WO2014057541A1 - Procédé et dispositif pour séparer des éléments de terres rares - Google Patents

Procédé et dispositif pour séparer des éléments de terres rares Download PDF

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WO2014057541A1
WO2014057541A1 PCT/JP2012/076210 JP2012076210W WO2014057541A1 WO 2014057541 A1 WO2014057541 A1 WO 2014057541A1 JP 2012076210 W JP2012076210 W JP 2012076210W WO 2014057541 A1 WO2014057541 A1 WO 2014057541A1
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rare earth
chloride
earth element
heat treatment
group
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PCT/JP2012/076210
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Japanese (ja)
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宮田　素之
山本　浩貴
元 村上
哲也 宇田
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株式会社日立製作所
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Priority to JP2014540658A priority Critical patent/JP5905592B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of 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 a technique for separating rare earth elements, and more particularly, to a method for separating rare earth elements from a composition containing a plurality of types of rare earth elements and a separation apparatus for performing the method.
  • Rare earth elements exhibit unique physical properties due to their characteristic electron arrangement, and various materials and products (for example, hydrogen storage alloys, secondary batteries, optical glasses, magnets, phosphors, Used in abrasives). Without knowing that the demand for higher performance of materials and products will not stop, demand for rare earth elements is expected to increase further in the future.
  • Rare earth elements have abundant reserves themselves, but their chemical properties are very similar to each other, making them difficult to separate and purify as a simple substance, and are therefore said to be rare elements.
  • Patent Document 1 discloses a divalent trivalent mixture in which the average valence of two or more rare earth ions is 2 or more and 3 or less by halogenating a rare earth element in a mixture containing a plurality of rare earth elements or compounds thereof. Producing a mixture containing a rare earth halide which is not dissolved in an aqueous solution or an organic solvent, and then utilizing the difference in properties between the divalent rare earth halide and the trivalent rare earth halide, There has been proposed a rare earth element separation method characterized by separating elements into at least two groups. According to Patent Document 1, it is said that the separation factor between rare earth elements can be dramatically increased, and mutual separation can be performed more efficiently than in the conventional method.
  • steps such as acid dissolution, filtration, precipitation removal of impurities, concentration, neutralization, and drying, which are essential for conventional wet methods, can be omitted. It is said that the cost can be greatly reduced.
  • Patent Document 2 discloses a method for recovering a rare earth element from a material containing a rare earth element and an iron group element, and a rare earth element such as a rare earth magnet scrap or sludge is added to a gaseous or molten iron chloride. Select a rare earth element as a chloride from the substance by contacting a substance containing an iron group element and proceeding the chlorination reaction of the rare earth element in the substance while maintaining the metallic state of the iron group element in the substance. There has been proposed a method for recovering a rare earth element characterized by having a step of recovering automatically.
  • Patent Document 2 it is possible to extract and separate only high-purity rare earth components from materials containing rare earth elements and iron group elements, such as rare earth magnet scraps or sludges, especially wastes, and thus lower cost rare earth elements. It is said that the magnet recycling law can be established.
  • JP 2001-303149 A Japanese Patent Laid-Open No. 2003-73754
  • rare earth elements As mentioned above, demand for rare earth elements is expected to continue to expand. On the other hand, in recent years, technology for separating, recovering, and recycling rare earth elements has become more important than ever due to the growing awareness of global environmental protection and the use of sustainable resources. In addition, since rare earth elements have similar chemical properties, a technique for separating specific rare earth elements from a mixture of a plurality of types of rare earth elements is particularly important.
  • an object of the present invention is to provide a method capable of easily separating a rare earth element from a composition containing a plurality of types of rare earth elements at a high separation rate, and a separation apparatus for executing the method. It is in.
  • One aspect of the present invention is a method for separating a plurality of rare earth elements, Producing a chloride / acid chloride mixture comprising a rare earth chloride of a first group of rare earth elements and a rare earth acid chloride of a second group of rare earth elements from a starting mixture comprising a plurality of rare earth oxides and a chlorinating agent.
