the form of a separate phase.
  • Example 1 Apatite processing without the addition of alkali metals.
  • Example 2 Apatite processing with addition of alkali metal.
  • Example 4 Apatite processing with the addition of alkali metal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The present invention relates to a method for producing rare-earth metals (REM) compounds by complex processing of apatite, in particularly to a method for concentrating rare-earth metals (REM) in phosphogypsum, where to a process of decomposition of the REM containing raw phosphate material with sulphuric acid, a sodium salt in the amount of 0.25-5.0 kg in terms of Na2O or a potassium salts in the amount of 0.25-5.0 kg in terms of K2O or a mixture thereof in the amount of 0.25-5 kg in terms of Na2O and K2O to 1 kg of REM (in terms of Ln2O3 present in raw phosphate material) is added. The yield of REM transfer into phosphogypsum is up to 98%.

Description

A METHOD FOR CONCENTRATING RARE-EARTH METALS IN PHOSPHOGYPSUM
Field of the invention
The present invention relates to technologies for producing rare-earth metal (REM) compounds during complex processing of apatite, in particular to a method for concentrating rare-earth metals in phosphogypsum and purification of wet process phosphoric acid from REM.
Background of the invention
Tens of millions of tons of phosphorus-containing minerals, such as apatite, rock phosphate, etc., are processed for producing phosphorus-containing fertilizers. Typically, the processing is carried out by treating these natural materials with concentrated nitric or sulphuric acid. During the treatment with sulphuric acid, apatite is decomposed with precipitation of calcium sulphate and formation of phosphoric acid solution. In the course of the hemihydrate process, 65%-85% of REM are precipitated with phosphogypsum, and the rest of REM are dissolved in the wet process phosphoric acid. For example, apatite of the Kola Peninsula contains up to 1 % of rare-earth metals, 70 to 80 % of which are precipitated with calcium sulphate in the course of the hemihydrate processing at apatite with sulphuric acid. All REM which remain in phosphoric acid further goes to fertilizers produced therefrom. Thus, to perform the complete extraction of REM from apatite, it is necessary to recover REM from both phosphogypsum and the acid. It is associated with the complexity of production and increasing the required capital investment. Therefore, it is desirable to concentrate REM in one of these products, either wet process phosphoric acid or phosphogypsum.
A method comprising treatment for 20-25 minutes with 22-30% sulfuric acid solution is carried out to provide extraction of rare earth elements and compounds of phosphorus in solution followed by separation of insoluble residue in the form of gypsum which contains a considerable amount of sulfuric and phosphoric acid is well-known (RU patent No. 2337897). The extraction solution also contains double sulfates of rare earth metals with sodium or potassium. The resulting crystalline gypsum is treated with Ca(OH)2 or CaO or CaC03 to neutralize residual sulfuric and phosphoric acid to reach pH>5. The content of phosphorus impurities in the mother liquor shall be monitored. And depending on the ratio of its content and residual humidity gypsum, the mother liquor is directed to the extraction step or subjected to purification treatment by adding T1OSO4 * H20 to reach an acceptable level of P2O5. This method allows the recovery of up to 82.1 % REM in the extraction solution with subsequent isolation thereof by crystallization in the form of concentrate with a degree of recovery up to 68.5%. The disadvantages of this method include obtaining crystalline gypsum with a pH which does not meet the standard requirements for construction and has a high content of P2O5. Isolation of the lanthanides from the oversaturated extraction solution requires a significant period of time (2 hours). Monitoring of content of phosphorus impurities in the acid extractant and residual moisture of gypsum precipitate is required. To remove the phosphorus excess, it is necessary to have the equipment to neutralize phosphorus compounds by titanium compounds in a dry form or in a mixture with concentrated sulfuric acid followed by separation of titanyl phosphate and obligatory treatment with concentrated sulphuric acid. If the concentration of sulphuric acid in the extraction solution is reduced to below 22%, an increase of its concentration is necessary in order to reuse it in the process. It requires a large number of reactors, capacitive, filtration and other equipment for extraction of rare earth elements, storage of various extraction solutions and neutralization of phosphorus compounds.
The method of recovering rare-earth elements from phosphogypsum disclosed in RU patent No. 2293781 seems to be the closest analog of the present invention. The method comprises treatment of phosphogypsum with sulphuric acid solution to recover rare-earth elements into solution, separation of gypsum precipitate, increasing the oversaturation rate of the solution in terms of rare-earth elements to crystalize rare-earth metal concentrate, and separation of the concentrate from mother liquor followed by concentrate processing. Phosphogypsum is treated with 22-30%) sulphuric acid solution at liquids-to-solids ratio 1.8-2.2 during 20-30 min to prevent spontaneous crystallization of rare-earth element concentrate in solution before insoluble precipitate is separated. An increase of the oversaturation rate of the solution is achieved by providing sodium concentration 0.4-1.2 g/L. The disadvantage of this method is the use of additional reagents, high acid concentrations and significant amounts thereof, a large number of basic technological operations with incomplete extraction of rare earth elements (up to 71.4%) and the overall complexity of the process.
