WO2021039875A1 - ベリリウム溶液の製造方法、ベリリウムの製造方法、水酸化ベリリウムの製造方法、酸化ベリリウムの製造方法、及び、ベリリウム酸化物 - Google Patents

ベリリウム溶液の製造方法、ベリリウムの製造方法、水酸化ベリリウムの製造方法、酸化ベリリウムの製造方法、及び、ベリリウム酸化物 Download PDF

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WO2021039875A1
WO2021039875A1 PCT/JP2020/032263 JP2020032263W WO2021039875A1 WO 2021039875 A1 WO2021039875 A1 WO 2021039875A1 JP 2020032263 W JP2020032263 W JP 2020032263W WO 2021039875 A1 WO2021039875 A1 WO 2021039875A1
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Prior art keywords
beryllium
solution
producing
oxide
main heating
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Ceased
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PCT/JP2020/032263
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English (en)
French (fr)
Japanese (ja)
Inventor
中道　勝
金　宰煥
孔明 赤津
優 中野
智彦 川上
和男 米原
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Kaken Inc
National Institutes For Quantum Science and Technology
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Kaken Inc
National Institutes For Quantum Science and Technology
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Priority to AU2020336502A priority Critical patent/AU2020336502B2/en
Priority to JP2021542982A priority patent/JP7610207B2/ja
Priority to BR112022003267A priority patent/BR112022003267A2/pt
Priority to US17/636,491 priority patent/US12467115B2/en
Publication of WO2021039875A1 publication Critical patent/WO2021039875A1/ja
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
    • 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
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C01F1/00—Methods of preparing compounds of the metals beryllium, magnesium, aluminium, calcium, strontium, barium, radium, thorium, or the rare earths, in general
    • 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
    • C01F3/00—Compounds of beryllium
    • 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
    • C01F3/00—Compounds of beryllium
    • C01F3/02—Oxides; Hydroxides
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • 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
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/32—Carboxylic 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B35/00—Obtaining beryllium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline 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 a production method for producing a beryllium solution from beryllium oxide.
  • the present invention also relates to a method for producing beryllium, beryllium hydroxide, and beryllium oxide, and beryllium oxide.
  • Beryllium is known to be contained in Be—Si—O ore and Be—Si—Al—O ore.
  • Be—Si—O ores include beltlandite and phenacite
  • examples of Be—Si—Al—O ores include beryl and chrysoberyl.
  • such ores containing beryllium will be referred to as beryllium ores.
  • Beryllium ore is an example of beryllium oxide.
  • beryllium When producing beryllium, a compound containing beryllium, or an alloy containing beryllium, first, beryllium is extracted from the beryllium ore by dissolving the beryllium ore in a solvent. However, it is not easy to dissolve beryllium ore in a solvent.
  • An acidic solution such as sulfuric acid is known as a solvent that easily dissolves beryllium ore, but beryllium ore is difficult to dissolve even in an acidic solution.
  • Non-Patent Document 1 describes that beryllium ore can be dissolved in a solvent by subjecting beryllium ore to pretreatment such as sintering treatment or melting treatment.
  • the pretreatment for dissolving beryllium ore in a solvent requires a very large amount of energy.
  • the temperature when the sintering treatment is performed is, for example, 770 ° C.
  • the temperature when the melting treatment is performed is, for example, 1650 ° C.
  • the invention according to one aspect of the present invention has been made in view of the above-mentioned problems, and an object of the present invention is a method for producing a beryllium solution by dissolving beryllium oxide, which is a novel method having high energy efficiency. To provide a manufacturing method.
  • the method for producing a beryllium solution according to one aspect of the present invention includes a main heating step of producing a beryllium solution by dielectrically heating an acidic solution containing beryllium oxide.
  • the method for producing beryllium according to one aspect of the present invention includes each step included in the method for producing a beryllium solution according to one aspect of the present invention, and an anhydration step for producing a beryllium salt by dehydrating the beryllium solution.
  • the present invention includes an electrolysis step of producing beryllium by performing melt salt electrolysis of the beryllium salt.
  • the method for producing beryllium hydroxide according to one aspect of the present invention produces beryllium hydroxide by neutralizing each step included in the method for producing a beryllium solution according to one aspect of the present invention and the beryllium solution with a base. Includes a neutralization step.
  • the method for producing beryllium oxide according to one aspect of the present invention includes each step included in the method for producing beryllium solution according to one aspect of the present invention and a third heating method for producing beryllium oxide by heating the beryllium solution. Includes steps and.
  • the beryllium oxide according to one aspect of the present invention is a beryllium oxide having crystallinity and having a plurality of recesses formed on the surface, and some or all of the plurality of recesses are ,
  • the shape of the opening reflects the shape of the unit cell of the crystal.
  • FIG. 1 is a flowchart of a method M10 for producing a beryllium solution.
  • the beryllium solution production method M10 is also simply referred to as a production method M10.
  • a method for producing a BeCl 2 solution which is an aqueous solution of beryllium chloride (BeCl 2 ), which is a hydrochloride salt of beryllium, will be described.
  • the beryllium solution produced using the production method M10 is not limited to the BeCl 2 solution, and may be a BeSO 4 solution which is an aqueous solution of beryllium sulfate (BeSO 4 ) which is a sulfate of beryllium.
