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WO2025037328A1 - Méthode de synthèse d'oxychlorure de terres rares et production de métal/alliage de terres rares - Google Patents

Méthode de synthèse d'oxychlorure de terres rares et production de métal/alliage de terres rares Download PDF

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Publication number
WO2025037328A1
WO2025037328A1 PCT/IN2024/051398 IN2024051398W WO2025037328A1 WO 2025037328 A1 WO2025037328 A1 WO 2025037328A1 IN 2024051398 W IN2024051398 W IN 2024051398W WO 2025037328 A1 WO2025037328 A1 WO 2025037328A1
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Prior art keywords
rare
earth
alloy
oxychloride
reoc1
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Prof. Chenna Rao BORRA
Borra Venkata Lakshmi
Dr. Prasanta JANA
Sonali ROUT
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Indian Institute of Technology Kharagpur
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Indian Institute of Technology Kharagpur
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/259—Oxyhalides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/271—Chlorides
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • TITLE A METHOD FOR SYNTHESIS OF RARE-EARTH OXYCHLORIDE AND PRODUCTION OF RARE-EARTH METAL/ALLOY
  • the present disclosure relates to method for production of rare earth metal/alloy. Particularly, but not exclusively, the present disclosure is directed towards method for synthesis of rare-earth oxychloride in low temperature and production of rare-earth metal/alloy.
  • Rare earth (RE) alloys are highly valued in various industries for their exceptional properties and wide-ranging applications. These alloys consist of a blend of different metals as the base metal and rare earth elements such as Scandium (Sc), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Samarium (Sm), Gadolinium (Gd), Dysprosium (Dy) and others.
  • Sc Scandium
  • La Lanthanum
  • Cerium Cerium
  • Neodymium Neodymium
  • Sm Samarium
  • Dysprosium (Dy) Dysprosium
  • Al-RE alloys There is extensive use of Al-RE alloys in industries including aerospace, automotive, electronics, and renewable energy.
  • the Al-RE alloy is highly sought after due to its lightweight properties, high strength-to-weight ratio, outstanding thermal conductivity, resistance to corrosion, and high temperatures.
  • Rare earth-aluminum alloys are utilized
  • rare earth alloys are produced from rare earth metals.
  • the production of rare earth metals involves several complex and often expensive technologies. Few of the existing notable methods used in the industry are illustrated below:
  • Fused Salt Electrolysis of Oxides The method involves first converting rare earth oxide compounds into rare earth chlorides or fluorides. An electric current is then conducted though the solution after these chemicals have been dissolved in a molten salt electrolyte. While oxygen or fluorine gas is produced at the anode, rare earth ions flow towards the cathode and are reduced to their metallic form.
  • the patent document EP0170372A1 describes a method for producing rare earth metal by dissolving rare earth oxide in CaCh molten salt.
  • the rare earth oxide is converted into oxychloride, resulting in the formation of CaO.
  • the presence of CaO limits the effectiveness of calico-thermic reduction of the RE compound to metal since the reduction product also contains CaO.
  • the solubility of CaO is limited to approximately 20 mol%.
  • the present disclosure is directed to overcome one or more limitations stated above, and any other limitation associated with the prior arts.
  • the present invention is directed to a method for external synthesis of rare-earth oxychloride and production of rare-earth metal/alloy.
  • the method comprises the steps of adding hydrochloric acid (HC1) to a portion of a pre-defined weight of rare-earth oxide (RE2O3) as obtained for converting the portion of RE2O3 to rare-earth chloride hydrate (RECI3.XH2O), heating the obtained rare-earth chloride hydrate (RECI3.XH2O) for evaporating water.
  • the method further comprises mixing the residual rare-earth oxide (RE2O3) with the rare-earth chloride hydrate (RECI3.XH2O) upon evaporation of water, and heating the mixture to a temperature exceeding 300°C to obtain rare-earth oxychloride (REOC1).
  • RE2O3 residual rare-earth oxide
  • REOC1 rare-earth chloride hydrate
  • the method includes making the obtained rare-earth oxychloride (REOC1) to react directly with calcium (Ca) or mixture of calcium (Ca) and alloying element in a temperature of 600°C - 1400°C for reducing the rare-earth oxychloride (REOC1) to rare-earth metal/alloy; and upon cooling, treating the reduced mass of rare- earth metal/alloy with water and dilute acid to remove reaction byproducts such as calcium chloride (CaCh) and calcium oxide (CaO).
  • REOC1 rare-earth oxychloride
  • the present disclosure relates to a method for producing rare- earth metal/alloy from externally synthesized rare-earth oxychloride.