Concentrating REM from solutions in solid phase is required not only after its recovery from phosphogypsum into the target solution, but also, for example, during REM extraction from wet process phosphoric acid in the course of apatite processing with sulphuric acid. A method for extracting REM from the wet process phosphoric acid and concentrating REM on the solid sorbent using the acid retention method applying the effect of isothermal saturation in adsorbing layers is cited below ( hamizov R.H., rachak A.N., Gruzdeva A.N., Bolotokov A.A., Khamizov S.H., Smirnov A.A., Zhiguleva T.I. "Sorption concentration and isolation of REM from wet process phosphoric acid". Sorption and chromatography processes (rus), 2012, V. 12, No. 1 , pp. 29-39). One of the simplest variants of the acid retention method was used in this work. Repetitive operating cycles are carried out: processed solution is passed upwards through ion- exchange column filled with a dense layer of strong base anion resin, previously equilibrated with the processed solution of the phosphoric acid and then washed out with water, until the acid concentration at the outlet is equal to the concentration of the initial solution and then inverse elution of the acid was carried out with water being passed down. The main effect is that the first passing fractions contain practically no or very little acid (up to pH 2-3). REM salt and some other components poorly soluble in such conditions form a precipitate at the column outlet. Salts soluble in such conditions, for example calcium and manganese compounds, are even concentrated and can be detected in outgoing fractions of solution, corresponding to phosphorus output. Part of REM remained in the solution is also detected in these fractions.
The main disadvantage of this method is its relatively low productivity limited by capacity of the ion-exchange resins and, therefore, high price thereof.
The present invention addresses the problem of concentrating REM in phosphogypsum in the course of processing apatite with sulphuric acid and removing REM from wet process phosphoric acid. 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 adding a sodium salt in the amount of 0.25-5.0 kg in terms of Na20 or a potassium salts in the amount of 0.25-5.0 kg in terms of K20 or a mixture thereof in the amount of 0.25-5 kg in terms of Na20 and K 0 to 1 kg of REM (in terms of Ln203 present in raw phosphate material) to a process of decomposition of the REM containing raw phosphate material with sulphuric acid. The technical effect is an increase in the degree of transfer of REM into phosphogypsum up to 98%.
The present invention is explained in more detail below.
The authors of the present inventions have found that REM in the phosphogypsum hemihydrate is present predominantly in the form of compounds MLn(S04)2 (wherein M is alkali metal atom, Na or ), forming a solid solution with the main phase of calcium sulfate. Ln3+soiution + + soiu,ion + 2S04 2" Soiution + nCaSO4.0.5H2O
MLn(SO4)2.(CaSO4.0.5H2O)n soM soiution.
Thus, adding sodium or potassium salts to apatite shifts the equilibrium towards the formation of the solid solution of REM within calcium sulfate hemihydrate.
Sulphates, chlorides, nitrates of sodium or potassium or mixtures thereof can be used. Use of sodium or potassium sulphates is preferable.
It is also well-known that the solubility of double sulphates MLn(S04)2 is much lower than solubility of sulfate Ln2(S04)3. Thus, the addition of sodium or potassium salts to apatite reduces the solubility of REM in the wet process phosphoric acid and promotes their precipitation in the form of a separate phase.
The present invention is explained in more detail below using Figures and 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. Apatite processing without the addition of alkali metals.
100 g of apatite concentrate was mixed with 97 g of 93% H2S04 and 295 g of phosphoric acid having 30% P205. The obtained slurry was stirred for 180 min at 90-100 °C and filtered. The obtained precipitate of phosphogypsum hemihydrate (CaS04 » 0.5 H20) was washed. Thus, a precipitate containing 0.535% Ln2(¾ and phosphoric acid having 36% P2O5 and 0.035% Ln2(¾ were obtained.
Example 2. Apatite processing with addition of alkali metal.
100 g of apatite concentrate was mixed with 97 g of 93% H2S04, 295 g of phosphoric acid having 30% P2Os and 0.6 g of Na2S04. The obtained slurry was stirred for 180 min at 90- 100 °C and filtered. The obtained precipitate of phosphogypsum hemihydrate (CaS04 » 0.5 H20) was washed. Thus, a precipitate containing 0.61 % Ln2(¾ and phosphoric acid having 36% P2O5 and 0.021% Ln203 were obtained. Example 3. Apatite processing with the addition of alkali metal.
100 g of apatite concentrate was mixed with 97 g of 93% H2SO4, 295 g of phosphoric acid having 30% P2O5 and 6.0 g of Na2SC>4. The obtained slurry was stirred for 180 min at 90- 100 °C and filtered. The obtained precipitate of phosphogypsum hemihydrate (CaS04 » 0.5 H2O) was washed. Thus, a precipitate containing 0.645% Ln2C>3 and phosphoric acid having 36% P2O5 and 0.009% Ln203 were obtained.
Example 4. Apatite processing with the addition of alkali metal.
100 g of apatite concentrate was mixed with 97 g of 93% H2SO4, 295 g of phosphoric acid having 30% P2O5 and 10.0 g of 2SO4. The obtained slurry was stirred for 180 min at 90- 100 °C and filtered. The obtained precipitate of phosphogypsum hemihydrate (CaSC>4 » 0.5 H2O) was washed. Thus, a precipitate containing 0.65% Ln2C>3 and phosphoric acid having 36% P2O5 and 0.01% Ln203 were obtained.
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 concentrating rare-earth metals (REM) in phosphogypsum, wherein to a process of decomposition of the REM containing raw phosphate material with sulphuric acid, a sodium salt in the amount of 0.25-5.0 kg in terms of Na20 or a potassium salts in the amount of 0.25-5.0 kg in terms of 20 or a mixture thereof in the amount of 0.25-5 kg in terms of Na20 and 20 to 1 kg of REM (in terms of Ln2C>3 present in raw phosphate material) is added.
2. The method of claim 1, wherein sulphate, chloride or nitrate of sodium or potassium or a mixture thereof is used as the sodium and/or potassium salt.
PCT/RU2013/000988 2013-03-18 2013-11-08 A method for concentrating rare-earth metals in phosphogypsum Ceased WO2014148945A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US14/775,241 US10011891B2 (en) 2013-03-18 2013-11-08 Methods for concentrating rare-earth metals in phosphogypsum and removing thereof from wet process phosphoric acid
CN201380074771.9A CN105051224B (en) 2013-03-18 2013-11-08 Method rare earth metal being enriched in ardealite
EP13879034.0A EP2989222B1 (en) 2013-03-18 2013-11-08 A method for concentrating rare-earth metals in phosphogypsum
MA38444A MA38444B1 (en) 2013-03-18 2013-11-08 Process for concentrating rare earth metals in phosphogypsum
TN2015000372A TN2015000372A1 (en) 2013-03-18 2015-08-31 A method for concentrating rare-earth metals in phosphogypsum