  • beryllium nitrate nitrates of beryllium (be (NO 3) 2) be (NO 3) an aqueous solution of it may be a 2 solution, beryllium fluoride beryllium hydrofluoric acid salt (BeF 2) It may be beryllium bromide (BeBr 2 ), which is beryllium hydrobromide, or beryllium iodide (BeI 2 ), which is beryllium hydroiodide. Good.
  • the manufacturing method M10 includes a crushing step S11, a preheating step S12, a main heating step S13, a first impurity removing step S14, and a second impurity removing step S15.
  • Berylium ore is used as a raw material for producing a berylium solution.
  • Beryllium ore is a general term for ores containing beryllium, and is also an example of beryllium oxide.
  • Beryllium ore is crystalline.
  • Beryllium ores are mainly classified into Be-Si—O-based ores containing beryllium and silicon, and Be—Si—Al—O-based ores containing beryllium, silicon, and aluminum.
  • Be—Si—O ores examples include beltlandite and phenacite, and examples of Be—Si—Al—O ores include beryl and chrysoberyl.
  • the production method M10 will be described using beryl as an example of the raw material.
  • the crushing step S11 is a step of crushing the lump beryl until it becomes granular.
  • the technique used for crushing beryl is not limited, and can be appropriately selected from existing techniques, and examples thereof include a hammer and a ball mill. Further, as a technique used for crushing beryl, a plurality of techniques (for example, a hammer and a ball mill) may be combined. In this case, a hammer may be used as the first step and a ball mill may be used as the second step of the crushing step S11.
  • beryl can be pulverized more finely, the ratio of the surface area to the total volume of beryl can be increased. Therefore, in the preheating step S12 and the main heating step S13 described later, beryllium contained in beryl is dissolved in the solution. It can be expected that the time required for this will be shortened. On the other hand, if beryl is to be crushed excessively finely, the time and cost required for the crushing step S11 will increase. Therefore, the particle size of beryl obtained after the execution of the crushing step S11 is determined in consideration of the time required for the preheating step S12 and the main heating step S13, the time required for the crushing step S11, the cost required for the crushing step S11, and the like. Is preferable.
  • any of the average diameter, the mode diameter, and the median diameter may be used.
  • the average diameter is the particle size which is the average value of the obtained particle size distribution
  • the mode diameter is the mode particle size of the particle size distribution
  • the median size is.
  • the particle size is such that the cumulative frequency in the particle size distribution is 50%.
  • the crushing step S11 is carried out so that the average diameter of beryl is 100 ⁇ m.
  • the preheating step S12 is a step to be carried out before the main heating step S13 described later, and is a step of dielectric heating a basic solution containing beryl.
  • the basic solution is not particularly limited, but an aqueous solution of sodium hydroxide (NaOH) or an aqueous solution of potassium hydroxide (KOH), which is a basic solute, can be adopted.
  • a NaOH solution is used as the basic solution.
  • the concentration of NaOH in the NaOH solution can be adjusted as appropriate, but it is preferable that the pH is adjusted to 14 or more.
  • Dielectric heating is a general term for technology that heats an object by applying an electromagnetic wave having a predetermined frequency to the object. Depending on the band of the applied electromagnetic wave, it may be called high frequency heating or microwave heating. To do. For example, high-frequency heating applies an electromagnetic wave contained in a band of 3 MHz or more and less than 300 MHz (so-called short wave or ultra-short wave) to an object, and microwave heating applies an electromagnetic wave contained in a band of 300 MHz or more and less than 30 GHz (so-called microwave). Apply to the object.
  • a microwave oven which is also widely used in homes, is an example of a device capable of performing microwave heating.
  • an electromagnetic wave having a frequency of 2.45 GHz is applied to the NaOH solution containing beryl.
  • the configuration of the device that applies electromagnetic waves to the NaOH solution containing beryl will be described later with reference to FIG.
  • a plurality of recesses are formed on the surface of the beryl. Some or all of these recesses have a shape in which the shape of the opening reflects the shape of the unit cell of the crystal.
  • the surface of the beryl on which the plurality of recesses are formed is fragile as compared with the surface of the beryl before the main heating step S13 is carried out.
  • the beryl after the preheating step S12 is dissolved in the acidic solution by carrying out the main heating step S13 described later.
  • the production method M10 includes the preheating step S12, Be-Si—Al—O-based ores (beryl, chrysoberyl, etc.) that are difficult to dissolve only by carrying out the main heating step S13 alone are melted. be able to. Therefore, not only Be-Si-O-based ores that are relatively easily dissolved in acidic solutions (berterandite, phenacite, etc.) but also Be-Si-Al-O-based ores that are difficult to dissolve in acidic solutions are used as starting materials. As a result, a beryllium chloride solution can be produced.
  • the production method M10 includes a preheating step S12. It may be left out or omitted.
  • beryl after the preheating step S12 and beryl and beryllium ion which are basic solutions after the preheating step S12 and are examples of beryllium oxide.
  • beryl having a plurality of recesses formed on the surface having a shape of the opening reflecting the shape of the unit cell of the crystal is dissolved in the acidic solution by the main heating step S13 described later. Therefore, beryl after the preheating step S12 is carried out is suitable as a raw material for producing a beryllium solution.