  • the method comprises the steps of adding the externally synthesized rare-earth oxychloride (RE0C1) to molten calcium chloride (CaCh) or a mixture of calcium chloride (CaCh) and sodium chloride (NaCl) at temperature above 600°C with continuous stirring in presence of calcium (Ca) or mixture of calcium (Ca) and alloying element under controlled atmosphere for reducing the rare-earth oxychloride (RE0C1) to rare-earth metal/alloy, and upon cooling, treating the reduced mass of rare-earth metal/alloy with water and dilute acid to remove reaction byproducts such as calcium chloride (CaCh) and calcium oxide (CaO).
  • RE0C1 externally synthesized rare-earth oxychloride
  • CaCh calcium chloride
  • CaCh calcium chloride
  • CaO calcium oxide
  • Figure 1 illustrates a process flow diagram for production of rare-earth metal/alloy, in accordance with an embodiment of the present disclosure
  • Figure 2 illustrates exemplary X-ray diffraction analysis (XRD) patterns of samples (LaOCl) heated at 300-900°C (including La2C>3 and synthesized LaC13.7H2O), in accordance with an embodiment of the present disclosure
  • FIG. 3 illustrates exemplary Scanning Electron Microscopy with Energy Dispersive X-Ray (SEM-EDX) analysis of the samples (LaOCl) heated at 500°C for 1 h, in accordance with an embodiment of the present disclosure
  • Figure 4 illustrates exemplary X-ray diffraction analysis (XRD) patterns of samples (LaOCl) heated at 500°C and 700°C (including La2O3 and LaCh.VfLO), in accordance with an embodiment of the present disclosure
  • FIG. 5 illustrate exemplary Scanning Electron Microscopy with Energy Dispersive X- Ray (SEM-EDX) analysis of Al-La master alloy, in accordance with an embodiment of the present disclosure
  • Figure 6 illustrate exemplary X-ray diffraction analysis (XRD) patterns of Al-30% La master alloy, in accordance with an embodiment of the present disclosure
  • Figure 7 illustrate exemplary X-ray diffraction analysis (XRD) patterns of Al-60% La master alloy, in accordance with an embodiment of the present disclosure
  • FIG. 8 illustrate exemplary Scanning Electron Microscopy with Energy Dispersive X- Ray (SEM-EDX) analysis of Al-60%La master alloy, in accordance with an embodiment of the present disclosure
  • FIG. 9 illustrate exemplary Scanning Electron Microscopy with Energy Dispersive X- Ray (SEM-EDX) analysis of Al-90%La master alloy, in accordance with an embodiment of the present disclosure.
  • Figure 10 illustrate exemplary X-ray diffraction analysis (XRD) patterns of Al-60% Nd master alloy, in accordance with an embodiment of the present disclosure.
  • Figure 11 illustrate exemplary X-ray diffraction analysis (XRD) patterns of Al-60% Sm master alloy, in accordance with an embodiment of the present disclosure.
  • Embodiments of the present disclosure provide a method for external synthesis of rare- earth oxychloride and production of rare-earth metal/alloy.
  • the method comprises the steps of adding hydrochloric acid (HC1) to a portion of a pre-defined weight of rare-earth oxide (RE2O3) as obtained for converting the portion of RE2O3 to rare-earth chloride hydrate (RECI3.XH2O), heating the obtained rare-earth chloride hydrate (RECI3.XH2O) for evaporating water.
  • HC1 hydrochloric acid
  • RE2O3 rare-earth oxide
  • RE2O3 rare-earth chloride hydrate
  • the method further comprises mixing the residual rare-earth oxide (RE2O3) with the rare-earth chloride hydrate (RECI3.XH2O) upon evaporation of water, and heating the mixture to a temperature exceeding 300°C to obtain rare-earth oxychloride (REOC1).
  • RE2O3 residual rare-earth oxide
  • REOC1 rare-earth chloride hydrate
  • the method includes making the obtained rare-earth oxychloride (REOC1) to react directly with a reductant or mixture of reductant and alloying element in a temperature of 600°C - 1400°C for reducing the rare-earth oxychloride (REOC1) to rare-earth metal/alloy; and upon cooling, treating the reduced mass of rare-earth metal/alloy with water and dilute acid to remove reaction byproducts such as calcium chloride (CaCh) and calcium oxide (CaO).