  • An extraction process Separation for separating the first group of rare earth elements and the second group of rare earth elements by solid-liquid separation of the liquid phase from which the rare earth chloride is extracted and the solid phase of the remaining rare earth acid chloride. And providing a method for separating rare earth elements.
  • the present invention can add the following improvements or changes to the above-described rare earth element separation method (I).
  • the chlorinating agent is ammonium chloride
  • the predetermined temperature in the selective chlorination / acidification heat treatment step is a temperature within a temperature range in which the oxide of the rare earth element of the first group becomes a chloride.
  • In the starting mixture 1 mol of the rare earth oxide is mixed with more than 6 mol and less than 15 mol of the ammonium chloride.
  • the selective chlorination / acidification heat treatment step includes a step of generating a rare earth ammonium chloride salt of the first group of rare earth elements from the plurality of rare earth oxides and the ammonium chloride by a heat treatment under normal pressure. , Subsequently, an elementary step of generating a rare earth chloride of the first group rare earth element from the rare earth ammonium chloride salt by a heat treatment under reduced pressure is included.
  • the first group rare earth elements are light rare earth elements, and the second group rare earth elements are heavy rare earth elements.
  • the first group rare earth element is neodymium or europium, and the second group rare earth element is at least one selected from yttrium, terbium and dysprosium.
  • the separation apparatus comprises a composition supply part to be separated, a heat treatment part, an atmosphere control part, a gas treatment part, and a separation part
  • the composition to be separated supply unit is connected to the heat treatment unit, prepares a starting mixture by mixing the composition to be separated and a chlorinating agent, and supplies the starting mixture to the heat treatment unit
  • the heat treatment section is connected to the atmosphere control section, the gas processing section, and the separation section in addition to the composition-to-be-separated composition supply section, and the rare earth chloride of the first group of rare earth elements from the starting mixture.
  • the heat treatment is a heat treatment performed at a predetermined temperature in a non-oxidizing atmosphere controlled by the atmosphere control unit, and ammonia gas generated by the heat treatment is processed in the gas processing unit,
  • the gas processing unit includes a chemical reaction monitoring mechanism for monitoring a chemical reaction by the heat treatment,
  • the separation unit puts the chloride / acid chloride mixture into a solvent to selectively dissolve the rare earth chloride and extract it into a liquid phase, and remains with the liquid phase from which the rare earth chloride has been extracted.
  • the present invention can add the following improvements and changes to the rare earth element separation device (II).
  • the chemical reaction monitoring mechanism includes an ammonia gas sensor.
  • the chlorinating agent powder is ammonium chloride powder, and the predetermined temperature in the selective chlorination / acid oxidization heat treatment is a temperature within a temperature region in which the oxide of the rare earth element of the first group becomes a chloride. And the temperature in the temperature region where the oxide of the second group rare earth element becomes an acid chloride.
  • 1 mol of the rare earth oxide is mixed with more than 6 mol and less than 15 mol of the ammonium chloride.
  • the selective chlorination / acidification heat treatment includes an elementary reaction for generating a rare earth ammonium chloride salt of the first group rare earth element from the plurality of types of rare earth oxides and the ammonium chloride by a heat treatment under normal pressure; Subsequently, an elementary reaction of generating a rare earth chloride of the rare earth element of the first group from the rare earth ammonium chloride salt by a heat treatment under reduced pressure, Pressure control during the heat treatment is performed by the atmosphere control device.
  • the first group rare earth elements are light rare earth elements, and the second group rare earth elements are heavy rare earth elements.
  • the first group rare earth element is neodymium or europium, and the second group rare earth element is at least one selected from yttrium, terbium and dysprosium.
  • separate rare earth elements easily with a high separation rate (namely, low cost) from the composition in which multiple types of rare earth elements are mixed, and the separation apparatus for performing this method Can provide.