  • Be-Si-Al-O-based ore such as beryl is difficult to dissolve when only the main heating step S13 is carried out without carrying out the preheating step S12.
  • a plurality of recesses are formed on the surface, even a Be—Si—Al—O ore can be melted by carrying out the main heating step S13.
  • the heating temperature in the preliminary heating step S12 can be appropriately set.
  • the heating temperature in the preheating step S12 is preferably equal to or lower than the heat resistant temperature of the container (for example, the container 14 according to the fifth embodiment) containing the basic solution containing beryl.
  • the heating temperature in the preheating step S12 is preferably 250 ° C. or lower.
  • the heating temperature in the preheating step S12 may exceed 250 ° C.
  • the heating temperature in the preheating step S12 is preferably 180 ° C. or higher.
  • the preheating step S12 having a heating temperature of 180 ° C. or higher and the main heating step S13 described later in combination a large amount of beryllium contained in beryl can be dissolved in the solution.
  • the heating time in the preheating step S12 can be appropriately set, but is preferably 60 minutes or more, for example.
  • the main heating step S13 is a step of producing a beryllium solution, which is an acidic solution in which beryllium is dissolved, by dielectrically heating an acidic solution containing beryl after the preheating step S12.
  • the acidic solution is not particularly limited, but is an acidic solute such as hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), hydrogen fluoride (HF), hydrogen bromide (HBr), and the like. And any aqueous solution of hydrogen iodide (HI) can be adopted.
  • an HCl solution is used as the acidic solution.
  • the concentration of HCl in the HCl solution can be adjusted as appropriate, but it is preferable that the pH is adjusted to 1 or less.
  • the basic solution containing beryllium becomes an acidic solution containing beryllium via neutrality.
  • the dielectric heating carried out in the main heating step S13 is the same as the dielectric heating carried out in the preheating step S12. That is, in the present embodiment, an electromagnetic wave having a frequency of 2.45 GHz is applied to the HCl solution containing beryl.
  • beryllium oxide By heating an acidic solution containing beryllium oxide using dielectric heating, beryllium oxide can be dissolved in the acidic solution with higher energy efficiency than before. Specifically, a hydrochloric acid solution in which beryllium chloride hydrate (BeCl 2 ⁇ xH 2 O) is dissolved can be obtained. Therefore, the manufacturing method M10 can provide a novel manufacturing method with high energy efficiency.
  • the heating temperature in the main heating step S13 can be appropriately set in the same manner as the heating temperature in the preheating step S12. That is, when the container (for example, the container 14 according to the fifth embodiment) containing the acidic solution containing beryl is made of polytetrafluoroethylene, the heating temperature in the main heating step S13 is 250 ° C. or lower. Is preferable. Further, the heating temperature in the main heating step S13 is preferably 180 ° C. or higher. Further, the heating time in the preheating step S12 can be appropriately set, but is preferably 60 minutes or more, for example.
  • the first impurity removing step S14 is a step carried out after the main heating step S13.
  • the first impurity removing step S14 is a step of removing the first element from the BeCl 2 solution obtained in the main heating step S13 by using an organic compound that adsorbs the first element.
  • the first element to be removed in the first impurity removing step S14 is determined by the organic compound used here.
  • the organic compound that can be used in the first impurity removing step S14 include tri-n-octylphosphine oxide (TOPO, Tri-n-octylphosphine oxide) and di- (2-ethylhexyl) phosphoric acid (D2EHPA, Di- (2-ethylhexyl). ) Phosphoric acid), tributyl phosphate (TBP, Tri-n-butyl phosphate), and ethylenediaminetetraacetic acid (EDTA).
  • TOPO Tri-n-octylphosphine oxide
  • D2EHPA Di- (2-ethylhexyl
  • Phosphoric acid tributyl phosphate
  • TBP Tri-n-butyl phosphate
  • EDTA ethylenediaminetetraacetic acid
  • TOPO can adsorb Al, Au, Co, Cr, Fe, Hf, Re, Ti, UO 2 2+, V, Zr, rare earth elements, and actinide elements.
  • D2EHPA can adsorb U, Co, Ni, Mn and the like.
  • TBP can adsorb U, Th, and the like.
  • the EDTA type can adsorb Mg, Ca, Ba, Cu, Zn, Al, Mn, Fe and the like.
  • the UTEVA (registered trademark) resin can adsorb U, Th, Pu, Am and the like. These elements are examples of the first element.
  • organic compounds are soluble in organic solvents (eg kerosene, cyclohexane, benzene, etc.).
  • organic solvents eg kerosene, cyclohexane, benzene, etc.
  • the organic compound adsorbs the first element by mixing the solution in which these organic compounds are dissolved with the HCl solution after carrying out the main heating step S13 and stirring the solution.
  • the liquidity of the HCl solution mixed with the organic compound solution is preferably acidic, and more preferably the pH is 2 or less. According to this configuration, the efficiency with which the organic compound adsorbs the first element can be increased without the organic compound adsorbing beryllium. The closer the liquid property of the HCl solution is to neutrality, the higher the efficiency of the organic compound adsorbing beryllium and the lower the efficiency of adsorbing the first element.
