WO2024180893A1 - タングステン粉末の製造方法及び炭化タングステン製品の製造方法 - Google Patents

タングステン粉末の製造方法及び炭化タングステン製品の製造方法 Download PDF

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WO2024180893A1
WO2024180893A1 PCT/JP2023/046939 JP2023046939W WO2024180893A1 WO 2024180893 A1 WO2024180893 A1 WO 2024180893A1 JP 2023046939 W JP2023046939 W JP 2023046939W WO 2024180893 A1 WO2024180893 A1 WO 2024180893A1
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adsorbent
tungsten
solution
powder
amino acids
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French (fr)
Japanese (ja)
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貴彦 牧野
直樹 岩井
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Kyocera Corp
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Kyocera Corp
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Priority to EP23925443.6A priority Critical patent/EP4674995A1/en
Priority to JP2025503604A priority patent/JPWO2024180893A1/ja
Priority to CN202380094561.XA priority patent/CN120659896A/zh
Publication of WO2024180893A1 publication Critical patent/WO2024180893A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • 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
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—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
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • 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
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • 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

  • This disclosure relates to a method for producing tungsten powder for use in the manufacture of cutting inserts and the like, and a method for producing tungsten carbide products.
  • Tungsten powder is used in the manufacture of tungsten carbide products, such as cutting inserts, by producing it from tungsten-containing ores (e.g., scheelite CaWO4 , wolframite MnWO4 , and ferrilite FeWO4 ) or by recovering it from tungsten-containing products, as described in U.S. Patent No. 5,399,633.
  • tungsten-containing ores e.g., scheelite CaWO4 , wolframite MnWO4 , and ferrilite FeWO4
  • a method for producing tungsten powder includes the steps of preparing a raw material containing tungsten oxide, obtaining a solution by dissolving the tungsten oxide from the raw material using an alkaline solvent, adding an adsorbent to the solution and allowing the adsorbent to adsorb the tungsten oxide, extracting the adsorbent with the tungsten oxide adsorbed thereto from the solution, mixing the adsorbent with the tungsten component adsorbed thereto with carbon powder to produce a mixture, and heating the mixture.
  • FIG. 1 is a flow chart outlining a method for producing tungsten powder according to one non-limiting example of the present disclosure.
  • Tungsten powder is used in the manufacture of tungsten carbide products, such as cutting inserts, by producing it from tungsten-containing ores (e.g., scheelite CaWO4 , wolframite MnWO4 , and ferrilite FeWO4 ) or by recovering it from tungsten-containing products, as described in U.S. Patent No. 5,399,633.
  • tungsten-containing ores e.g., scheelite CaWO4 , wolframite MnWO4 , and ferrilite FeWO4
  • a method for producing tungsten powder includes the following steps (A) to (G).
  • A) a step of preparing a raw material containing tungsten;
  • B) a step of oxidizing tungsten in the raw material to obtain tungsten oxide;
  • C) a step of obtaining a solution by dissolving tungsten oxide from the raw material using an alkaline solvent;
  • D) a step of adding a metal compound adsorbent (hereinafter sometimes referred to as an adsorbent) to the solution, reacting the adsorbent with the solution containing the dissolved tungsten, and obtaining a compound containing the adsorbent and tungsten;
  • E) a step of extracting the compound from the solution;
  • F) a step of mixing the compound with carbon powder to produce a mixture;
  • G) a step of heating the mixture.
  • a raw material containing tungsten is prepared.
  • the raw material include ores and scraps containing tungsten.
  • ores containing tungsten include scheelite (CaWO 4 ), wolframite (MnWO 4 ), ferrite (FeWO 4 ), and wolframite ((Fe,Mn)WO 4 ).
  • Scraps containing tungsten are waste materials generated in the production process of products mainly composed of metal tungsten, tungsten carbide (WC), and the like. Specifically, scraps generated in the manufacturing process of cemented carbide tools, hard scraps such as used tools, powdery soft scraps such as grinding sludge, and the like can be cited.