  • the rare earth element is yttrium, europium or terbium
  • the chlorination reaction (chemical reaction formula (1)) of the rare earth oxide the acidification reaction of the rare earth oxide (chemical reaction formula (2)), and the rare earth acid chloride
  • the present inventors aim to separate specific rare earth elements from a composition in which a plurality of types of rare earth elements are mixed at a high separation rate and easily, in particular, chemical reactions of rare earth elements (especially chloride reactions, The acidification reaction) was investigated in detail. As a result, the present inventors have found that the behavior of the chemical reaction differs depending on the type of rare earth element. And it discovered that a specific rare earth element could be isolate
  • FIG. 1 is a flowchart showing an example of steps of a method for separating rare earth elements according to the present invention. The outline of the separation method will be described with reference to FIG. First, a plurality of rare earth oxides and a chlorinating agent are mixed to prepare a starting mixture. Next, a selective chlorination / acidification heat treatment is performed to produce a chloride / acid chloride mixture containing a first group of rare earth element chlorides and a second group of rare earth element acid chlorides from the prepared starting mixture. Do. The present invention has the greatest feature in this selective chlorination / acidification heat treatment step.
  • the resulting chloride / acid chloride mixture is then charged into a solvent to selectively dissolve the rare earth chloride and extract into the liquid phase. Finally, the liquid phase from which the rare earth chloride is extracted and the solid phase of the remaining rare earth oxychloride are subjected to solid-liquid separation to recover the first group of rare earth elements and the second group of rare earth elements, respectively.
  • This step is a step of preparing a starting mixture by mixing a powder in which a plurality of kinds of rare earth oxides are mixed with a powder of a chlorinating agent.
  • a chlorinating agent it is preferable not to leave an excess element (cation) in the rare earth compound generated in the selective chlorination / acidification heat treatment step of the next step, and for example, ammonium chloride (NH 4 Cl) is preferable.
  • the mixing method is not particularly limited as long as the rare earth oxide and the chlorinating agent are mixed uniformly.
  • This step is a step of performing a heat treatment for generating a chloride / acid chloride mixture containing a first group rare earth element chloride and a second group rare earth element acid chloride from the prepared starting mixture.
  • the heat treatment atmosphere is preferably a non-oxidizing atmosphere (an atmosphere in which oxygen components are not substantially mixed, for example, in an inert gas (argon, nitrogen, etc.) stream or in a vacuum).
  • the heat treatment temperature is a temperature within a temperature region where the oxide of the first group rare earth element becomes a chloride, and a temperature within a temperature region where the oxide of the rare earth element of the second group becomes an acid chloride. Is preferred.
  • Rare earth oxide (RE 2 O 3) of rare earth chloride chloride reaction to produce (RECL 3) is, (RE what is believed to be a chemical reaction such as chemical reaction formula (1) below represents a rare earth element. Less The same).
  • the acidification reaction for producing rare earth acid chloride (REOCl) from rare earth oxide (RE 2 O 3 ) is considered to be a chemical reaction represented by the following chemical reaction formula (2).
  • the chlorination reaction that generates rare earth chloride (RECl 3 ) from rare earth acid chloride (REOCl) is considered to be a chemical reaction represented by the following chemical reaction formula (3).
  • FIG. 2 shows the case where the rare earth element is neodymium or dysprosium, the rare earth oxide chlorination reaction (chemical reaction formula (1)), the rare earth oxide acidification reaction (chemical reaction formula (2)), and the rare earth acidification. It is a graph which shows the relationship between the standard Gibbs energy change and temperature in the chlorination reaction (chemical reaction formula (3)) of a thing.
  • the standard Gibbs energy change decreases as the temperature increases. However, when the standard Gibbs energy change reaches a negative value, the chemical reaction can proceed continuously. Note that the standard Gibbs energy change can discuss thermodynamic stability / instability by negative / positive, but we can discuss the activation energy for starting a chemical reaction, and the chemical reaction rate. Not what you want.