  • TOPO and kerosene are adopted as the organic compound and the organic solvent used in the first impurity removing step S14.
  • each of the organic compound and the organic solvent is not limited to TOPO and kerosene, and can be appropriately selected from the combinations exemplified above.
  • the BeCl 2 solution which is an aqueous solution obtained in the main heating step S13, and the organic solvent are separated into two layers by leaving them for a while. Therefore, the BeCl 2 solution in which the content of the first element is suppressed by carrying out the first impurity removing step S14 and the organic solvent containing the first element can be easily separated.
  • the concentration of the first element contained in the beryllium solution can be reduced.
  • concentration of the first element contained in the production of any of beryllium, beryllium hydroxide, and beryllium oxide from the beryllium solution can be reduced.
  • the first element include uranium, thorium, plutonium, americium and the like.
  • the second impurity removing step S15 is a step carried out after the main heating step S13, and adjusts the polarity of the BeCl 2 solution obtained in the main heating step S13 from acidic to basic via neutral. This further comprises the step of removing the second element from the BeCl 2 solution.
  • the first impurity removing step S14 and the second impurity removing step S15 are described as being carried out in this order after the main heating step S13, but the first impurity removing is performed.
  • the order of the step S14 and the second impurity removing step S15 can be interchanged.
  • baking soda NaHCO 3
  • beryllium solution HCl solution containing beryllium
  • hydroxides for example, Al (OH) 3 and Fe (OH) 3
  • Be (OH) 2 is dissolved in the beryllium solution and does not precipitate.
  • aluminum (Al) and iron (Fe) are examples of the second element.
  • Hydroxides of elements other than beryllium precipitated in the beryllium solution by carrying out the second impurity removing step S15 can be easily removed from the beryllium solution by filtering the beryllium solution.
  • HCl again to the beryllium solution from which the second element has been removed by carrying out the second impurity removing step S15.
  • the polarity of the Be (OH) 2 solution is adjusted to be acidic via neutrality, and the beryllium chloride hydrate having high purity is contained in the solution. BeCl 2 ⁇ xH 2 O) is produced.
  • the concentration of the second element contained in the beryllium solution can be reduced.
  • a beryllium solution is produced by dissolving beryllium ore in an acidic solution, even if the beryllium ore contains a second element other than beryllium as described above.
  • the concentration of the second element contained can be reduced.
  • the basic solution containing beryllium oxide is dielectrically heated by applying microwaves, and in the main heating step S13, beryllium is applied by applying microwaves. It is preferable to dielectrically heat the acidic solution containing the oxide.
  • the technology of dielectric heating using microwaves (that is, microwave dielectric heating) is a technology used in so-called microwave ovens and is a widely used technology. Therefore, the manufacturing method M10 can reduce the cost required for implementation as compared with the conventional manufacturing method.
  • the beryllium solution is preferably a beryllium chloride solution.
  • a beryllium chloride solution can be easily produced without passing through beryllium hydroxide.
  • Beryllium chloride, beryllium hydroxide, and beryllium oxide can be easily produced from the beryllium chloride solution as described later. Therefore, as the beryllium solution, a beryllium chloride solution is suitable.
  • each of the beryllium production method M20, the beryllium hydroxide production method M30, and the beryllium oxide production method M40 are also simply referred to as the production method M20, the production method M30, and the production method M40, respectively. ..
  • the manufacturing method M20 includes a crushing step S11, a preheating step S12, a main heating step S13, a first impurity removing step S14, and a second, which are included in the manufacturing method M10 shown in FIG.
  • the impurity removing step S15, the dehydration step S21, and the electrolysis step S22 are included.
  • the crushing step S11, the preheating step S12, the main heating step S13, the first impurity removing step S14, and the second impurity removing step S15 are also simply referred to as the respective steps S11 to S15.
  • the steps S11 to S15 of the manufacturing method M10 included in the manufacturing method M20 are the same as the steps S11 to S15 described in the first embodiment. Therefore, the description of each of the steps S11 to S15 will be omitted here. That is, assuming that BeCl 2 solution BeCl 2 is dissolved in HCl solution is obtained, for the manufacturing method M20, a dehydration step S21, a description will be given only with the electrolysis step S22.
  • BeCl 2 which is an example of beryllium salt is produced by anhydrousing BeCl 2 ⁇ xH 2 O contained in the BeCl 2 solution obtained in each step S11 to S15 of the production method M10. It is a process to do.
  • ammonium chloride is added to beryllium chloride hydrate, and the beryllium chloride hydrate is heated in vacuum at 90 ° C. for 24 hours to bring the water content as close to 0 as possible. be able to. That is, beryllium chloride hydrate can be made anhydrous.
  • Ammonium chloride reacts with water in beryllium chloride hydrate to become ammonium hydroxide and hydrochloric acid.
  • the produced ammonium hydroxide and hydrochloric acid react again and return to ammonium chloride while releasing water.
  • Anhydrous beryllium chloride can be obtained from beryllium chloride hydrate in such a process.