  • Cemented carbide a type of cemented carbide, is mainly composed of composite carbides such as metal tungsten and tungsten carbide.
  • This composite carbide-based component has iron, nickel, cobalt, etc. as a binder phase, and may contain TiC, TaC, NbC , VC, Cr3C2 , etc. as additive components as necessary.
  • Targeted materials containing cemented carbide include cutting tools (cutting inserts, drills, end mills, etc.), dies (forming rolls, forming dies, etc.), civil engineering and mining tools (oil drilling tools, rock crushing tools, etc.), etc.
  • Process B When tungsten is contained in the raw material in a non-oxide state, the tungsten in the raw material is oxidized to obtain tungsten oxide.
  • the cutting tool when preparing a used cutting tool as the raw material, the cutting tool contains tungsten in the form of tungsten carbide. Therefore, the tungsten carbide is oxidized to obtain tungsten oxide.
  • a method for oxidizing tungsten includes, for example, oxidizing roasting.
  • a cutting tool containing tungsten carbide and cobalt is oxidizing roasted to obtain a mixture of tungsten oxide (WO 3 ) and cobalt tungstate (CoWO 4 ).
  • steps A and B since the purpose of steps A and B is to obtain tungsten oxide from raw materials, these steps may be collectively expressed as a process for preparing raw materials containing tungsten oxide.
  • the recovery method includes an alkali extraction/alkali fusion process in which the metal components of the cemented carbide scrap are dissolved in an alkali solution to obtain a tungsten compound solution in which tungsten compound ions are dissolved.
  • Methods for obtaining a metal compound solution include an alkali extraction method and an alkali fusion method.
  • the alkali extraction method is a method in which scrap that has been previously oxidized and roasted is subjected to alkali extraction using, for example, an aqueous NaOH solution.
  • the alkali dissolution method is a method in which the scrap is oxidized and dissolved at the same time using a molten salt of a sodium salt such as NaNO3, Na2SO4, Na2CO3 , or NaOH .
  • soft scrap is highly reactive and difficult to control, so it is more efficient to use the alkaline extraction method, while hard scrap is more efficient to use the alkaline dissolution method, because only the surface can be oxidized by oxidizing roasting.
  • the adsorbent of this embodiment is added to the tungsten compound solution obtained in step C.
  • the adsorbent of this embodiment adsorbs the metal compound present as an anion in the solution.
  • the adsorbent of this embodiment for example, the first adsorbent and/or the second adsorbent shown below can be used.
  • the first adsorbent contains at least one first amino acid selected from alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, proline, threonine, asparagine, glycine, isoleucine, ornithine, arginine, serine, citrulline, and cystathionine as a free amino acid.
  • the first adsorbent may contain 10 mol% or more of the first amino acid as a free amino acid (sometimes called the first free amino acid) with respect to the total amount of free amino acids.
  • the free amino acids in the adsorbent may exist as a solid, or may exist as free amino acids when dissolved in solution. In either case, the solution contains free amino acids, and by using these adsorbents, metal compounds can be recovered through a simple processing process.
  • the first adsorbent is a substrate having free amino acids supported on its surface.
  • the substrate can be, for example, a peptide containing free amino acids, a protein, or a substance that forms a living organism such as a microorganism (hereinafter sometimes referred to as a biological substance), an organic substance such as a resin, or an inorganic substance.
  • Microorganisms include bacteria such as E. coli (Escherichia coli), Bacillus sp., Thiobacillus ferrooxidans, Streptomyces rimosus, Pseudomonas sp., Bacillus thuringiensis, Arthrobacternicotianae, Shewanella algae, and Shewanella oneidensis, yeasts such as Saccharomyces cerevisiae, Schizosaccharomyces pombe, Candida albicans, Yarrowialipolytica, Pichiapastoris, Hansenula polymorpha, and Kluyveromyces lactis, and koji mold.