  • Fig. 2 shows that in the rare earth oxide chlorination reaction (chemical reaction formula (1)), neodymium oxide (Nd 2 O 3 ) shows a negative value of standard Gibbs energy change at about 200 ° C or higher.
  • Dysprosium oxide (Dy 2 O 3 ) shows a negative standard Gibbs energy change at about 350 ° C. or higher.
  • neodymium oxide (Nd 2 O 3 ) is about 200 ° C or higher and dysprosium oxide (Dy 2 O 3 ) is about 350 ° C or higher.
  • the chlorination reaction of formula (1) can proceed.
  • neodymium oxide (Nd 2 O 3 ) shows a negative standard Gibbs energy change in the calculated total temperature range (0 to 600 ° C)
  • Dysprosium oxide (Dy 2 O 3 ) shows a negative standard Gibbs energy change at about 180 ° C or higher.
  • neodymium oxide (Nd 2 O 3 ) is 0 ° C or higher
  • dysprosium oxide (Dy 2 O 3 ) is about 180 ° C or higher
  • the acidification reaction can proceed.
  • neodymium oxychloride (NdOCl) shows a negative standard Gibbs energy change at about 330 ° C
  • dysprosium oxychloride (DyOCl) about 420 ° C.
  • the standard Gibbs energy change shows a negative value.
  • neodymium oxychloride (NdOCl) is about 330 ° C
  • dysprosium oxychloride (DyOCl) is about 420 ° C or higher, and the chlorination reaction of chemical reaction formula (3) proceeds. It becomes possible.
  • thermodynamically stable temperature varies greatly depending on the type of rare earth element and the type of chemical reaction. From this fact, it is possible to coexist the chlorination reaction and the acidification reaction by utilizing the difference in temperature that is thermodynamically stable.
  • FIG. 3 shows a case where a rare earth element is yttrium, europium, or terbium, and a rare earth oxide chlorination reaction (chemical reaction formula (1)), a rare earth oxide acidification reaction (chemical reaction formula (2)), It is a graph which shows the relationship between the standard Gibbs energy change and temperature in the chlorination reaction (chemical reaction formula (3)) of an acid chloride.
  • the standard Gibbs energy change decreases with increasing temperature, and the chemical reaction can proceed continuously when the standard Gibbs energy change reaches a negative value. become.
  • yttrium oxide (Y 2 O 3 ) is about 350 ° C. or higher
  • europium oxide (Eu 2 O 3 ) is Above about 250 ° C.
  • terbium oxide (Tb 2 O 3 ) shows a negative value of standard Gibbs energy change at about 330 ° C. or more. In other words, if the activation energy of the chemical reaction is exceeded, the chlorination reaction of the chemical reaction formula (1) can proceed at those temperatures or higher.
  • yttrium oxide (Y 2 O 3 ) is about 220 ° C or higher
  • europium oxide (Eu 2 O 3 ) is about 70 ° C or higher
  • terbium oxide (Tb 2 O 3 ) shows a negative value of the standard Gibbs energy change at about 200 ° C. or higher. In other words, if the activation energy of the chemical reaction is exceeded, the acidification reaction of the chemical reaction formula (2) can proceed at those temperatures or higher.
  • yttrium oxychloride (YOCl) is about 380 ° C or higher
  • europium oxychloride (EuOCl) is about 350 ° C or higher
  • terbium oxychloride (TbOCl) Shows a negative value of standard Gibbs energy change at about 370 ° C or higher. In other words, if the activation energy of the chemical reaction is exceeded, the chlorination reaction of the chemical reaction formula (3) can proceed at those temperatures or higher.
  • the temperature at which the chlorination reaction of chemical reaction formula (1) occurs in light rare earth elements (elements with atomic numbers smaller than gadolinium (Gd) in lanthanides) such as neodymium and europium is It is found that the temperature is about 100 ° C. lower than the temperature at which the chlorination reaction of the chemical reaction formula (1) in yttrium and heavy rare earth elements such as dysprosium and terbium (elements having an atomic number of gadolinium (Gd) or higher among lanthanoids) occurs. .
