WO2016129009A1 - Procédé de fabrication de vanadium métallique - Google Patents

Procédé de fabrication de vanadium métallique Download PDF

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Publication number
WO2016129009A1
WO2016129009A1 PCT/JP2015/000594 JP2015000594W WO2016129009A1 WO 2016129009 A1 WO2016129009 A1 WO 2016129009A1 JP 2015000594 W JP2015000594 W JP 2015000594W WO 2016129009 A1 WO2016129009 A1 WO 2016129009A1
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vanadium
molten salt
compound
calcium
anode
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PCT/JP2015/000594
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English (en)
Japanese (ja)
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鈴木　亮輔
完二 佐藤
英樹 古川
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国立大学法人北海道大学
Ｌｅシステム株式会社
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Priority to CN201580078650.0A priority Critical patent/CN107532236B/zh
Priority to JP2016574524A priority patent/JP6524492B2/ja
Priority to PCT/JP2015/000594 priority patent/WO2016129009A1/fr
Publication of WO2016129009A1 publication Critical patent/WO2016129009A1/fr

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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
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

Definitions

  • the present invention relates to a method for producing metal vanadium, particularly high-purity metal vanadium.
  • Metal vanadium is widely used as a coating material, additives for titanium, aluminum, zirconium and steel, heat-resistant materials such as jets and induction missiles, sputtering targets, vacuum tube deposition, alloy superconducting materials, etc., and does not activate It is also used as a reactor material due to its characteristics.
  • metal vanadium is expected to be a single metal and a hydrogen storage material because it has a hydrogen storage / release characteristic of about 2.2 mass% at room temperature and pressure.
  • a vanadium-based hydrogen storage alloy as a cathode of a Ni-hydrogen battery that can be a substitute for a nickel cadmium battery.
  • it is also considered to be used in the electrolyte of vanadium redox flow batteries and vanadium-air batteries with higher energy density, and is expected as a basic material for future technology.
  • a method for producing metal vanadium there is a method of repeatedly using a thermite reaction and an electron beam melting method. Briefly, in this production method, first, vanadium pentoxide is thermally reduced with aluminum to produce crude vanadium containing a large amount of aluminum and oxygen. Thereafter, the vanadium obtained is repeatedly melted and solidified using an electron beam to produce metal vanadium. According to this method, high purity vanadium can be produced by achieving high purity by repeating dissolution and solidification. However, this manufacturing method requires apparatus and large energy, and is troublesome, so that the manufactured metal vanadium is very expensive.
  • Patent Document 1 a Ca thermal reduction method of vanadium oxide has been developed (see Patent Document 1). If this manufacturing method is used, metal vanadium can be manufactured from vanadium pentoxide at a lower cost than the manufacturing method described above. However, since vanadium pentoxide has a relatively low melting point, the metal vanadium that is produced tends to stick to the reaction vessel used in the production process, and it is easy to prevent the introduction of impurities such as reducing substances in the reaction vessel. Not. *
  • the “OS method” is a reduction method using molten calcium chloride, and is a technology in which “calcium chloride-calcium oxide electrolysis method” and “calcium thermal reduction method” are integrated (patent document). 2).
  • vanadium pentoxide having a low melting point is used as a raw material, and as described above, impurities may be mixed in during the production stage. Manufacture is not easy. It is conceivable to improve this problem by using vanadium trioxide having a higher melting point, but in this case, it is necessary to reduce vanadium pentoxide to vanadium trioxide. Production efficiency decreases.
  • the present invention has been made in view of such problems, and provides a method for producing metal vanadium that can produce high-purity metal vanadium more easily, at lower cost and with less energy. .