  • bacteria such as E. coli (Escherichia coli), Bacillus sp., Thiobacillus ferrooxidans, Streptomyces rimosus, Pseudomonas sp., Bacillus thuringiensis, Arthrobacternicotianae, Shewanella algae
  • Adsorbents made from biological substances come in various forms, such as powders, pellets made from powders, gels, and aqueous solutions. Powders and pellets are easy to store and handle. If the adsorbent is a solid such as a powder or pellets, the solid can be dissolved in another liquid such as water and then added to a solution containing the metal compound, or the solid can be added directly to a solution containing the metal compound and stirred.
  • the first adsorbent may contain, as free amino acids, at least one of the first amino acids alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, and proline (hereinafter, sometimes referred to as the 1-1 amino acid), at least one of the first amino acids threonine, asparagine, glycine, isoleucine, ornithine, and arginine (hereinafter, sometimes referred to as the 1-2 amino acid), and at least one of the first amino acids serine, citrulline, and cystathionine (hereinafter, sometimes referred to as the 1-3 amino acid).
  • the first adsorbent may contain, as free amino acids, at least one of the second amino acids phosphoserine, aspartic acid, leucine, and phenylalanine at a ratio of 40 mol% or less to the total amount of free amino acids.
  • An adsorbent containing the 1-1 amino acid, the 1-2 amino acid, and the 1-3 amino acid as free amino acids can increase the recovery efficiency of metal compounds.
  • the 1-1 amino acid may be contained in a ratio of 5 mol% or more as a free amino acid when the total amount of free amino acids is 100 mol%.
  • lysine may be contained in a ratio of 10 mol% or more as a free amino acid.
  • the recovery efficiency of metal compounds is improved.
  • the total amount of the 1-1 amino acid contains 10 mol% or more as a free amino acid. This improves the recovery efficiency of metal compounds.
  • the total amount of free amino acids consisting of the first amino acid may be 0.5% by mass or more relative to the total amount of solids obtained by drying the adsorbent, i.e., the solid content of the adsorbent. In such a case, the recovery efficiency of the metal compound is improved.
  • the free amino acids contain aspartic acid and at least one of glutamic acid and valine as free amino acids
  • the content of at least one of glutamic acid and valine may be greater than that of aspartic acid.
  • the free amino acids consisting of glutamic acid and valine have a positive zeta potential when the pH of the solution is adjusted to the acidic side, and adsorb metal compound ions (anions) in the solution.
  • aspartic acid has a low ability to adsorb metal compounds (ions). Therefore, when the content of at least one of glutamic acid and valine in the free amino acids is greater than the content of aspartic acid, the adsorption efficiency of metal compounds can be improved.
  • the type and content of free amino acids contained in the adsorbent can be confirmed by free amino acid analysis (also called bioamino acid analysis).
  • the content ratio of the total amount of free amino acids to the solid content of the adsorbent can be calculated from the mass of the free amino acids in the adsorbent and the mass of the solid content of the adsorbent.
  • the adsorbent is a solid such as a powder
  • the adsorbent is added to pure water at a liquid temperature of 25°C, and the adsorbent is suspended by stirring for 10 minutes while rotating a magnetic stirrer at a rotation speed of 500 rpm. Free amino acid analysis is performed using this suspension.
  • the adsorbent is a solution
  • free amino acid analysis is performed in the solution, and the total amount of free amino acids can be calculated from the mass of the solid content of the adsorbent obtained by centrifuging the adsorbent solution.
  • the mass of the solid content of the adsorbent is measured after it has been thoroughly dried under drying conditions such as 60°C for 24 hours.
  • the free amino acids contained in the biological material are supported on the surface of a substrate, which is a peptide or protein.
  • a substrate which is a peptide or protein.
  • the substrate may be a biological material, a resin or an inorganic material, but if it is a biological material, the free amino acids can be easily increased.
  • the free amino acids are supported on the body surface of a microorganism.
  • the base of the adsorbent is a resin or inorganic material
  • the base is in the form of a powder or porous body with a large specific surface area
  • a large number of free amino acids can be supported on the surface of the base.
  • amino acids can also be supported on the inner walls of the pores.