  • heavy rare earth elements and yttrium acid chlorides are stable in the temperature range from the temperature at which light rare earth oxides generate chloride to the time at which heavy rare earth elements and yttrium oxides generate chloride.
  • the temperature is within a temperature range in which the standard Gibbs energy change of the chlorination reaction of oxides of light rare earth elements (defined as first group rare earth elements) is negative, and heavy rare earth elements and yttrium (second group)
  • the rare earth oxide chlorination reaction and the acidification reaction can coexist by heat treatment at a temperature within the temperature range in which the standard Gibbs energy change of the chlorination reaction of the oxide of the .
  • the chlorination reaction of the chemical reaction formula (1) can be divided into the following two elementary reactions.
  • a rare earth ammonium chloride salt is produced by heat treatment in an inert gas stream at normal pressure.
  • An example of this reaction is chemical reaction formula (4) (see, for example, Meyer, et. Al., Mat. Res. Bull. 17 (1982) 1447-1455).
  • the second stage elementary reaction it is considered that ammonium chloride present in the rare earth ammonium chloride salt and unreacted ammonium chloride in the starting mixture are removed to produce rare earth chloride (RECl 3 ).
  • An example of this reaction is chemical reaction formula (5) (see, for example, Meyer, et. Al., Mat. Res. Bull. 17 (1982) 1447-1455).
  • the second stage elementary reaction is preferably performed in a reduced-pressure atmosphere (for example, a reduced-pressure atmosphere using a rotary pump or the like). This is because vaporization / decomposition of ammonium chloride tends to proceed in a reduced pressure atmosphere.
  • the solvent for example, pure water, lower alcohol, or a mixture thereof can be preferably used.
  • the lower alcohol it is particularly preferable to use methanol or ethanol. Since these solvents have a small adverse effect on the environment and the human body, they contribute to improvement in workability and simplification of work facilities (that is, cost reduction).
  • the heating temperature is preferably equal to or lower than the boiling point of the solvent.
  • This step is a step of separating the first group of rare earth elements and the second group of rare earth elements by performing a solid-liquid separation process on the solution obtained above.
  • a solid-liquid separation process For example, filtration can be utilized.
  • This step is a step of recovering the first group of rare earth elements and the second group of rare earth elements from the liquid phase and solid phase separated by solid-liquid separation.
  • the liquid phase containing the rare earth chloride can be recovered as a rare earth chloride powder, for example, by spraying in a heated atmosphere using a spray dryer.
  • a precipitant for example, ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium hydrogen carbonate (NH 4 HCO 3 ), sodium carbonate (Na 2 CO 3) ), Sodium bicarbonate (NaHCO 3 ), oxalic acid ((COOH) 2 ), sodium oxalate ((COONa) 2 ), sodium hydroxide (NaOH), etc.
  • the precipitate is filtered and dried, and then roasted at about 900 ° C. in the atmosphere, whereby the first group rare earth elements can be recovered as oxides.
  • a solid phase composed of a rare earth acid chloride can be recovered as a rare earth acid chloride powder by drying it. Moreover, after dissolving with an acid (dilute hydrochloric acid, dilute nitric acid, etc.) to produce a hydrate, and adjusting the pH of the hydrate, a precipitating agent (for example, (NH 4 ) 2 CO 3 , NH 4 HCO 3 , Na 2 CO 3 , NaHCO 3 , (COOH) 2 , (COONa) 2 , NaOH, etc.) can be added to form a hardly soluble rare earth precipitate. After filtering and drying the precipitate, the second group of rare earth elements can be recovered as oxides by roasting at about 900 ° C. in the atmosphere.
  • a precipitating agent for example, (NH 4 ) 2 CO 3 , NH 4 HCO 3 , Na 2 CO 3 , NaHCO 3 , (COOH) 2 , (COONa) 2 , NaOH, etc.