  • REOC1 rare-earth oxychloride
  • rare earth metals have special qualities including catalytic activity, luminescence, and magnetism that make them indispensable in many important technologies. They are used in the production of permanent magnets for electric motors, generators, and speakers, as well as in the manufacturing of rechargeable batteries, catalysts, high-performance alloys, and advanced electronics like smartphones, computers, and televisions.
  • aluminum rare earth alloys combine the lightweight and corrosionresistant properties of aluminum with the enhanced mechanical and thermal characteristics provided by rare earth elements. These alloys find applications in aerospace, automotive, and defence industries, where lightweight materials with high strength and heat resistance are crucial for fuel efficiency, structural integrity, and performance.
  • Fe-RE alloys containing Neodymium (Nd), Dysprosium (Dy), Praseodymium (Pr) can be used as a raw material for the production of permanent magnets.
  • Sm-Co alloys can be used for the production of Sm-Co magnets.
  • Mg-RE alloys, Gd-Si alloys can use in some niche applications.
  • One aspect of the invention relates to a synthesis process for RE0C1.
  • the present invention introduces a novel and simple process that eliminates the need for high temperatures or the use of alkali or alkaline earth salt mediums as disclosed by the conventional techniques.
  • Figure 1 is an exemplary method of the present disclosure and illustrates various steps of the method (100) for method for synthesis of rare-earth oxychloride in low temperature and production of rare-earth metal/alloy.
  • the method (100) enables manufacturers to synthesize rare-earth oxychloride (REOC1) from rare- earth oxides and further produce rare-earth metal/alloy from the synthesized rare-earth oxychloride (REOC1).
  • the method (100) therefore eliminates the requirement of involving high-temperature processes for obtaining REOC1 by reacting rare earth oxides with molten salts comprising alkali and alkaline earth chlorides.
  • the method (100) also eliminates the requirement of additional processing such as water washing to eliminate calcium chloride (CaCh), mild acid leaching to eliminate calcium oxide (CaO) for the recovery of REOC1.
  • the method (100) according to present disclosure aids in mitigating the problems of limited solubility of CaO in a CaCh melt and effect of amount of CaO in solubility of calcium (Ca) that is used as reductant. Therefore, the present invention eliminates the need for high temperatures or the use of alkali or alkaline earth salt mediums.
  • the size and configuration of the required set of machinery for accomplishing the method (100) may be variable in accordance with the requirement of the different types of installation environment. Any such variation/modification shall be construed to be within the scope of the present disclosure.
  • the method (100) comprises one or more blocks to be performed for synthesis of rare-earth oxychloride in low temperature and production of rare-earth metal or alloy from the rare-earth oxychloride.
  • the order in which the method (100) is described is not intended to be construed as a limitation, and any number of the described method blocks can be combined in any order to implement the method. Additionally, individual blocks may be deleted from the methods without departing from the spirit and scope of the subject matter described herein.
  • hydrochloric acid (HC1) is added to a portion of a pre-defined weight of rare-earth oxide.
  • hydrochloric acid (HC1) is added to a portion of a pre-defined weight of rare-earth oxide (RE2O3) as obtained for converting the portion of RE2O3 to rare-earth chloride hydrate (RECI3.XH2O).
  • RE2O3 rare-earth oxide
  • REOC1 synthesis is achieved by addition of HC1 to convert 1/3 of the rare-earth oxide as obtained.
  • the addition of HC1 converts the part of RE2O3 to rare-earth chloride hydrate (RECI3.XH2O) as depicted in the following reactions:
  • RECI3.XH2O can also be used as a raw material along with RE2O3 for the production of REOC1.
  • water from the dissolved solution is evaporated for obtaining rare-earth chloride hydrate.
  • the dissolved solution is heated in certain temperature for evaporating water from the dissolved solution and obtaining rare-earth chloride hydrate.
  • the residual rare-earth oxide is mixed to the obtained rare-earth chloride hydrate.
  • the residual 2/3 of the obtained rare-earth oxide is mixed with the rare-earth chloride as produced upon treating the 1/3 portion the rare-earth oxide with hydrochloric acid (HC1).
  • the mixture heated to temperature exceeding 300°C for converting to rare-earth oxychloride is heated to temperature exceeding 300°C and in a range of 300°C - 1000°C.
  • the heating process facilitated the conversion of the mixture of RE2O3 and RECI3 into the rare-earth oxychloride (RE0C1) as depicted in the following reactions.
  • the rare-earth oxychloride is made to react with calcium or calcium along with alloying element for extracting rare-earth metal or alloy.