  • Inventors of the present invention have developed a vanadium battery such as a redox flow battery, and thought that a manufacturing technique capable of easily and inexpensively manufacturing metal vanadium necessary for these batteries is necessary. Further, as described above, metal vanadium is widely used in various applications, and it is considered that the demand is increased in this respect as well. Therefore, we concluded that there is a need for a manufacturing technology that can produce metal vanadium easily and at low cost, and that the need for high-purity metal vanadium will increase in the future. We decided to develop a simple and low-cost manufacturing method. Accordingly, paying attention to a method for producing metal vanadium by applying the above-mentioned “OS method”, research and development have been promoted from the viewpoint of preventing contamination of impurities, and the present invention as described below has been achieved.
  • OS method a method for producing metal vanadium by applying the above-mentioned “OS method”
  • a part of the inorganic molten salt forming the molten salt electrolytic bath in the reaction tank is electrolyzed to generate a reductive decomposition product, and the reductive decomposition product
  • the reductive decomposition product contains calcium obtained by electrolyzing the part of the inorganic molten salt, and the vanadium compound includes vanadium sulfide, vanadium sulfate compound, Metal vanadium, which is a mixed vanadium compound containing one or more selected from the group consisting of vanadium thiosulfate, ammonium metavanadate and vanadyl sulfate This is a method for producing palladium.
  • vanadium sulfide or vanadium sulfate compound having a high melting point As a raw material, attention was paid to the use of a vanadium sulfide or vanadium sulfate compound having a high melting point as a raw material, and further research and development were advanced to the present invention.
  • These vanadium compounds having a high melting point are easy to handle at the production stage, for example, when introduced into a molten salt electrolytic bath. Therefore, mixing of impurities due to the raw material and its handling can be more easily prevented, and high-purity metal vanadium can be more easily produced.
  • V 2 S 3 is about 2,400 ° C.
  • V 2 O 3 is about 1,970 ° C.
  • V 2 O 5 is about 690 ° C.
  • vanadium sulfide or vanadium sulfate compound is included as a raw material vanadium compound, it is composed of calcium sulfide and calcium sulfate as a part of the inorganic molten salt necessary for the production of the reductive decomposition product. It has been found that high purity metal vanadium can be easily produced by including one or more selected from the group, and has led to the following invention.
  • Another invention according to the present application is to generate a reductive decomposition product by electrolyzing a part of the inorganic molten salt forming the molten salt electrolysis bath in the reaction tank to produce a reductive decomposition product.
  • the reductive decomposition product contains calcium obtained by electrolysis of the part of the inorganic molten salt, and the vanadium compound includes vanadium sulfide, vanadium oxide, vanadium sulfate compound, Mixed vanadium containing one or more selected from the group consisting of vanadium thiosulfate, ammonium metavanadate and vanadyl sulfate It is those, a method for producing a metal vanadium.
  • the vanadium compound as a raw material includes one or more selected from the group consisting of vanadium sulfide and vanadium sulfate compound, It is considered that high-purity metal vanadium can be more easily produced in combination with the inclusion of calcium sulfide and calcium sulfate in the inorganic molten salt.
  • the inorganic molten salt to form a vanadium compound and an electrolytic bath which is a raw material, if it contains a compound containing sulfur, components discharged from the molten salt electrolytic bath reacts with S 2 gas or anode carbon product
  • This CS 2 gas is excellent in that it is not discharged from the reaction vessel into the environment but is precipitated by cooling and can be easily recovered as a solid and a liquid, respectively.
  • metal vanadium can be manufactured continuously. It can be said that a production method capable of continuously producing metal vanadium is advantageous in industrialization and mass production.
  • granular or powdery metal vanadium can be easily produced.
  • metal vanadium is used in a wide variety of applications such as a catalyst, a hydrogen storage alloy, and a chemical battery. In these applications, powder metal vanadium is required.
  • metal vanadium that is not powder is manufactured, then it takes time and effort to make the powder, and the cost increases accordingly.
  • the above-described production methods of both inventions are extremely excellent in that granular or powdery metal vanadium can be easily produced, and low cost can be realized.
  • granular or powdery and porous metal vanadium can be easily produced.