  • the separation rate between the first group of rare earth elements and the second group of rare earth elements can be further improved.
  • the separation and recovery method according to the present invention to materials containing multiple types of rare earth elements and waste products, the first group of rare earth elements and the first group can be easily combined with a high separation rate. Two groups of rare earth elements can be separated and recovered.
  • FIG. 4 is a schematic diagram showing a configuration example of a rare earth element separation device according to the present invention.
  • the rare earth element separation apparatus 100 includes a composition supply unit 10 to be separated, a heat treatment unit 20, an atmosphere control unit 30, a gas treatment unit 40, and a separation unit 50. .
  • the composition-to-be-separated supply unit 10 is connected to the heat treatment unit 20 and is a part that supplies the starting mixture obtained by performing the above-described mixing process to the heat treatment unit 20.
  • a composition container 11 to be separated that contains powder mixed with a plurality of types of rare earth oxides
  • an ammonium chloride container 12 that contains ammonium chloride powder
  • a raw material powder mixing device 13 and a starting mixture supply device 14 And have.
  • the heat treatment unit 20 is connected to the atmosphere control unit 30, the gas processing unit 40, and the separation unit 50 in addition to the composition supply unit 10 to be separated, and performs the above-described selective chlorination / acidification heat treatment step. It is. Specifically, it has a heater 21 and a core tube 22. Furthermore, a mechanism (for example, a core tube rotation mechanism (not shown)) for stirring the material to be heat-treated is provided so that the chemical reaction in the selective chlorination / acidification heat treatment step proceeds smoothly. preferable.
  • the atmosphere control unit 30 is a part that controls the atmosphere during the heat treatment in the selective chlorination / acidification heat treatment step.
  • the vacuum evacuation device 31 and the gas supply device 32 are provided, and a non-oxidizing atmosphere under normal pressure and a non-oxidizing atmosphere under reduced pressure are controlled in the selective chlorination / acidification heat treatment step.
  • the vacuum exhaust device 31 There is no particular limitation on the vacuum exhaust device 31, and for example, a rotary pump can be suitably used.
  • the gas treatment unit 40 is a part for detoxifying the ammonia gas and the hydrogen chloride gas generated by the selective chlorination / acidification heat treatment.
  • the gas processing unit 40 includes a chemical reaction monitoring mechanism (for example, an ammonia gas sensor 41) in addition to the ammonia processing device 42 and the hydrogen chloride processing device 43.
  • a chemical reaction monitoring mechanism for example, an ammonia gas sensor 41
  • the concentration of the gas generated by the chemical reaction by the ammonia gas sensor 41 and monitoring the average gas concentration per unit time (gas concentration change rate)
  • the concentration of the generated gas can be detected from a sharp drop.
  • the chemical reaction monitoring mechanism is not limited to the gas sensor, and may be a mechanism that detects a change in the weight of the object to be heat treated, for example.
  • the separation unit 50 is a part that performs the above-described selective extraction step and separation step. Specifically, it has a solvent container 51 that contains the solvent used in the selective extraction step, a dissolution tank 52 that performs selective extraction / solid-liquid separation processing, and an extraction liquid container 53 that contains the extracted liquid phase components. .
  • the extraction liquid stored in the extraction liquid container 53 and the solid phase component remaining in the dissolution tank 52 proceed to the recovery step described above, respectively.
  • rare earth elements were separated from a mixture of rare earth oxides.
  • starting materials for rare earth oxides neodymium oxide powder (Nd 2 O 3 , manufactured by High Purity Chemical Laboratory Co., Ltd., product number: NDO01PB) and dysprosium oxide powder (Dy 2 O 3 , High Purity Chemical Laboratory Co., Ltd.) Manufactured, product number: DYO01PB).
  • the chlorinating agent ammonium chloride powder (NH 4 Cl, manufactured by Wako Pure Chemical Industries, Ltd., product number: 017-02995) was used.
  • Table 1 shows the identification results of the crystalline phase of the powder obtained in the selective chlorination / acidification heat treatment step.