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RU2013111926 2013-03-18
RU2013111926/02A RU2543160C2 (en) 2013-03-18 2013-03-18 Method of sulphuric acid decomposition of rem-containing phosphate raw material

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EP (1) EP2989222B1 (en)
CN (1) CN105051224B (en)
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TN (1) TN2015000372A1 (en)
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* Cited by examiner, † Cited by third party
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WO2018190737A1 (en) 2017-04-14 2018-10-18 Ferin Sp. Z.O.O. Method for the management of phosphogypsum
WO2026005585A1 (en) 2024-06-28 2026-01-02 Ocp Sa Method for extracting and concentrating rare earths from phosphogypsum

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
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
FR3086672B1 (en) * 2018-09-28 2020-11-13 Ocp Sa PROCESS FOR PURIFICATION AND CONCENTRATION OF RARE EARTHS FROM PHOSPHOGYPSE
WO2026005812A1 (en) * 2024-06-26 2026-01-02 Village Enterprises, Inc. Systems and processes for the recovery of 226ra from phosphogypsum

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647361A (en) 1969-12-03 1972-03-07 Molybdenum Corp Two-stage countercurrent leaching process for the recovery of phosphates, yttrium and rare earth values
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
PL272533A2 (en) * 1988-05-16 1989-02-20 Politechnika Krakowska Method of recovering lanthanides from phospogypsum wastes
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
RU2337897C1 (en) 2007-03-19 2008-11-10 Юлия Алексеевна Щепочкина Method of thermodressing of building materials and products
RU2381178C1 (en) 2008-07-11 2010-02-10 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method for extraction of lanthanides from extractive phosphorous acid
RU2471011C1 (en) * 2011-11-16 2012-12-27 Общество с ограниченной ответственностью "Научно-производственное предприятие Уралхим" Extraction method of rare-earth metals from phosphogypsum