  • the heating temperature in the anhydrous step S21 is not limited to 90 ° C., and can be appropriately selected from a temperature range of 80 ° C. or higher and 110 ° C. or lower. However, if the heating temperature is too high, the anhydrous beryllium chloride hydrate tends to be insufficient. Therefore, the heating temperature is preferably 80 ° C. or higher and 90 ° C. or lower, and more preferably 90 ° C. or lower.
  • the time for performing the anhydrous treatment in the anhydrous step S21 is not limited to 24 hours, and can be appropriately determined.
  • the electrolysis step S22 is a step of producing metallic beryllium by molten salt electrolysis of BeCl 2 obtained in the anhydrous step S21.
  • metal beryllium can be produced from beryllium ore via a BeCl 2 solution.
  • beryllium can be produced from beryllium ore without passing through beryllium hydroxide.
  • beryllium hydroxide which is in high general demand, is produced from beryllium ore, and then beryllium is produced from beryllium hydroxide. Therefore, the production method M20 can produce beryllium more easily than the currently commercialized method for producing beryllium.
  • the manufacturing method M30 includes steps S11 to S15 of the manufacturing method M10 and a neutralization step S31. As in the case of the manufacturing method M20, only the neutralization step S31 will be described here.
  • the neutralization step S31 produces Be (OH) 2 by neutralizing BeCl 2 ⁇ xH 2 O contained in the BeCl 2 solution obtained in each step S11 to S15 of the production method M10 with a base. It is a process.
  • Be (OH) 2 can be produced from beryllium ore by carrying out the production method M30.
  • the manufacturing method M40 includes steps S11 to S15 of the manufacturing method M10 and a heating step S41. As in the case of the manufacturing method M20, only the heating step S41 will be described here.
  • the heating step S41 includes a third heating step of producing BeO by heating the BeCl 2 solution obtained in each of the steps S11 to S15 of the production method M10. This step, BeCl 2 ⁇ xH 2 O dissolved in BeCl 2 solution is hydrolyzed, BeO is generated.
  • BeO can be produced from beryllium ore by implementing the production method M40.
  • beryllium, beryllium hydroxide, and beryllium oxide can be produced by using a novel energy-efficient production method.
  • Each of the anhydrous step S21, the electrolysis step S22, the neutralization step S31, and the heating step S41 can be carried out by using the existing technology.
  • FIG. 3 is a schematic view of the heating device 10.
  • the heating device 10 is a heating device that carries out each of the preheating step S12 and the main heating step S13 included in the manufacturing method M10 shown in FIG.
  • the induction heating is classified into either high frequency heating or microwave heating according to the band of the applied electromagnetic wave.
  • the heating device 10 is a device that performs microwave heating of high-frequency heating and microwave heating on an object.
  • the heating device 10 includes a microwave oscillator 11, a waveguide 12, a microwave application unit 13, a container 14, a rotary table 15, a stirrer 16, and a thermometer 17. It has. Further, the heating device 10 further includes a control unit (not shown in FIG. 3).
  • the microwave oscillating unit 11 is configured to oscillate an electromagnetic wave having a predetermined frequency.
  • the predetermined frequency can be appropriately selected, for example, within the microwave band, but in the present embodiment, the predetermined frequency is 2.45 GHz.
  • the frequency of 2.45 GHz is the same frequency as the electromagnetic waves used in household microwave ovens.
  • the waveguide 12 is a metal tubular member, one end of which is connected to the microwave oscillator 11 and the other end of which is connected to the microwave application unit 13.
  • the waveguide 12 guides the electromagnetic wave oscillated by the microwave oscillating unit 11 from one end to the other end, and radiates this electromagnetic wave from the other end to the internal space of the microwave applying unit 13.
  • the microwave application unit 13 is a metal box-shaped member having a hollow internal space, and is configured to accommodate the container 14 in the internal space.
  • the microwave application unit 13 applies an electromagnetic wave radiated from the other end of the waveguide 12 to the container 14 and the object to be heated housed in the container 14.
  • the microwave application unit 13 is configured to confine electromagnetic waves in the internal space and prevent them from leaking to the outside.
  • the container 14 is a container composed of a main body and a lid.
  • the main body is composed of a tubular side wall and a bottom that seals one end of the side wall.
  • the container 14 is configured so that the internal space formed by the main body and the lid can be sealed by connecting the main body and the lid.
  • the container 14 is preferably made of a material having a high transmittance for an electromagnetic wave (2.45 GHz in this embodiment) oscillated by the microwave oscillating unit 11.
  • the container 14 is made of a fluororesin typified by polytetrafluoroethylene.
  • the container 14 has a pressure resistance that can withstand even when the pressure in the internal space becomes higher than the atmospheric pressure.
  • the container 14 is applied with an electromagnetic wave because the internal space can be sealed and has a pressure resistance that can withstand a predetermined pressure, and the temperature of the object to be heated housed in the internal space rises. However, the object can be kept in the internal space.
  • the rotary table 15 is a sample table provided on the bottom surface of the internal space of the microwave application unit 13, and is configured so that the container 14 can be placed on the upper surface.
  • the rotary table 15 has a circular shape when viewed in a plan view, and is configured to rotate at a predetermined speed with its central axis as a rotation axis. According to this configuration, since the container 14 placed on the upper surface of the rotary table 15 rotates periodically, the object can be heated more uniformly.