  • neodymium acid chloride NaCl
  • Table 1 shows the identification results of the crystalline phase of the powder obtained in the selective chlorination / acidification heat treatment step.
  • neodymium acid chloride NaCl
  • Table 1 shows the identification results of the crystalline phase of the powder obtained in the selective chlorination / acidification heat treatment step.
  • dysprosium compound unreacted dysprosium oxide (Dy 2 O 3 ) and dysprosium chloride (DyCl 3 ) were detected when the first-stage heat treatment temperatures were 200 ° C. and 250 ° C. In the case of 300 to 500 ° C., dysprosium chloride (DyOCl) and dysprosium chloride (DyCl 3 ) were detected. As chloride, some hydrates were also detected. From the above results, it was confirmed that NdCl 3 and DyOCl were formed at the same time when the first-stage heat treatment temperature was 300 to 500 ° C.
  • Table 2 shows the XRD peak intensity ratio (REOCl / RECl 3 ) between the detected rare earth acid chloride (REOCl) and the rare earth chloride (RECl 3 ).
  • the peak intensity ratio was calculated using the peak intensity values of the (102) plane of DyOCl, the (001) plane of DyCl 3 , the (102) plane of NdOCl, and the (201) plane of NdCl 3 .
  • Table 3 is a table showing the NH 4 Cl mixing amount with respect to the rare earth oxide, the heat treatment temperature of the selective chlorination / acidification heat treatment step, and the identification result of the crystal phase of the obtained powder.
  • Table 3 at a heat treatment temperature of 300 ° C., when the mixed amount of NH 4 Cl was 6 mol or less with respect to 1 mol of Nd 2 O 3 , NdOCl was detected and an NdCl 3 single phase was not obtained. However, when the NH 4 Cl mixing amount was 9 mol, it became an NdCl 3 single phase. In addition, when the amount of NH 4 Cl mixed was 15 mol with respect to 1 mol of Dy 2 O 3 , DyOCl was not detected but a single DyCl 3 phase was detected.
  • the amount of NH 4 Cl mixed with 1 mol of rare earth oxide is preferably more than 6 mol and less than 15 mol, more preferably 9 mol or more and 13.5 mol or less. It was confirmed.
  • Experiment 3 Separation experiment of neodymium and dysprosium First, a starting mixture was prepared in the same manner as in Experiment 1. Next, a selective chlorination / acidification heat treatment step was performed. The heat treatment conditions were as follows: heat treatment was held at 300 ° C. for 4 hours in an Ar gas flow and then held at 400 ° C. for 2 hours while being evacuated by a rotary pump. The obtained chloride / acid chloride mixed powder was subjected to a selective extraction step, and the solution was filtered and solid-liquid separated as a separation step.
  • the composition of the separated solid phase was analyzed by fluorescent X-ray analysis.
  • a measurement sample was press-molded using a molding binder (boric acid powder) and subjected to measurement.
  • An X-ray fluorescence analyzer (manufactured by Rigaku Corporation, model: ZSX Primus II) was used as the measuring device.
  • the measurement conditions were as follows: Rh-K ⁇ ray was used as X-ray, X-ray output was 3 kW, and analysis diameter was 20 mm.
  • the quantitative value obtained in this analysis was calculated by the fundamental parameter method (FP method). The results are shown in Table 4.
  • Dy separation rate (Dy separation) 100 x ⁇ [Dy] / ([Dy] + [Nd]) ⁇ ... Formula (1)
  • rare earth elements for example, yttrium, terbium, neodymium, europium, dysprosium, etc.
  • Elements can be regenerated as raw materials. As a result, it can contribute to effective utilization of resources and stable securing of rare earth materials.