  • inactive amino acids When the adsorbent is made of a biological substance, in addition to free amino acids, there are amino acids that do not contribute to the adsorption reaction (hereinafter sometimes referred to as inactive amino acids).
  • inactive amino acids include amino acids that are located in the middle position of amino acids linked by peptide bonds, and amino acids that are located in the interior of the adsorbent and are not exposed on the surface.
  • the adsorbent When the adsorbent is made of a biological substance, it is effective to increase the content of free amino acids in the adsorbent by carrying out a process that breaks the peptide bonds of inactive amino acids present in the adsorbent and converts the inactive amino acids into free amino acids.
  • the peptide bonds present in the microorganism can be cleaved by existing processing methods.
  • the proteins that constitute the microorganism are decomposed with proteolytic enzymes such as trypsin, LYSYLENDOPEPTIDASE (registered trademark), and V8 Protease. This allows at least a portion of the inactive amino acids contained in the body of the microorganism to be converted into free amino acids.
  • a method for converting inactive amino acids into free amino acids a method in which the adsorbent is subjected to a heating treatment at 60°C or higher, a boiling treatment, or a heating and pressurizing treatment using an autoclave or the like to decompose the proteins is also effective.
  • the adsorbent is a living organism such as a microorganism and does not need to be stored in a solution, but can be stored as a solid like a decomposed inanimate object, then large-scale facilities for cultivation and storage and maintenance are not required, and the facilities can be made smaller.
  • the second adsorbent contains at least one first amino acid selected from the group consisting of alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, proline, threonine, asparagine, glycine, isoleucine, ornithine, arginine, serine, citrulline, and cystathionine, and at least a portion of the first amino acid is present as a free amino acid in the solution.
  • the second adsorbent may also contain a total amount of the first amino acid in the form of free amino acid of 10 mol% or more relative to the total amount of free amino acids.
  • the second adsorbent exists as a solid and does not contain free amino acids in the solid state, but has free amino acids in solution.
  • An example of the second adsorbent is a salt of the first amino acid.
  • salts include hydrochloride, nitrate, sulfate, acetate, and carbonate.
  • An adsorbent made of an amino acid salt dissolves in a liquid to supply free amino acids. Then, similar to the first adsorbent, the adsorbent is added to a solution in which a metal compound has been dissolved, and the pH is adjusted so that the zeta potential of the free amino acid of the adsorbent is positive. At this time, the metal compound exists as an anion, and the anion of the metal compound is adsorbed to the positively charged free amino acid of the adsorbent.
  • the content ratio of free amino acids in the adsorbent can be made higher than in the case where free amino acids are supported on the surface of a substrate. This makes it possible to achieve high adsorption efficiency of metal compounds, and a large amount of metal compounds can be adsorbed with a small amount of adsorbent. In addition, when recovering metal compounds after adsorption, the content of unnecessary materials that need to be disposed of is small, making handling easy and reducing manufacturing costs. Furthermore, since the adsorbent is not a living organism like bacteria or microorganisms, it is easy to store and manage the adsorbent.
  • the second adsorbent which is an adsorbent made of salt, may be in the form of a solution, but is easier to handle, store, and manage if it is a solid, and is particularly easy to dissolve in a solution if it is in powder form.
  • the adsorbent may also be in the form of pellets to facilitate handling.
  • the adsorbent has good adsorption efficiency.
  • a salt containing lysine may be used as the adsorbent.
  • examples of salts containing lysine include lysine hydrochloride, lysine sulfate, lysine nitrate, and lysine acetate.
  • lysine hydrochloride for example, L-lysine hydrochloride
  • lysine hydrochloride is stable and inexpensive. Furthermore, when lysine hydrochloride is used as an adsorbent, it is less likely that unnecessary elements will be introduced during the acid treatment in the subsequent process.
  • “having at least one salt of lysine or arginine as the main component” means that the total mass ratio of the lysine salt or arginine salt in the adsorbent is 50 mass% or more relative to the total amount of the adsorbent.
