WO2020233826A1 - Procédé de lixiviation d'éléments des terres rares - Google Patents

Procédé de lixiviation d'éléments des terres rares Download PDF

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Publication number
WO2020233826A1
WO2020233826A1 PCT/EP2019/084738 EP2019084738W WO2020233826A1 WO 2020233826 A1 WO2020233826 A1 WO 2020233826A1 EP 2019084738 W EP2019084738 W EP 2019084738W WO 2020233826 A1 WO2020233826 A1 WO 2020233826A1
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WO
WIPO (PCT)
Prior art keywords
leaching
iron
rare earth
solution
ree
Prior art date
Application number
PCT/EP2019/084738
Other languages
English (en)
Inventor
Bernd Kunze
Marat SULTANOV
Aziz Sultanov
Original Assignee
ABDULKHALEK, Ahmed
ABDULSALAM SALEH, Khalid, Mohd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ABDULKHALEK, Ahmed, ABDULSALAM SALEH, Khalid, Mohd filed Critical ABDULKHALEK, Ahmed
Publication of WO2020233826A1 publication Critical patent/WO2020233826A1/fr

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Classifications

    • 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
    • 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
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • 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 present invention relates to the field of mining industry and specifically to the leaching of rare earth elements (REE).
  • REE rare earth elements
  • the direct leaching of rare earth elements takes place by means of hydrochloric acid, sulphuric acid, nitric acid or mixtures thereof.
  • a temperature of up to 200 °C and a pressure of 1 to 51.7 bar can be used.
  • the following substances are used for leaching:
  • FeS04, FeCh, FeCte and other halogen-containing compounds are reacted as auxiliary materials.
  • Surfactants primarily reduce the surface tension of water, with a decreasing dissolution of oxygen in the water. The majority of synthetic surfactants
  • surfactants is poorly decomposed or not at all decomposed by the microbiological flora of the purification plants and this result in swamp formation in the bodies of water into which they are introduced.
  • many surfactants can form stable compounds with heavy metals (the elimination thereof requires temperatures up to 100 °C, lasts up to 8 hours and is carried out using expensive materials suitable for the decomposition of these compounds), which also strongly suppress aerobic microflora, leading to swamp formation.
  • ozone Use of ozone.
  • the solubility of ozone in water at a pressure of 1 bar is about 10 mg per 1 litre.
  • higher concentrations are required, which are achieved under high pressure.
  • Iron sulphates and chlorides are used as auxiliary substances in connection with acids in order to shift the equilibrium in acid leaching of the required metals, namely by forming insoluble compounds with the acid residues of the mineral raw materials.
  • This mixture is placed in an autoclave made of high-alloy steel with Teflon protection. In the autoclave, the pressure is increased to 7-9 bar and the temperature to 170-190 °C. The process is carried out for 20-40 minutes. The mixture is then cooled and filtered.
  • Chatelier it is necessary to convert the reaction products into non-reactive substances (to be removed from the reaction zone by the extraction of water-insoluble substances or with a gas) or into other substances that would not react with the mineral residue in order to shift the equilibrium of the chemical process to the right.
  • nitric acid acts on the phosphorite of a rare earth element, rare earth nitrate and free phosphoric acid are formed.
  • a water-soluble iron salt is used so that the phosphoric acid does not react with the REE nitrate and no equilibrium occurs. Iron reacts with the phosphoric acid to form insoluble iron phosphate. In this way the degree of leaching of REE increases, which are converted from insoluble phosphates into soluble nitrates. At high pressure peroxides and ozonides are not formed.
  • the process is not ecologically clean: in part the nitric acid will decompose into nitrogen oxides that pollute the atmosphere and in part the nitric acid will remain in the solid residue (filter cake) and thus contaminate the soil and the groundwater.
  • wastes were used as raw materials, which result from the extraction of rare earth elements from the mineral raw materials of the Sichuan deposit (China) according to a standard process and had a content of 12% REE.
  • the raw materials, which are subjected to leaching in accordance with the present process include the following components:
  • the raw materials presented can be processed with conventional acid thermal processes, however thereby fluorine is released into the gaseous medium or - if nitric acid is used - the nitrogen oxides, i.e. substances which have a negative influence on the environment and on the conditions of industrial leaching.
  • the aim of the present invention is to develop an environmentally friendly and cost- effective process for the industrial leaching of rare earth elements, which makes it possible to dispense with the use of expensive equipment made of corrosion-resistant materials and is feasible on a broad basis of raw materials of minerals containing REE.
  • the basis for the development of the new process was the fact that the REE to be leached were in a bi-trivalent state and it was necessary to choose the conditions for the chemical exchange with an available hydrolysable salt whose metal could be in a bi- trivalent state.
  • the most easily accessible salt for this process is iron trichloride, which is hydrolysable to hydrochloric acid and is an oxidizing agent that can be easily reduced from a trivalent to a divalent state.
  • iron trichloride can be used, which is produced in the course of chlorine reuse in the production of NaOH from NaCI, which makes the cost of iron trichloride with 100% concentration about 2 times lower than the cost of hydrochloric acid with 40% concentration.
  • iron trichloride it is also sufficient to use equipment based on widely used chromium steels having a chromium content of 13 to 17%.
  • the leaching agent preferably of a hydrolysable iron salt, particularly preferably of iron trichloride
  • solvent preferably water