  • the obtained rare-earth oxychloride (REOC1) is reacted directly with a reductant or reductant (Ca, Mg, Al) along with alloying element in a temperature of 600°C - 1400°C under inert atmosphere for reducing rare-earth oxychloride (REOC1) to rare-earth metal or alloy, calcium chloride (CaCh), and calcium oxide (CaO) as depicted in the following reaction:
  • the reduced mass of rare-earth metal or alloy is treated with water to remove one of the reaction product, i.e. CaCh followed by a weak acid leaching such as dilute acetic acid for the removal of CaO/Ca(OH)2 to yield RE metal or alloy.
  • the acid used for removal of CaO/Ca(OH)2 can be one of organic or inorganic acid such as citric, acetic, HC1, H2SO4.
  • the calcium content in the alloy can be reduced by carefully adjusting the Ca to REOC1 ratio during the alloy formation.
  • two additional methods can be employed: either subjecting the alloy to vacuum treatment, which helps remove additional calcium impurities by exposing the alloy to low pressure conditions, or by adding it to a specific dilute alloy formation designed to selectively remove calcium from the alloy.
  • the proposed process eliminates the requirement of addition of extra CaCh as a reaction medium or a solvent for dissolving CaO. As a result, the process becomes highly energy-efficient and straightforward. The need to heat a large volume of CaCh is also eliminated, reducing energy consumption significantly. Additionally, the requirement for the removal and recovery of large volumes of CaCh is also eliminated. Thus, the solid-state process shows to be a major improvement in addressing the previous limitations and streamlining the overall production of rare-earth metal or alloy.
  • the solid-state process plays a crucial role in shaping and transforming metals and alloys without involving melting or liquid phases. These processes are used to modify the microstructure, mechanical properties, and overall characteristics of metals.
  • RE0C1 is used as an input material for the synthesis of rare earth metal or alloy production.
  • RE0C1 is added to molten CaCh or a mixture of CaCh-NaCl at temperatures above 800°C with continuous stirring in the presence of Ca under inert atmosphere.
  • the method for producing rare-earth metal or alloy from externally synthesized rare-earth oxychloride comprises the step of adding the externally synthesized rare-earth oxychloride (RE0C1) to molten calcium chloride (CaCh) or a mixture of calcium chloride (CaCh) and sodium chloride (NaCl) at temperature above 800°C with continuous stirring in presence of calcium (Ca) under controlled atmosphere for reducing the rare-earth oxychloride (RE0C1) to rare-earth metal or alloy.
  • the method also includes treating the reduced mass of rare-earth metal or alloy, upon cooling, with water and dilute weak acid to remove reaction byproducts such as calcium chloride (CaCh) and calcium oxide (CaO).
  • the production of rare earth (RE) metal is influenced by the limited solubility of CaO in a CaCh melt (approximately 20 mol%). Additionally, the solubility of calcium, which is used as a reductant in the process, is also affected by the amount of CaO.
  • an external synthesis of REOC1 is carried out and used as a substitute for RE2O3. Such substitution reduces the production of CaO since CaO is only generated during the reduction phase, not during dissolution. Furthermore, the consumption of CaCh for the conversion of RE2O3 to REOC1 also can be avoided with the proposed process.
  • the CaCh required for the dissolution of CaO formed during reaction of RE2O3 with CaCh and during reduction of REOC1 with Ca is about 5.5 kg per kg RE metal production.
  • the requirement of CaCh is brought down to 3 kg. As a result, this modification significantly increases productivity by about 50%.
  • La2C>3 was dissolved in 9.08g acid (37% HC1) and kept on hot plate for the removal water at 90 °C for 6 h.
  • the residue (LaCh.xfTO) obtained was mixed with 10g of La2Os and heated at different temperatures from 300 to 900°C for 1 h to 4 hs.
  • the obtained samples were examined using X-Ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analysis as illustrated in Figure 2 and Figure 3 respectively.
  • XRD X-Ray diffraction
  • SEM-EDX scanning electron microscopy-energy dispersive X-ray
  • NdOCl was produced by combining 1.23g of HC1 acid with 2g of Nd2Os, leading to the conversion of one-third of the Nd2Os. Subsequently, the mixture was heated to a temperature of 500°C and maintained at this temperature for one h. The addition of HC1 converts the part of Nd2Os to NdCh.xH2O. The heating process facilitated the conversion of the mixture of Nd2Os and NdCh.xH2O into NdOCl, as per the following reactions:
  • LaOCl was mixed with reductant (10% excess of stoichiometric Ca) and required amount of Al powders to produce different alloys.
  • reductant 10% excess of stoichiometric Ca
  • Al powders required amount of Al powders to produce different alloys.