Family Cites Families (29)

* 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
SE364187B (en) 1972-01-24 1974-02-18 Stora Kopparbergs Bergslags Ab
FR2391953A1 (en) 1976-11-02 1978-12-22 Ugine Kuhlmann NITRIC EFFLUENT TREATMENT PROCESS
DE3064641D1 (en) 1979-09-21 1983-09-29 Rhone Poulenc Chim Base Process for global recovery of uranium, rare earth metals, thorium and yttrium from an acid solution
SU950684A1 (en) 1980-08-01 1982-08-15 Кингисеппское Ордена Трудового Красного Знамени Производственное Объединение "Фосфорит" Method for purifying fluorinaceous effluents from phosphorous production
SU1370076A1 (en) 1986-01-20 1988-01-30 Донецкий государственный университет Method of extracting rare-earth elements from sulfate solutions
US5030424A (en) 1989-04-03 1991-07-09 Alcan International Limited Recovery of rare earth elements from Bayer process red mud
RU2031842C1 (en) * 1991-07-01 1995-03-27 Юрий Георгиевич Горный Method of rare-earth elements extraction from phosphate ore
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
RU2118613C1 (en) 1997-06-04 1998-09-10 Александр Васильевич Вальков Method of rare-earth elements extraction
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
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
RU2258036C1 (en) * 2004-06-09 2005-08-10 Открытое акционерное общество "СОДА" (ОАО "СОДА") Phosphogypsum integrated processing method
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
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
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
CN101440430A (en) * 2007-11-19 2009-05-27 贵州光大能源发展有限公司 Method for recycling rare earth from phosphogypsum leaching solution by fluoride precipitation method
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
RU2416654C1 (en) * 2009-11-10 2011-04-20 Закрытое акционерное общество "Российские редкие металлы" Procedure for extraction of rare earth elements from phospho-gypsum
CN101823750A (en) 2010-04-30 2010-09-08 汪晋强 Method for producing calcium chloride dihydrate and gypsum by using phosphogypsum
KR101690819B1 (en) * 2010-09-14 2016-12-28 오브쉐스트보 에스 오그라니쉐노이 오?스트베노스트유 ˝트윈 테크놀로지 컴퍼니˝ Method for extracting rare earth elements from phosphogypsum
CN102876889B (en) 2012-09-29 2014-05-07 广州有色金属研究院 Method for extracting rare earth from rare-earth-contained apatite ores
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
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
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
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
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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647361A (en) 1969-12-03 1972-03-07 Molybdenum Corp Two-stage countercurrent leaching process for the recovery of phosphates, yttrium and rare earth values
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
PL272533A2 (en) * 1988-05-16 1989-02-20 Politechnika Krakowska Method of recovering lanthanides from phospogypsum wastes
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
RU2337897C1 (en) 2007-03-19 2008-11-10 Юлия Алексеевна Щепочкина Method of thermodressing of building materials and products
RU2381178C1 (en) 2008-07-11 2010-02-10 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук Method for extraction of lanthanides from extractive phosphorous acid
RU2471011C1 (en) * 2011-11-16 2012-12-27 Общество с ограниченной ответственностью "Научно-производственное предприятие Уралхим" Extraction method of rare-earth metals from phosphogypsum

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. JAROSINSKI ET AL., JOURNAL OF ALLOYS AND COMPOUNDS, vol. 200, 1993, pages 147 - 150
E.P. LOKSHIN: "Recovery of lanthanides from Extraction Phosphoric Acid Produced by the Dihydrate Process", RUSSIAN JOURNAL OF APPLIED CHEMISTRY, vol. 83, no. 6, 2010, pages 951 - 957, XP055322307, DOI: 10.1134/S1070427210060042
KHAMIZOV R.H.KRACHAK A.N.GRUZDEVA A.N.BOLOTOKOV A.A.KHAMIZOV S.H.SMIMOV A.A.ZHIGULEVA T.I.: "Sorption concentration and isolation of REM from wet process phosphoric acid", SORPTION AND CHROMATOGRAPHY PROCESSES (RUS, vol. 12, no. 1, 2012, pages 29 - 39
See also references of EP2989222A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018190737A1 (en) 2017-04-14 2018-10-18 Ferin Sp. Z.O.O. Method for the management of phosphogypsum
WO2026005585A1 (en) 2024-06-28 2026-01-02 Ocp Sa Method for extracting and concentrating rare earths from phosphogypsum
FR3163953A1 (en) 2024-06-28 2026-01-02 Ocp Sa METHOD FOR EXTRACTION AND CONCENTRATION OF RARE EARTHS FROM PHOSPHOGYPSE

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