  • the reasons why powder metal vanadium is required include, for example, excellent mixing, solubility, and reactivity, and a large surface area. This is a property that further improves the characteristics. Therefore, granular or powdery and porous metal vanadium is more preferable as the metal vanadium used in the above-described catalyst, hydrogen storage alloy, chemical battery and the like. That is, both of the above-described inventions are extremely excellent in that it is possible to easily produce granular or powdery and porous metal vanadium and to realize low cost.
  • metal vanadium having a lower oxygen concentration can be easily produced.
  • Metal vanadium with a low oxygen concentration is excellent in that the hydrogen storage characteristics are greatly improved and the activation of impurities is reduced when used for nuclear reactor materials. That is, both the above-described inventions are extremely excellent in that low-concentration metal vanadium can be easily manufactured and low cost can be realized.
  • said one part inorganic molten salt is produced
  • generated inorganic molten salt is the said molten salt.
  • the manufacturing method which forms a part of electrolytic bath may be sufficient.
  • generates sulfur by the anode reaction in an anode may be sufficient.
  • at least one of the vanadium compound and the partial inorganic molten salt contains an oxide, and a carbon material is used as an anode for electrolysis, and carbon dioxide gas is generated by an anode reaction at the anode. This may be a method for producing metal vanadium.
  • the part of the inorganic molten salt in the molten salt electrolysis bath is electrolyzed, and at least sulfur gas is generated by the anode reaction at the anode, along with the generation of metal vanadium.
  • a method for producing metal vanadium in which at least calcium sulfide is generated and the product is dissolved in a molten salt electrolytic bath, may be used.
  • the part of the inorganic molten salt in the molten salt electrolytic bath is electrolyzed, and at least carbon dioxide gas is generated by an anode reaction at the anode, and at least along with the generation of metal vanadium.
  • dissolves the said product in molten salt electrolysis bath may be sufficient.
  • the carbon material as an anode for electrolysis the part of the inorganic molten salt in the molten salt electrolytic bath is electrolyzed, and at least one of the vanadium compound and the part of the inorganic molten salt is used.
  • At least calcium sulfide is generated as metal vanadium is generated, and the product is dissolved in a molten salt electrolytic bath.
  • at least sulfurous acid gas may be generated by the anode reaction at the anode.
  • vanadium compounds containing a part of sulfur are removed by sulfurization as sulfurous acid gas by thermal decomposition due to temperature rise, and vanadium pentoxide V 2 Can be O 5 .
  • the vanadium compound containing a part of sulfur other than the vanadium sulfide may be a vanadium compound that becomes vanadium pentoxide V 2 O 5 containing a residual sulfur content at the reaction temperature.
  • the part of the inorganic molten salt is a calcium compound, and the addition amount of the calcium compound is preferably 0.01 mol% to 30 mol%.
  • the amount of calcium compound added is more preferably 0.01 mol% to 20 mol%.
  • the temperature (reaction temperature) of the molten salt electrolysis bath in electrolysis is preferably 873 K or more and 1423 K, and the electrolysis voltage is preferably 1.6 V or more and 3.21 V or less.
  • the vanadium sulfide is one or more selected from the group consisting of VS, V 2 S 3 , V 5 S 8 , V 3 S 4 , V 2 S 5
  • the vanadium thiosulfate is It is VS 2 O 3 and the vanadium sulfate compound is preferably one or more selected from the group consisting of VSO 4 , V 2 (SO 4 ) 3 and VOSO 4 .
  • metal vanadium that is the invention according to the present application, high-purity metal vanadium can be produced more easily and at low cost.
  • the present invention is generally a method for producing metal vanadium by thermally reducing a vanadium compound in a molten salt.
  • vanadium compounds include vanadium oxides and sulfides.
  • a crucible 3 installed in a stainless steel sealed container 4 that can be heated by a heater 5 is prepared.
  • a crucible made of dense magnesium oxide was used.
  • an anode 1 and a cathode 2 arranged in the crucible 3 were prepared.
  • the anode 1 includes an upper titanium rod (titanium rod) 1a and a lower end carbon rod 1b.
  • the cathode 2 is comprised by the titanium rod 2a and the container 2b for accommodating a vanadium compound.