  • the stirrer 16 is a metal pinnate member provided on the ceiling surface of the internal space of the microwave application unit 13. It is rotatably fixed to the ceiling surface by a support rod connected to the center of the pinnate member. The stirrer 16 rotates at a predetermined speed with the support rod as a rotation axis, so that the electromagnetic wave oscillated by the microwave oscillating unit 11 is reflected and scattered in the internal space of the microwave applying unit 13. According to this configuration, the stirrer 16 scatters electromagnetic waves, so that the object can be heated more uniformly.
  • the thermometer 17 is a radiation thermometer that measures the temperature of the container 14 by detecting the infrared rays emitted by the container 14.
  • the temperature of the container 14 becomes about the same as the temperature of the object housed in the internal space of the container 14 after a predetermined temperature relaxation time has passed.
  • This temperature relaxation time depends on the material (fluorine-based resin in this embodiment) constituting the container 14 and its thickness (for example, 1 mm). In the case of the container 14 made of a fluororesin having a thickness of 1 mm as in the present embodiment, the temperature relaxation time is expected to be about 3 minutes.
  • thermometer 17 can be regarded as capable of measuring the temperature of the object.
  • the thermometer 17 outputs a temperature signal indicating the temperature of the measured container 14 or the object to the control unit.
  • the control unit may control the output of the microwave oscillator 11 so that the output becomes a predetermined value, or the micro so that the temperature of the temperature signal received from the thermometer 17 becomes a predetermined temperature.
  • the output of the wave oscillator 11 may be controlled.
  • the predetermined temperature may be constant with respect to time or may change with time.
  • the control unit controls the output of the microwave oscillation unit 11 so as to change the value of the output according to time.
  • An example of an output value that changes with time is a pattern of changing from 0 W to 600 W over 30 minutes and then maintaining 600 W for 60 minutes.
  • the preheating step S12 can be carried out by accommodating the beryl crushed in the crushing step S11 and the basic solution in the internal space of the container 14 using the heating device 10 configured as described above.
  • the main heating step S13 can be carried out by accommodating the beryl and the acidic solution after the preheating step S12 in the internal space of the container 14 using the heating device 10.
  • FIG. 4 is a table summarizing the experimental conditions of Experiments 1 to 6 including the Example group and the Comparative Example group of the present invention.
  • FIG. 5 is a graph showing the temperature change of the container in the main heating step S13 included in the embodiment of the present invention.
  • FIG. 6 is a microscope image of beryl before and after the preheating step S12 in one embodiment of the present invention.
  • FIG. 7 is a table summarizing the dissolved amounts of Be, Al, and Si in Experiments 1 to 6 shown in FIG.
  • FIG. 8 is a table summarizing the experimental results of Experiments 1 to 6 shown in FIG. Fenasite, which is an example of Be—Si—O ore, contains almost no Al. Therefore, it is considered that the dissolved amount of Al contained in the column of phenacite shown in FIG. 7 is due to a small amount of Al contained as an impurity in phenacite.
  • the main heating step S13 was carried out after the preliminary heating step S12 shown in 1 was carried out.
  • each of Experiments 1, 3 and 5 is an experiment corresponding to Experiments 2, 4 and 6, respectively, and each solution is left at room temperature (RT) without microwave heating. ..
  • RT room temperature
  • FIGS. 4, 7, and 8 for the experiment in which microwave heating was performed, the subscript with (MW) was added, and for the experiment in which microwave heating was not performed, (RT. ) And added a subscript.
  • the value of the output of the heating device 10 was changed according to the time. Specifically, the output value was increased from 0 W to 600 W over 30 minutes, then the output value was maintained at 600 W for 60 minutes, and then the output value was rapidly decreased to 0 W.
  • the temperature of the container 14 continues to rise even after the output value reaches 600 W, and the maximum temperature reached is as shown in FIG. It was about 220 ° C.
  • the temperature change of the container 14 is common to the preheating step S12 of Experiment 2, the main heating step S13 of Experiment 4, and the preheating step S12 and the main heating step S13 of Experiment 6.
  • beryllium, chrysoberyl, phenacite, and beryllandite were used as raw material beryllium ore.
  • the preheating step S12 was carried out to obtain beryl. It was found that a plurality of recesses that did not exist before the preheating step S12 were formed on the surface. In addition, among these plurality of recesses, the recesses excluding the recesses that existed before the preheating step S12 is performed have a shape (rectangular shape) in which the shape of the opening reflects the shape of the unit cell of the crystal. It turned out.
  • the surface roughness Ra of beryl was roughened from 0.93 ⁇ m to 21.48 ⁇ m by carrying out the preheating step S12.
  • This beryl is a mass having a particle size of about 7 mm, and one surface of the beryl is polished.
  • the surface is etched by carrying out the preheating step S12, that is, the surface structure is corroded, melted, or collapsed. I found that I could do it.
  • FIG. 7 shows a part of the results of Experiments 1 to 6.
  • the amount of each element of Be, Al, and Si dissolved in the solution was analyzed using an ICP mass spectrometer (ICP-MS).