  • the total amount of the lysine salt and the arginine salt present in the adsorbent is preferably 90% by mass or more. This allows a large amount of metal compound to be adsorbed with a small amount of adsorbent. A more preferable range for the total amount of the lysine salt and the arginine salt present in the adsorbent is 95% by mass or more.
  • the cost of the adsorbent can be reduced by including a salt of glutamic acid as the salt of the first amino acid.
  • a salt of glutamic acid as the salt of the first amino acid.
  • sodium glutamate is stable and inexpensive.
  • the content of glutamic acid salts in the adsorbent is preferably 90% by mass or more. This allows the metal compounds to be recovered inexpensively.
  • the preferred range for the total amount of glutamic acid salts in the adsorbent is 95% by mass or more.
  • the free amino acid is not limited to one type.
  • salts of other first amino acids such as lysine and arginine, can be added along with the salt of glutamic acid.
  • the adsorbent when the adsorbent is made of a microorganism, 1 g to 10 kg of the adsorbent is added per 1 m3 of tungsten compound solution in which the tungsten concentration has been adjusted to 0.1 to 10 mmol/l (0.1 to 10 mmol of tungsten per 1 liter of alkaline solution).
  • the adsorbent is made of a salt of a first amino acid
  • the total amount of the salt of the first amino acid added in the adsorbent is added at a content ratio of 0.2 to 1.1 mol per mol of the metal component of the metal compound. This makes it possible to adsorb a large amount of metal compounds, such as tungsten compounds, with a small amount of adsorbent.
  • the total amount of the salt of the first amino acid added may be 10 to 300 g/l of the metal compound solution. In such a case, the viscosity of the solution does not increase, and the recovery efficiency of the metal compound is less likely to decrease. In particular, when the adsorbent is made of a salt of an amino acid, the viscosity of the solution does not increase easily, and workability is good.
  • the temperature can be adjusted according to the activity of the free amino acid, and can usually be room temperature.
  • the tungsten compound solution with added adsorbent is adjusted using hydrochloric acid or the like so that the zeta potential of the free amino acid is positive. This causes the adsorbent to adsorb the anionic tungsten compound ions.
  • the pH of the solution is less than 7 (acidic).
  • the free amino acids are lysine and arginine
  • the preferred pH is 4 or less, preferably 1 to 3, and more preferably 1 to 2.3.
  • the free amino acid is glutamic acid
  • the preferred pH is 1.5 or less. This can increase the recovery rate of the tungsten compound. Note that the step of adjusting the pH of the solution and the step of adding an adsorbent to the solution containing the metal compound can be carried out in any order.
  • the recovery efficiency of the adsorbent is higher if the adsorption reaction lasts for less than one hour. In other words, if the adsorption reaction lasts for more than one hour, some of the adsorbed metal compound may be released from the free amino acid.
  • removing includes a step of filtering the compound from the solution and a step of drying and powdering the compound recovered by filtering.
  • the adsorbent that has adsorbed tungsten compound ions is filtered with filter paper or the like to recover the compound in a slurry form on the filter paper.
  • the recovered compound is then dried and powdered to extract the tungsten compound containing the powdered adsorbent.
  • the tungsten compound containing the adsorbent refers to, for example, lysine- WO4 when the adsorbent is lysine.
  • FG process A predetermined amount of carbon powder (carbon black, graphite powder, activated carbon, etc.) or carbon slurry is added as a reducing agent to the extracted tungsten compound and mixed (step F). Then, the mixture is heated to 1100 to 2000°C under a predetermined atmosphere for a predetermined time to perform carbonization treatment, thereby obtaining tungsten powder mainly composed of tungsten carbide (step G).
  • main component means that tungsten carbide is the largest component in mass% among the components contained in the powder. Specifically, tungsten carbide is contained in an amount of 99 mass% or more, while unavoidable impurities of less than 1 mass% may be contained.