  • the container 2 is a squirrel-shaped container composed of a titanium mesh, and is installed at a position surrounding the titanium rod 2a in the manufacture of metal vanadium (see FIG. 1).
  • a DC power source (not shown) for applying a DC voltage between the anode 1 and the cathode 2 was prepared.
  • the raw material of the mixed molten salt 8 is put into the crucible 3, vacuum dehydration treatment is performed in the sealed container 4, and argon gas Ar is injected into the sealed container 4 from the intake port 9, under an argon gas atmosphere. Increase the temperature. Here, the temperature was raised to 900 ° C. In this way, a mixed molten salt 8 was prepared in the crucible 3. As described later, the mixed molten salt 8 is a mixture of calcium chloride (CaCl 2 ), calcium sulfide and calcium oxide.
  • thermometer such as a thermocouple 6
  • voltage and current during energization are measured with a measuring device (not shown).
  • the measurement values were recorded on a personal computer by a data logger.
  • the anode 2 in which the vanadium compound 12 is accommodated in the anode 1 and the container 2b, which are arranged in advance in the sealed container 4 before sealing the sealed container 4, are immersed in the molten salt 8, Start electrolysis.
  • the ratio (Q / Q 0 ) was used.
  • the applied voltage was fixed at 3.0V.
  • the amount of electricity supplied was 200 to 307% of the theoretical electricity ratio.
  • the cathode 2 drawn from the molten salt 8, that is, the titanium rod 2a container 2b was cooled to room temperature in argon gas and then washed.
  • cleaning was performed using distilled water, acetic acid, distilled water, ethanol, and acetone in this order as cleaning liquids.
  • the washed cathode 2 was vacuum dried.
  • the two reactions proceed simultaneously in the mixed molten salt.
  • the mixed molten salt contains calcium chloride, calcium sulfide and calcium oxide
  • the vanadium compound is a sulfide and oxide of vanadium
  • the two reactions proceeding simultaneously are the following formulas (1) and Thermal reduction reaction as shown in formula (3) (thermal reduction reaction of vanadium compound with calcium) and high temperature chemical reaction as shown in formula (2) and formula (4) (sulfur in reduced vanadium and It is a high temperature chemical reaction that is desulfurization and deoxidation of oxygen.
  • the reducing agent CaS oxidized in the thermal reduction reaction performs an electrochemical reaction that is electrolysis / regeneration (see formulas (5), (6), and (7)).
  • the reducing agent CaO oxidized in the high temperature chemical reaction similarly performs an electrochemical reaction that is electrolysis / regeneration (see formulas (8), (9), (10), (11), and (12)).
  • Oxygen which is more reactive than sulfur, reacts with anodic carbon to produce carbon monoxide and carbon dioxide.
  • Such a reaction is simultaneously performed in one container, and the thermal reduction of the vanadium compound and the electrolysis of CaS and CaO are continuously performed.
  • the cathode 2 calcium having a reducing power is generated.
  • the generated calcium exists in a form dissolved in liquid calcium or calcium chloride.
  • the vanadium compound is reduced and deoxidized.
  • the carbon rod 1b which is the anode 1 when vanadium sulfide is contained in the vanadium compound, S 2 gas (and / or CS 2 gas) is generated, and vanadium oxide is contained in the vanadium compound.
  • CO 2 gas (and / or CO gas) is generated.
  • the generated gas is released from the molten salt and discharged from the exhaust port 10 (see FIG. 1).
  • S 2 gas (CS 2 gas) can be easily deposited and recovered by cooling, and is effective as a countermeasure for exhaust gas.
  • the metal vanadium obtained by reducing the vanadium compound on the cathode 1 side is in a powder form (see FIGS. 7 and 8). Therefore, metal vanadium powder taken out from the crucible after electrolysis is washed (washing with water, washing with acetic acid, etc.) to remove calcium chloride and the like adhering to the surface and dried to easily obtain metal vanadium powder.