  • the dissolved amount shown in FIG. 7 indicates the ratio of the amount of each dissolved element to the entire ore. That is, when an element contained in the ore is completely dissolved, its solubility is equal to the ratio of the element in the ore.
  • the polarity of the solution containing beryllium ore was adjusted from basic to acidic in the process of transitioning from the preheating step S12 to the main heating step S13.
  • the compound containing Si could be precipitated in the acidic solution, and as a result, Si could be removed from the solution.
  • the precipitate of the compound containing Si is obtained by changing Na 2 SiO 3 dissolved in a basic solution to H 2 SiO 3 in an acidic solution and precipitating. it is conceivable that.
  • Na 2 SiO 3 is soluble in water, H 2 SiO 3 are not soluble in acidic solutions.
  • Preheating step S12 SiO 2 + 2 NaOH ⁇ Na 2 SiO 3 + H 2 O
  • the main heating step S13 Na 2 SiO 3 + 2HCl ⁇ H 2 SiO 3 ⁇ + 2NaCl
  • FIG. 8 summarizes the results of Experiments 1-6.
  • each of the cross, the triangle, the circle, and the double circle indicates that beryllium was not dissolved, slightly dissolved, almost dissolved, or completely dissolved, respectively.
  • the judgment of the cross, triangle, circle, and double circle in each of Experiments 1 to 6 is based on the analysis result by the ICP mass spectrometer and the result of visually confirming the state of the solution after each experiment. I went.
  • any one of HCl, H 2 SO 4 , and HNO 3 is used as the solute of the acidic solution after the preheating step S12 in which NaOH or KOH is used as the solute of the basic solution. It was found that berylium can be sufficiently dissolved by carrying out the main heating step S13 in which the above is adopted.
  • FIG. 9 is a graph showing the correlation between the maximum temperature of the acidic solution and the solubility of beryllium when the main heating step S13 is carried out in the phenacite of Experiment 4 and the beryl of Experiment 6 shown in FIG.
  • beryl B1 sets the output value of the microwave oscillator 11 from 0 W to 300 W in both the preheating step S12 and the main heating step S13. After that, the output value was maintained at 300 W for 60 minutes, and then the output value was rapidly lowered to 0 W.
  • the phenacite P1 raises the output value of the microwave oscillator 11 from 0 W to 300 W over 30 minutes, then maintains the output value at 300 W for 60 minutes, and then maintains the output value at 300 W. The value is quickly lowered to 0W.
  • Beryl B2 raises the output value of the microwave oscillator 11 from 0 W to 600 W over 30 minutes in both the preheating step S12 and the main heating step S13, and then maintains the output value at 600 W for 60 minutes. After that, the output value was quickly lowered to 0W.
  • the phenacite P2 raises the output value of the microwave oscillator 11 from 0 W to 600 W over 30 minutes, then maintains the output value at 600 W for 60 minutes, and then maintains the output value at 600 W. The value is quickly lowered to 0W.
  • the maximum temperatures during the main heating step S13 were 180 ° C. and 190 ° C., respectively. Further, in each of the phenacite P2 and the beryl B2, the maximum temperature during the main heating step S13 was 250 ° C. In beryl B1 and beryl B2, the maximum temperature during the preheating step S12 was about the same as the maximum temperature during the main heating step S13, although not shown.
  • a plurality of HCl solutions whose pH was changed from 1 to 7 were prepared, kerosene in which TOPO was dissolved was mixed and stirred with each HCl solution, and for a while. I left it for a while.
  • the HCl solution mixed with kerosene in which TOPO was dissolved was separated into two layers. After separating this solution into an aqueous layer and an organic layer, the concentrations of beryllium and uranium in the aqueous layer were measured.
  • the pH of the HCl solution (that is, the HCl solution after carrying out the main heating step S13) when the first impurity removing step S14 is carried out is preferably 2 or less.
  • the method for producing a beryllium solution according to the first aspect of the present invention includes a main heating step of producing a beryllium solution by dielectrically heating an acidic solution containing beryllium oxide.
  • the method for producing a beryllium solution according to the second aspect of the present invention is a preheating step carried out before the main heating step in the first aspect, wherein the basic solution containing the beryllium oxide is dielectriced. It further includes a preheating step of heating.
  • the method for producing a beryllium solution according to a third aspect of the present invention is the first impurity removing step carried out after the main heating step in the first aspect or the second aspect, and is the first aspect. It further includes a first impurity removing step of removing the first element from the beryllium solution obtained by the main heating step using an organic compound that adsorbs the element.
  • the concentration of the first element contained in the beryllium solution can be reduced.
  • the concentration of the first element contained in the case of producing any of beryllium, beryllium hydroxide, and beryllium oxide using the beryllium solution can be reduced.
  • the first element include uranium, thorium, plutonium, americium and the like.
  • the organic compound in the third aspect, in the first impurity removing step, is dissolved in an organic solvent, and the beryllium solution is Adopts a composition that is acidic.
  • the efficiency with which the organic compound adsorbs the first element can be increased.
  • the method for producing a beryllium solution according to a fifth aspect of the present invention is a second impurity removing step carried out after the main heating step in any one of the first aspect to the fourth aspect.
  • a second impurity removing step of removing the second element from the beryllium solution by adjusting the polarity of the beryllium solution obtained by the main heating step from acidic to basic is further included.