  • the solution is then filtered and the sediment is first dried for about 4 hours at 90- 100 °C, whereby the peroxide and ozonide compounds of the REE decompose and transform into REE oxide hydrates, while iron (III) is still present in the dried sediment.
  • the dried sediment is then treated at room temperature with an amount of oxalic acid, which is equimolar to the trivalent iron contained therein, whereby only the trivalent iron dissolves to form oxalates and the REE oxide hydrates remain in the solid sediment.
  • Patent claim 2 (dependent claim) focusses on a specific claim
  • the final leaching degree of REE according to the claimed process can be up to 100%, which is not characteristic for acid-thermal leaching processes, which result in a lower leaching degree of REE.
  • the invention preferably concerns a process for stepwise leaching of rare earth elements from minerals containing these elements, namely from bastnaesites, orthites, chevkinites, britholites, which have previously been comminuted to at least the particle size of 75 micrometres, comprising the following steps:
  • an initial stage comprising the following steps: a first step of preparing the reaction mixture consisting of a leaching agent, a solvent and mineral raw materials containing rare earth elements; a second step of leaching REE by heating the obtained reaction mixture to the working temperature of 80-100 °C and maintaining it at the given temperature with simultaneous stirring and a pH between 1 and 3; and a third step of subsequently filtering the resulting suspension to form the liquid solution of REE compounds and a solid residue;
  • a final stage comprising the following steps: a first step of treating the solution obtained as a result of the previous process steps with air until the divalent iron contained in the solution is completely transformed into trivalent iron; a second step of treating the solution obtained in the previous step with sodium hydroxide at room temperature until a pH between 9 and 12 is reached; a third step of filtering the solution obtained in the previous step and drying the sediment obtained thereby at 90-100 °C for about 4 hours; a fourth step of processing the sediment dried in the previous step with oxalic acid at room temperature, thereby forming a solution; a fifth step of final filtration of the solution obtained in the previous step, thereby forming a solid REE concentrate in pure form, wherein iron trichloride is used as leaching agent and water is used as solvent, and wherein the ratio solid: liquid in the reaction mixture is 1 :5, the duration of holding the reaction mixture at the working temperature is at least about 1 hour and all intermediate stages of the process are repetitions of the initial stage thereof, the total number of intermediate stages typically
  • iron trichloride is 5% in relation to the initial mass of the raw materials studied. This can be explained by the fact that the degree of hydrolysis of iron trichloride increases with decreasing concentration and that the hydrochloric acid released during hydrolysis interacts intensively with the components of the mineral raw materials. It should be noted that under these conditions practically all of Fe +3 is converted to Fe +2 and the rare earth elements are converted to the water-soluble chloride, peroxide and ozonide compounds. This is shown by the fact that upon further processing of the resulting solution with oxalic acid, oxalates of the divalent iron precipitate, while the oxalate of the trivalent iron is a water-soluble compound. All ozonide compounds of rare earth elements are sublimable when heated, this effect was observed when the water soluble products were carefully evaporated and dried.
  • Example 2 Process as in example 1 , except that only 50 g iron trichloride was added. Thereafter, the reaction mixture was thoroughly mixed, then heated to 80-100 °C with simultaneous stirring and kept at this temperature for 1 hour, also with simultaneous stirring, then filtered, dried, weighed and analysed. The same sequence of process steps was then repeated twice with the solid residue obtained after the previous repetition of this sequence. In total, all the above-mentioned process steps were carried out three times, with a corresponding decrease in the mass of the starting raw materials or the solid residue, respectively, after each repetition. The results of the analyses are shown in Table 2.
  • the solution obtained is then processed by treatment with air to convert the divalent iron into the trivalent state.
  • the solution is treated with NaOH up to a pH of 9 to 12, thereby precipitating rare earth elements and iron.
  • the solution is filtered and the sediment is first dried for about 4 hours at 90-100 °C and then treated with an equimolar amount of oxalic acid in relation to the iron.
  • the solution is filtered and a concentrate of rare earth elements is obtained in the sediment.
  • Fe +3 Fe +2 - e
  • the oxalates of divalent iron are insoluble in water and those of trivalent iron are soluble in water.
  • the claimed invention has the following significant differences:
  • the leaching of rare earth elements requires the use of iron(lll) salts.
  • chloride, peroxide and ozonide compounds of rare earth elements are formed.
  • the trivalent iron is converted into a divalent compound.
  • the solution is first treated with air, then with sodium hydroxide, the sediment is then separated, dried and treated with an equimolar amount of oxalic acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de lixiviation par étapes de tous les éléments des terres rares pouvant former des composés peroxyde et superoxyde, en particulier le cérium, le lanthane, le néodyme, l'europium, à partir de minéraux contenant ces éléments, à savoir à partir de bastnaesites, d'orthites, de chevkinites, de britholites, qui ont été préalablement broyés jusqu'à au moins la taille de particules de 75 micromètres.
PCT/EP2019/084738 2018-06-21 2019-12-11 Procédé de lixiviation d'éléments des terres rares WO2020233826A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102018004972 2018-06-21
DE102019003556.9 2019-05-21
DE102019003556.9A DE102019003556B3 (de) 2018-06-21 2019-05-21 Verfahren zur Auslaugung von Seltenerdenelementen.