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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un procédé, dans lequel des éléments de terres rares peuvent être facilement séparés à un rapport de séparation élevé à partir d'un mélange contenant plusieurs types d'éléments de terres rares, et un dispositif de séparation pour conduire le procédé. Le procédé pour séparer des éléments de terres rares selon la présente invention, dans lequel des types multiples d'éléments de terres rares sont séparés, comprend : une étape de traitement thermique pour chloration / oxychloration sélective, ladite étape étant une étape de production d'un mélange de chlorure / oxychlorure contenant un chlorure de terre rare d'un élément de terre rare du groupe 1 et un oxychlorure de terre rare d'un élément de terre rare du groupe 2 à partir d'un mélange de départ contenant des types multiples d'oxydes de terres rares et du chlorure d'ammonium, pour effectuer un traitement thermique à une température prédéfinie dans une atmosphère non oxydante ; une étape d'extraction sélective pour transférer le mélange de chlorure / oxychlorure dans un solvant, dissoudre sélectivement le chlorure de terre rare dans le solvant, puis extraire celui-ci dans une phase liquide ; et une étape de séparation pour la séparation solide-liquide de la phase liquide ayant été extraite à partir d'une phase solide résiduelle de l'oxychlorure de terre rare et ainsi la séparation de l'élément de terre rare du groupe 1 de l'élément de terre rare du groupe 2.
PCT/JP2012/076210 2012-10-10 2012-10-10 Procédé et dispositif pour séparer des éléments de terres rares WO2014057541A1 (fr)

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PCT/JP2012/076210 WO2014057541A1 (fr) 2012-10-10 2012-10-10 Procédé et dispositif pour séparer des éléments de terres rares

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105969974A (zh) * 2016-05-20 2016-09-28 辽宁科技大学 一种从稀土矿石中选择性提取稀土金属的方法
JP2017098456A (ja) * 2015-11-26 2017-06-01 国立大学法人大阪大学 粒界拡散処理剤製造方法及びＲＦｅＢ系磁石製造方法
CN109112317A (zh) * 2018-10-16 2019-01-01 内蒙古科技大学 还原-氧化分离稀土混合物La2O3-Re2O3的方法
CN114377597A (zh) * 2021-12-08 2022-04-22 谢桂明 一种稀土元素提取用稀土溶液制作设备

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JPH0551208A (ja) * 1991-08-22 1993-03-02 Kinya Adachi 気相錯体の形成を利用した希土類元素の相互分離
JP2001303149A (ja) * 2000-04-24 2001-10-31 Tetsuya Uda 希土類元素の分離方法及び希土類元素分離用組成物
WO2009119720A1 (fr) * 2008-03-26 2009-10-01 財団法人生産技術研究奨励会 Procédé et appareil pour la collecte d'éléments terres rares
WO2012137727A1 (fr) * 2011-04-08 2012-10-11 株式会社日立製作所 Procédé de séparation et de récupération de terres rares

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0551208A (ja) * 1991-08-22 1993-03-02 Kinya Adachi 気相錯体の形成を利用した希土類元素の相互分離
JP2001303149A (ja) * 2000-04-24 2001-10-31 Tetsuya Uda 希土類元素の分離方法及び希土類元素分離用組成物
WO2009119720A1 (fr) * 2008-03-26 2009-10-01 財団法人生産技術研究奨励会 Procédé et appareil pour la collecte d'éléments terres rares
WO2012137727A1 (fr) * 2011-04-08 2012-10-11 株式会社日立製作所 Procédé de séparation et de récupération de terres rares

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017098456A (ja) * 2015-11-26 2017-06-01 国立大学法人大阪大学 粒界拡散処理剤製造方法及びＲＦｅＢ系磁石製造方法
CN105969974A (zh) * 2016-05-20 2016-09-28 辽宁科技大学 一种从稀土矿石中选择性提取稀土金属的方法
CN109112317A (zh) * 2018-10-16 2019-01-01 内蒙古科技大学 还原-氧化分离稀土混合物La2O3-Re2O3的方法
CN114377597A (zh) * 2021-12-08 2022-04-22 谢桂明 一种稀土元素提取用稀土溶液制作设备

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