  • unavoidable impurities include carbon, hydrogen, nitrogen, oxygen, chromium, vanadium, tantalum, niobium, titanium, etc. More specifically, the powder may contain 99.2 mass% or more of tungsten carbide and substantially does not contain at least one carbide, nitride, or carbonitride selected from IVa, Va, and VIa group elements except W. Furthermore, the above-mentioned predetermined atmosphere may be, for example, a reducing atmosphere containing carbon monoxide, nitrogen, hydrogen, methane, and the like.
  • the carbonization process is performed in a mixed atmosphere containing nitrogen and hydrogen as the main components.
  • the mixed atmosphere contains nitrogen and hydrogen as the main components
  • the production costs are reduced compared to when nitrogen and hydrogen are treated separately in their respective atmospheres.
  • main component means that, among the components contained in the gas, nitrogen and hydrogen are more abundant in mole percent than the components other than nitrogen and hydrogen. More specifically, this refers to the case where the proportions of nitrogen and hydrogen are 40 mole percent or more and 10 mole percent or more, respectively.
  • the powder extracted in the E step is incinerated to remove the adsorbent and extract WO3 .
  • Metallic tungsten is extracted by removing oxygen from this WO3 through a reduction process.
  • tungsten carbide powder is obtained by carbonizing this metallic tungsten.
  • the process of removing the adsorbent and extracting WO3 requires incineration at a temperature of 300 (°C) or higher, and the reduction process of WO3 requires heat treatment at a temperature of 800 (°C) to 950 (°C) in a reducing atmosphere (for example, a hydrogen gas atmosphere). Therefore, a large burden was required to produce tungsten carbide powder.
  • the tungsten compound extracted in the above-mentioned step E is directly carbonized to produce WC without going through the above-mentioned oxidation and reduction treatments. This reduces the burden of producing tungsten carbide powder. Furthermore, when carbonizing the above-mentioned tungsten compound, carbon powder is mixed in to produce a mixture, and this mixture is then heated.
  • the carbon component contained in the adsorbent can be used to carbonize tungsten to obtain WC.
  • the carbon component contained in the adsorbent alone is likely to be insufficient in the G step in which tungsten is carbonized, and therefore not only WC but also W2C is likely to be produced in this G step.
  • step F of the production method of this embodiment since carbon powder is mixed with the tungsten compound, the above-mentioned carbon shortage is eliminated, W 2 C is less likely to be produced, and it is possible to produce WC powder with high purity.
  • the amount of carbon powder added in the step F may be adjusted so that the carbon content in the mixture is 5 mass% or more. In this case, tungsten is easily and stably carbonized in the step G, so that W2C is not easily generated and WC is easily generated.
  • the amount of carbon powder added in step F may be adjusted so that the carbon content in the mixture is 6% by mass or less.
  • the more carbon there is in the mixture the more stable the carbonization of tungsten becomes.
  • the process of removing the excess carbon that has not bonded with tungsten after step G may become complicated.
  • the carbon content in the mixture is 6% by mass or less, the load required to remove the excess carbon is small.
  • the amount of carbon powder may be adjusted taking into account the amount of carbon components contained in the adsorbent.
  • the carbon components in tungsten carbide may not only be derived from the carbon powder, but may also be derived from the carbon components in the adsorbent. In other words, the carbon in the tungsten powder may contain the carbon in the adsorbent. If the adsorbent is an organic material as described above and contains carbon, and the carbon in the tungsten powder contains the carbon in the adsorbent, the amount of carbon powder added in step F can be reduced.
  • the hydrogen content may be less than or equal to that of nitrogen. If there is less hydrogen than nitrogen, coarse particles are less likely to form. Note that the nitrogen and hydrogen content ratios being approximately the same does not require them to be strictly the same. If the nitrogen content ratio/hydrogen content ratio is between 0.9 and 1.1, it is considered to be "approximately the same.”
  • the metal compound recovery method of this embodiment can reduce the number of steps, as well as the amount of chemicals used and waste liquid, making it possible to recover tungsten compounds at low cost.
  • the total amount of CO2 emitted by the process of the present application may be about 40% of the total amount of CO2 (energy equivalent) emitted by a conventional ion exchange method for producing tungsten carbide via ammonium paratungstate and W metal powder.
