WO2023145520A1 - 酸化タングステン粉末 - Google Patents

酸化タングステン粉末 Download PDF

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Publication number
WO2023145520A1
WO2023145520A1 PCT/JP2023/001031 JP2023001031W WO2023145520A1 WO 2023145520 A1 WO2023145520 A1 WO 2023145520A1 JP 2023001031 W JP2023001031 W JP 2023001031W WO 2023145520 A1 WO2023145520 A1 WO 2023145520A1
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WO
WIPO (PCT)
Prior art keywords
tungsten oxide
tungsten
sodium
oxide powder
potassium
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PCT/JP2023/001031
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 岩井
貴彦 牧野
志賢 青木
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京セラ株式会社
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Priority to JP2023576801A priority Critical patent/JPWO2023145520A1/ja
Priority to CN202380016519.6A priority patent/CN118613446A/zh
Publication of WO2023145520A1 publication Critical patent/WO2023145520A1/ja

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    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides

Definitions

  • the disclosed embodiments relate to tungsten oxide powder.
  • tungsten is a component that constitutes cemented carbide and cemented carbide such as cermet, and is used together with cobalt, niobium, etc., and is widely used in cutting tools and the like.
  • tungsten since tungsten has a high melting point, it is used in various applications such as heating elements, structural members, catalysts for the petrochemical industry, environmental equipment, wiring for ceramic wiring boards, and heat dissipation members. In order to effectively utilize these resources, a method of recycling tungsten from waste materials (scrap) has been devised (see Patent Document 1).
  • a tungsten oxide powder according to one aspect of the embodiment contains a powder containing tungsten oxide crystal grains as a main component.
  • the tungsten oxide grains contain sodium and potassium. Further, the tungsten oxide crystal grains have a structure in which the sodium concentration is higher than the potassium concentration over the entire depth direction.
  • FIG. 1 is a flow chart showing an example of a procedure for producing tungsten oxide powder and tungsten carbide according to an embodiment.
  • FIG. 2 is a flow chart showing an example of a procedure for producing tungsten oxide powder and tungsten carbide in a reference example.
  • FIG. 3 is a diagram showing the depth direction distribution of sodium and potassium in the tungsten oxide powder according to the embodiment.
  • FIG. 4 is a diagram showing the depth direction distribution of sodium and potassium in the tungsten oxide powder in Reference Example.
  • the tungsten oxide powder according to the embodiment contains powder containing tungsten oxide crystal grains as a main component.
  • the tungsten oxide powder according to the embodiment contains powder composed of tungsten oxide crystal grains and unavoidable impurities.
  • the tungsten oxide crystal grains according to the embodiment contain sodium and potassium instead of being composed of only tungsten oxide.
  • the tungsten oxide crystal grains contained in the tungsten oxide powder have a structure in which the sodium concentration is higher than the potassium concentration throughout the depth direction.
  • the reaction promoting effect can be enhanced in the hydrogen reduction treatment for producing metallic tungsten, which is an intermediate in producing tungsten carbide from tungsten oxide powder. The reason will be explained below.
  • the melting point of sodium is 98 (°C) and the boiling point is 883 (°C)
  • the melting point of potassium is 64 (°C) and the boiling point is 759 (°C).
  • the treatment temperature for reducing tungsten oxide powder to metal tungsten with hydrogen gas is generally 800 (° C.) to 950 (° C.).
  • the temperature for the hydrogen reduction treatment of the tungsten oxide powder as described above is 800 (° C.) to 950 (° C.), which is close to the boiling point of sodium.
  • the temperature for the hydrogen reduction treatment of the tungsten oxide powder as described above is 800 (° C.) to 950 (° C.), which is close to the boiling point of sodium.
  • potassium since potassium reaches the boiling point, it evaporates during the treatment and disappears. Therefore, due to the effect of heat of vaporization when potassium volatilizes, the volatilization of sodium is suppressed even though the temperature is close to the boiling point of sodium. For these reasons, sodium tends to exist in a molten state when the tungsten oxide powder is subjected to hydrogen reduction treatment.