  • the obtained metal vanadium is porous (refer FIG.7 and FIG.8), pulverization is easy also about the part which is not powder.
  • vanadium sulfide is used as the vanadium compound, the carbon electrode (carbon rod) 1b of the anode 1 is not consumed, so that powder metal vanadium can be manufactured more efficiently.
  • a crucible 3 (mixed molten salt) 8 obtained by adding 0.5 mol% of calcium sulfide (made by Wako Pure Chemical, special grade reagent) to 600 g of calcium chloride (made by Wako Pure Chemical, special grade reagent) is used. (Inner diameter 90 mm, depth 200 mm). The crucible 3 was placed in a sealed container 4 (inner diameter 105 mm, depth 480 mm) and sealed with a flange. After vacuum dehydration, the temperature was raised to 900 ° C. in an argon gas atmosphere.
  • a titanium rod 1a and a carbon rod 1b of the anode 1 and a container 2b attached so as to surround the titanium rod 2a and the titanium rod of the cathode 2 were prepared.
  • this vessel 2b 1.502 g of vanadium sulfide 12 (Furuuchi Chemical purity 99%) was inserted.
  • both electrodes 1 and 2 were inserted into the molten salt 8 to start electrolysis.
  • the applied voltage was fixed at 3.0 V, and the amount of electricity necessary for generating Ca necessary for the reduction was applied in accordance with the amount of vanadium sulfide in the loaded sample.
  • electrolysis was performed using an electric quantity of 307% of the theoretical electric quantity.
  • the cathode 2 was drawn out from the molten salt 8 and cooled to room temperature in argon gas. And the sample after cooling was wash
  • crucible 3 (inner diameter 90 mm, depth) obtained by adding 0.5 mol% of calcium sulfide (made by Wako Pure Chemicals, special grade reagent) to 600 g of calcium chloride (made by Wako Pure Chemicals, special grade reagent) as molten salt 8. 200mm).
  • the crucible 3 was placed in a sealed container 4 (inner diameter 105 mm, depth 480 mm) and sealed with a flange. After vacuum dehydration, the temperature was raised to 900 ° C. in an argon gas atmosphere.
  • a titanium rod 1a and a carbon rod 1b of the anode 1 and a container 2b attached so as to surround the titanium rod 2a and the titanium rod of the cathode 2 were prepared.
  • 1.488 g of vanadium trioxide 12 (purity 99% or more by Taiyo Mining Co., Ltd.) was inserted into the container 2b.
  • both electrodes 1 and 2 were inserted into the molten salt 8 to start electrolysis.
  • the applied voltage was fixed at 3.0 V, and the amount of electricity necessary for generating Ca necessary for the reduction was supplied corresponding to the amount of vanadium trioxide in the loaded sample.
  • electrolysis was performed using an electric quantity of 200% of the theoretical electric quantity.
  • the cathode 2 was drawn out from the molten salt 8 and cooled to room temperature in argon gas. And the sample after cooling was wash
  • each of ammonium metavanadate (Wako Pure Chemicals special grade reagent) and vanadyl sulfate (Emerging Chemicals) were prepared as raw materials (vanadium compound 12). Then, each prepared raw material was subjected to heat treatment (heating temperature 600 ° C., heating time 10 minutes) as a pretreatment to obtain a treated material. The resulting material was analyzed, it was both vanadium pentoxide oxide (V 2 O 5). Each vanadium pentoxide oxide (V 2 O 5 ) thus obtained was used to produce metal vanadium. At this time, the amount of vanadium oxide (V 2 O 5 ) put into the container 2 was 1.500 g in any case. Since the production conditions other than the amount of vanadium oxide (V 2 O 5 ) were the same as those in Example 2, the description thereof was omitted here.
  • the analysis results of the sulfur content and oxygen content (oxygen concentration) of the sample (manufactured sample) manufactured by molten salt electrolytic reduction in each example are shown in Table 1 below.
  • the analysis method of sulfur content is the dissolution infrared spectroscopy in oxygen gas stream
  • the analysis method of oxygen content is the dissolution infrared spectroscopy in helium gas stream.