  • the concentration of the second element contained in the beryllium solution can be reduced.
  • the concentration of the second element contained in the case of producing any of beryllium, beryllium hydroxide, and beryllium oxide using the beryllium solution can be reduced.
  • the second element include aluminum and iron.
  • the method for producing a beryllium solution according to a sixth aspect of the present invention is any one of the first aspect to the fifth aspect, and the main heating step is to apply microwaves to the beryllium oxide. It is stipulated that the above acidic solution containing the above-mentioned acidic solution is dielectrically heated.
  • microwave dielectric heating is a technology used in so-called microwave ovens and is a widely used technology. Therefore, this manufacturing method can reduce the cost required for implementation as compared with the conventional manufacturing method.
  • the beryllium solution is a beryllium chloride solution.
  • a beryllium chloride solution can be easily produced without passing through beryllium hydroxide.
  • Beryllium chloride, beryllium hydroxide, and beryllium oxide can be easily produced from the beryllium chloride solution as described later. Therefore, as the beryllium solution, a beryllium chloride solution is suitable.
  • each step included in the method for producing a beryllium solution according to any one of the first to sixth aspects and the beryllium solution are electrolyzed. This includes an anhydration step of producing beryllium salt and an electrolysis step of producing beryllium by melt salt electrolysis of the beryllium salt.
  • the method for producing beryllium hydroxide according to the tenth aspect of the present invention is based on each step included in the method for producing a beryllium solution according to any one of the first to sixth aspects and the beryllium solution. It includes a neutralization step of producing beryllium hydroxide by neutralizing with.
  • the method for producing beryllium oxide according to the eleventh aspect of the present invention heats each step included in the method for producing a beryllium solution according to any one of the first to sixth aspects and the beryllium solution. This includes a third heating step, which produces beryllium oxide.
  • beryllium, beryllium hydroxide, and beryllium oxide can be produced by using a novel production method having high energy efficiency.
  • metal beryllium can be produced from the beryllium solution produced by the method for producing beryllium solution according to one aspect of the present invention without passing through beryllium hydroxide. it can.
  • beryllium hydroxide which is in high general demand, is produced from beryllium ore, and then beryllium is produced from beryllium hydroxide. Therefore, the method for producing beryllium according to the seventh aspect can produce beryllium more easily than the method for producing beryllium currently on the market.
  • the beryllium solution is a beryllium chloride solution
  • the hydration step is the beryllium chloride contained in the beryllium chloride solution.
  • the hydrate is configured to be heated in vacuum and at a temperature of 80 ° C. or higher and 110 ° C. or lower.
  • the beryllium chloride hydrate can be reliably anhydrous-treated.
  • the beryllium oxide according to the twelfth aspect of the present invention is a beryllium oxide having crystallinity and having a plurality of recesses formed on the surface, and a part or all of the plurality of recesses.
  • the recess has a shape in which the shape of the opening reflects the shape of the unit cell of the crystal.
  • this beryllium oxide has a plurality of recesses formed on the surface having a shape in which the shape of the opening reflects the shape of the unit cell of the crystal, it can be easily converted into an acidic solution by dielectric heating in the acidic solution. Dissolves in. Therefore, the beryllium oxide according to one aspect of the present invention is suitable as a raw material for producing a beryllium solution.
  • the beryllium oxide according to the thirteenth aspect of the present invention further contains silicon and aluminum in the twelfth aspect.
  • Beryllium oxide containing silicon and aluminum is difficult to dissolve even when it is dielectrically heated in an acidic solution. However, since a plurality of recesses are formed on the surface, the beryllium oxide containing silicon and aluminum can be easily dissolved by dielectric heating in an acidic solution.
  • a beryllium solution containing beryllium oxide and beryllium ions according to the twelfth and thirteenth aspects described above is also one aspect of the present invention.

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PCT/JP2020/032263 2019-08-30 2020-08-27 ベリリウム溶液の製造方法、ベリリウムの製造方法、水酸化ベリリウムの製造方法、酸化ベリリウムの製造方法、及び、ベリリウム酸化物 Ceased WO2021039875A1 (ja)

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BR112022003267A BR112022003267A2 (pt) 2019-08-30 2020-08-27 Método para produção de solução de berílio, método para produção de berílio, método para produção de hidróxido de berílio, método para produção de óxido de berílio e óxido de berílio
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CN105734309A (zh) * 2016-03-17 2016-07-06 湘潭大学 一种从金绿宝石型铍矿石中提取铍的方法
CN105907962A (zh) * 2016-04-26 2016-08-31 新疆有色金属研究所 高纯含铍反萃液及其制备方法、氟铍酸铵、氟化铍和金属铍的制备方法
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CN112813288A (zh) * 2020-12-29 2021-05-18 东方电气集团科学技术研究院有限公司 一种以工业铍制备高纯铍的方法
CN112813288B (zh) * 2020-12-29 2022-08-12 东方电气集团科学技术研究院有限公司 一种以工业铍制备高纯铍的方法
CN113981491A (zh) * 2021-12-20 2022-01-28 郑州大学 一种低温熔盐电解制备金属铍的方法

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