  • the process of the present application for producing tungsten carbide it is possible to significantly reduce the amount of CO2 emitted.
  • tungsten carbide products a method for manufacturing a tungsten carbide product according to a non-limiting example of the present disclosure will be described. Specifically, a method for manufacturing a tungsten carbide product using tungsten carbide powder obtained by the production method of the present disclosure as a raw material will be described. Here, a method for manufacturing a cutting insert using tungsten carbide powder obtained by the production method of the present disclosure as a raw material will be described in detail as an example.
  • a method for manufacturing a machined product includes the following steps (X) and (Y). (X) mixing tungsten carbide powder with cobalt powder to form a compact; (Y) firing the compact.
  • a suitable amount of cobalt powder is added to the tungsten carbide powder obtained by the production method disclosed herein.
  • metal powders other than cobalt powder and/or carbon powder may also be added.
  • the mixture is then wet mixed in a ball mill for a predetermined time, dried, and then molded into a predetermined tool shape using a known molding method such as press molding, casting, extrusion molding, or cold isostatic pressing to obtain a molded body.
  • the molded body is sintered in a vacuum or a non-oxidizing atmosphere to produce a cutting insert.
  • the surface of the produced cutting insert may be polished or honed.
  • the surface of the cutting insert may be coated with a coating by chemical vapor deposition (CVD) or physical vapor deposition ( PVD ) techniques, with coating compositions including titanium carbide (TiC), titanium nitride (TiN), titanium carbonitride (TiCN), and alumina ( Al2O3 ).
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • a method for producing tungsten powder mainly composed of tungsten carbide may include the steps of preparing a raw material containing tungsten oxide, obtaining a solution by dissolving the tungsten oxide from the raw material using an alkaline solvent, adding an adsorbent to the solution and reacting the adsorbent with the solution containing the dissolved tungsten to obtain a compound containing the adsorbent and tungsten, extracting the compound from the solution, mixing the compound with carbon powder to produce a mixture, and heating the mixture.
  • the adsorbent may be a salt containing lysine.
  • the adsorbent may be lysine hydrochloride.
  • the atmosphere in the step of heating the mixture may be a mixed atmosphere containing nitrogen and hydrogen as main components.
  • the carbon in the tungsten powder may contain carbon in the adsorbent.
  • the carbon content in the mixture may be 6 mass% or less.
  • the carbon content in the mixture may be 5 mass% or more.
  • a method for producing a tungsten carbide product may include a step of mixing tungsten powder obtained by any one of the above tungsten powder production methods (1) to (7) with cobalt powder to form a molded body, and a step of sintering the molded body.

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PCT/JP2023/046939 2023-03-01 2023-12-27 タングステン粉末の製造方法及び炭化タングステン製品の製造方法 Ceased WO2024180893A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2617140B2 (ja) * 1990-01-12 1997-06-04 東京タングステン株式会社 超微粒ｗｃ粉，及びその製造方法
JP2015098641A (ja) * 2013-10-18 2015-05-28 京セラ株式会社 タングステン化合物の回収方法
WO2015129835A1 (ja) 2014-02-26 2015-09-03 京セラ株式会社 金属化合物吸着剤およびそれを用いた金属化合物の回収方法
JP2015224225A (ja) * 2014-05-28 2015-12-14 京セラ株式会社 金属化合物吸着材およびそれを用いた金属化合物の回収方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2617140B2 (ja) * 1990-01-12 1997-06-04 東京タングステン株式会社 超微粒ｗｃ粉，及びその製造方法
JP2015098641A (ja) * 2013-10-18 2015-05-28 京セラ株式会社 タングステン化合物の回収方法
WO2015129835A1 (ja) 2014-02-26 2015-09-03 京セラ株式会社 金属化合物吸着剤およびそれを用いた金属化合物の回収方法
JP2015224225A (ja) * 2014-05-28 2015-12-14 京セラ株式会社 金属化合物吸着材およびそれを用いた金属化合物の回収方法

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Title
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