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WO2020233826A1 true WO2020233826A1 (fr) 2020-11-26

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AU (1) AU2020200816A1 (fr)
DE (1) DE102019003556B3 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220228237A1 (en) * 2021-01-15 2022-07-21 Colorado School Of Mines Advanced systems and methods for leaching rare earths from ore

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111180017B (zh) * 2020-01-09 2023-07-28 江西理工大学 离子型稀土浸矿剂用量的计算方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD48194A1 (de) * 1965-07-21 1966-05-20 rost Jochen Salpetersaurer aufschluss von monazitsand
EP0265547A1 (fr) 1986-10-30 1988-05-04 URAPHOS CHEMIE GmbH Procédé de fabrication de terres rares et, le cas échéant, de l'uranium et du thorium à partir de minerais phosphatés lourds
WO2012149642A1 (fr) 2011-05-04 2012-11-08 Orbite Aluminae Inc. Procédés d'extraction d'éléments de terres rares dans divers minerais
RU2547369C2 (ru) 2012-03-12 2015-04-10 Товарищество с ограниченной ответственностью "Фирма "Балауса" Способ комплексной переработки остатков доманиковых образований
WO2016164600A1 (fr) 2015-04-08 2016-10-13 Ecolab Usa Inc. Aide à la lixiviation pour la récupération de métaux
WO2016201558A1 (fr) * 2015-06-17 2016-12-22 Innord Inc. Système et procédé destinés à l'extraction métallurgique de terres rares et de niobium

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
DD48194A1 (de) * 1965-07-21 1966-05-20 rost Jochen Salpetersaurer aufschluss von monazitsand
EP0265547A1 (fr) 1986-10-30 1988-05-04 URAPHOS CHEMIE GmbH Procédé de fabrication de terres rares et, le cas échéant, de l'uranium et du thorium à partir de minerais phosphatés lourds
WO2012149642A1 (fr) 2011-05-04 2012-11-08 Orbite Aluminae Inc. Procédés d'extraction d'éléments de terres rares dans divers minerais
RU2013153535A (ru) 2011-05-04 2015-06-10 Орбит Элюминэ Инк. Способы извлечения редкоземельных элементов из различных руд
RU2547369C2 (ru) 2012-03-12 2015-04-10 Товарищество с ограниченной ответственностью "Фирма "Балауса" Способ комплексной переработки остатков доманиковых образований
WO2016164600A1 (fr) 2015-04-08 2016-10-13 Ecolab Usa Inc. Aide à la lixiviation pour la récupération de métaux
WO2016201558A1 (fr) * 2015-06-17 2016-12-22 Innord Inc. Système et procédé destinés à l'extraction métallurgique de terres rares et de niobium

Non-Patent Citations (1)

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Title
LEE, SUNG OH, ET AL: "Dissolution of iron oxide using oxalic acid", HYDROMETALLURGY, ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, NL, vol. 87, no. 3-4, 19 June 2007 (2007-06-19), pages 91 - 99, XP022120187, ISSN: 0304-386X, DOI: 10.1016/J.HYDROMET.2007.02.005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220228237A1 (en) * 2021-01-15 2022-07-21 Colorado School Of Mines Advanced systems and methods for leaching rare earths from ore

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AU2020200816A1 (en) 2020-12-10
DE102019003556B3 (de) 2019-11-28

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