  • Table 1 and FIGS. 4 and 5 powder metal vanadium having a low sulfur content and a low oxygen content was obtained by the manufacturing method of each example.
  • data publication was omitted here.
  • vanadium oxide and sulfide for example, vanadium sulfate, thiosulfate, ammonium metavanadate (NH 4 VO 3 ), and vanadyl sulfate (VOSO 4 ) can be used as the vanadium compound.
  • vanadium oxide include V 2 O, VO, V 2 O 3 , VO 2 , and V 2 O 5 .
  • Vanadium sulfide includes VS, V 2 S 3 , V 5 S 8 , V 3 S 4 , V 2 S 5 , V 3 S, V 5 S 4 , VS, V 2 S 3 , V 2 S 5 , V 7 S 8 , V 3 S 8 , VS 4 can be mentioned.
  • examples of the vanadium sulfate compound include VSO 4 , V 2 (SO 4 ) 3 , VOSO 4 , and V (SO 4 ) 2 .
  • examples of vanadium thiosulfate compounds include VS 2 O 3 .
  • a thermal decomposition process it is preferable to implement a thermal decomposition process as a pre-process.
  • vanadium oxide is obtained by pyrolysis.
  • a condition for the pyrolysis step for example, when a pyrolysis step is performed in air at 550 ° C. for 4 hours, vanadium pentoxide is obtained by pyrolysis. Further, when vanadium pentoxide is reduced in hydrogen gas at 600 ° C. for 4 hours using a rotary kiln, vanadium trioxide is obtained.
  • inorganic molten salt mixed with calcium chloride when constituting the molten salt in addition to calcium sulfide and calcium oxide, for example, calcium thiosulfate compound and calcium sulfate can be mentioned.
  • FIG. 3 is a graph showing the X-ray diffraction measurement result of the sample manufactured in Example 1.
  • FIG. 6 is a graph showing the X-ray diffraction measurement result of the sample manufactured in Example 2.
  • 2 is a scanning electron micrograph of the sample manufactured in Example 1.
  • FIG. 2 is a scanning electron micrograph of a sample manufactured in Example 2.

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Abstract

La présente invention a pour but de fournir un procédé qui permette de fabriquer du vanadium métallique de pureté élevée à peu de frais et de façon efficace sur le plan énergétique. Pour atteindre ce but, l'invention consiste en un procédé de fabrication de vanadium métallique dans lequel une partie d'un sel fondu inorganique, destiné à former un bain électrolytique de sel fondu dans une cuve réactionnelle, est électrolysée pour générer du calcium, et un composé de vanadium est réduit thermiquement par le calcium afin de fabriquer du vanadium métallique, au moins l'une des conditions suivantes étant satisfaite par ledit procédé de fabrication de vanadium métallique : la partie du sel fondu inorganique contient un ou plusieurs composés choisis dans le groupe constitué de composés sulfures et sulfates de calcium ; le composé de vanadium est un composé de vanadium mixte contenant un ou plusieurs composés choisis dans le groupe constitué de sulfure de vanadium, de composés de sulfate de vanadium, de composés de thiosulfate de vanadium, de métavanadate d'ammonium et de sulfate de vanadyle.
PCT/JP2015/000594 2015-02-09 2015-02-09 Procédé de fabrication de vanadium métallique WO2016129009A1 (fr)

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CN201580078650.0A CN107532236B (zh) 2015-02-09 2015-02-09 金属钒的制造方法
JP2016574524A JP6524492B2 (ja) 2015-02-09 2015-02-09 金属バナジウムの製造方法
PCT/JP2015/000594 WO2016129009A1 (fr) 2015-02-09 2015-02-09 Procédé de fabrication de vanadium métallique

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CN107532236A (zh) 2018-01-02
JPWO2016129009A1 (ja) 2017-12-07
CN107532236B (zh) 2019-09-17
JP6524492B2 (ja) 2019-06-05

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