  • the composition of different mixtures is shown in the Table 1.
  • the mixture was pelletized with die and punch using a press and placed in an alumina boat and kept it in a horizontal tubular furnace at 900°C for 1 h under argon atmosphere to form the Al-La alloys as per the following reaction:
  • NdOCl, Ca and aluminum powders were thoroughly mixed and pelletized as discussed in the above example (5).
  • the pellet was placed in the alumina boat and kept at 900°C for 1 h under argon atmosphere.
  • the alumina boat was removed from the furnace once it got cool down.
  • CaCh and CaO from the mixture was removed by water and dilute acetic acid washing as explained in the previous examples.
  • Figure 10 depicts the XRD pattern of Al-60% Nd alloy. About 97% purity Nd- Al alloy was recovered.
  • Nd-Fe alloy can also be produced, such alloy could be combined with B and melted to obtain Nd-Fe-B magnet raw material.
  • the Nd-Al alloy was formed according to the following reaction.
  • the present invention by introducing pre-synthesized rare-earth oxychloride into the process, enhances the productivity as the salt demonstrates a higher ability to dissolve CaO.
  • Such modification overcomes the issue of CaO formation, allowing for a more efficient calico-thermic reduction and increasing the overall output of the process.
  • the present invention also tackles the solubility limitation of CaO, even when it is formed during calico-thermic reduction. Consequently, a solid-state process has been devised wherein RE0C1 can be directly reduced using calcium, with or without the inclusion of alloying elements or their oxides. Such innovative approach enables the direct reduction of RE0C1, bypassing the use of CaCh to melt and overcoming the challenges associated with CaO solubility.
  • the present invention for the production rare earth alloy is indigenous technology of strategically important rare earth metals or rare earth alloys which can have significant implications for a society's technological advancement, economic development, and national security. These metals and alloys can be considered as "vitamins" for a society due to their critical role in various high-tech industries and applications.
  • the present invention also incurs cost of RE0C1 production that is significantly lower than REF3 production and also consumption of acid or chlorine is low.

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Abstract

La présente invention concerne une méthode de synthèse externe d'oxychlorure de terres rares et de production de métal ou d'alliage de terres rares. La méthode comprend les étapes consistant à ajouter de l'acide chlorhydrique (HCl) à une partie d'un poids prédéfini d'oxyde de terres rares (RE2O3) convertissant la partie de RE2O3 en hydrate de chlorure de terres rares (RECl3.xH2O). La méthode comprend en outre le mélange de l'oxyde de terres rares résiduel (RE2O3) avec le RECl3.xH2O et le chauffage du mélange à une température supérieure à 300°C pour obtenir de l'oxychlorure de terres rares (REOCl). La méthode comprend la réaction directe du REOCl obtenu avec un réducteur ou un mélange de réducteur et d'élément d'alliage à une température de 600°C à 1400°C pour réduire l'oxychlorure de terres rares (REOCl) en métal ou alliage de terres rares ; et lors du refroidissement, le traitement de la masse réduite de métal ou d'alliage de terres rares avec de l'eau et de l'acide dilué pour éliminer des sous-produits de réaction tels que du chlorure de calcium (CaCl2) et de l'oxyde de calcium (CaO).
PCT/IN2024/051398 2023-08-11 2024-07-27 Méthode de synthèse d'oxychlorure de terres rares et production de métal/alliage de terres rares Pending WO2025037328A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4680055A (en) * 1986-03-18 1987-07-14 General Motors Corporation Metallothermic reduction of rare earth chlorides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4680055A (en) * 1986-03-18 1987-07-14 General Motors Corporation Metallothermic reduction of rare earth chlorides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ARIDE, J. ; CHAMINADE, J.-P. ; POUCHARD, M.: "Flux growth of NdOCl single crystals", JOURNAL OF CRYSTAL GROWTH, ELSEVIER, AMSTERDAM, NL, vol. 57, no. 1, 1 March 1982 (1982-03-01), AMSTERDAM, NL , pages 194 - 196, XP024429413, ISSN: 0022-0248, DOI: 10.1016/0022-0248(82)90267-6 *
OKAMOTO, K. IMANAKA, N. ADACHI, G.: "Chloride ion conduction in rare earth oxychlorides", SOLID STATE IONICS, NORTH HOLLAND PUB. COMPANY. AMSTERDAM; NL, NL, vol. 154-155, 2 December 2002 (2002-12-02), NL , pages 577 - 580, XP004396265, ISSN: 0167-2738, DOI: 10.1016/S0167-2738(02)00496-4 *

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