  • the reduction treatment can proceed while adjoining particles are adhered to each other.
  • grain growth of metallic tungsten can be achieved with lower energy (that is, at a lower temperature and in a shorter time) than in the case of containing only sodium without containing potassium.
  • the sodium concentration in the powder is higher than the potassium concentration. Since the sodium concentration is relatively high, the effect of adhering adjacent particles due to the molten state of sodium is high. In addition, since the potassium concentration is relatively small but not 0, the effect of suppressing the volatilization of sodium can be simultaneously obtained while ensuring a high effect of adhering adjacent particles due to the molten state of sodium.
  • the tungsten oxide crystal grains are configured such that the sodium concentration is higher than the potassium concentration throughout the depth direction.
  • formation of metallic tungsten tends to proceed not only on the surface of the powder but also on the entire powder toward the center. Therefore, the production efficiency of metallic tungsten is improved. Therefore, tungsten carbide can be efficiently produced from tungsten oxide powder.
  • a region having a higher sodium concentration than the inside of the tungsten oxide crystal grain may be formed on the surface of the tungsten oxide crystal grain.
  • tungsten carbide can be more efficiently produced from tungsten oxide powder.
  • the high sodium concentration region formed on the surface of the tungsten oxide crystal grain may exist at a depth of up to 100 (nm) from the surface of the tungsten oxide crystal grain.
  • tungsten carbide can be more efficiently produced from tungsten oxide powder.
  • the tungsten oxide crystal grains may have a sodium concentration of 5 (ppm) to 100 (ppm), and may have a sodium concentration of 20 (ppm) to 100 (ppm). preferable.
  • tungsten carbide can be more efficiently produced from tungsten oxide powder.
  • the sodium contained in the tungsten oxide crystal grains decomposes and disappears when exposed to a high temperature of 1200 (°C) or higher in the carbonization process that produces tungsten carbide from metallic tungsten. Therefore, even if tungsten oxide crystal grains themselves contain sodium, there is no particular problem with the quality of tungsten carbide.
  • a region having a higher sodium concentration than the inside of the tungsten oxide crystal grain is formed on the surface of the tungsten oxide crystal grain, thereby facilitating the decomposition and disappearance of sodium in the carbonization process. . Therefore, according to embodiments, high quality tungsten carbide can be produced.
  • FIG. 1 is a flow chart showing an example of a procedure for producing tungsten oxide powder and tungsten carbide according to an embodiment. As shown in FIG. 1, in the step of producing tungsten oxide powder and tungsten carbide according to the embodiment, first, cemented carbide scrap was prepared.
  • Cemented carbide which is a kind of cemented carbide, is mainly composed of composite carbides such as metal tungsten and tungsten carbide, and has iron, nickel, cobalt, etc. as a binding phase, and if necessary, as additive components TiC, TaC, NbC, VC, Cr 3 C 2 and the like. Moreover, the scrap in the examples further contains sodium and potassium in addition to these additive components.
  • Materials to be treated containing cemented carbide are, for example, cutting tools (cutting inserts, drills, end mills, etc.), molds (forming rolls, molds, etc.), civil engineering and mining tools (oil drilling tools, rock crushing tools, etc.).
  • the prepared cemented carbide scrap was then oxidatively roasted to obtain a mixture of tungsten oxide (WO 3 ) and cobalt tungstate (CoWO 4 ). If the amount of sodium and potassium contained in the cemented carbide scrap is small, sodium and potassium may be added when obtaining the mixture. Then, the resulting mixture was refluxed with an aqueous sodium hydroxide (NaOH) solution and then extracted to obtain a tungsten compound solution containing sodium tungstate (Na 2 WO 4 ).
  • NaOH aqueous sodium hydroxide
  • the adsorbent in the present disclosure is not limited to containing lysine, Alanine, Cystine, Methionine, Tyrosine, Valine, Glutamic acid, Histidine ( Histidine, Proline, Threonine, Asparagine, Glycine, Isoleucine, Ornithine, Arginine, Serine, Citrulline and Cystathionine ( Cystathionine).
  • the total addition amount of the salt of the first amino acid in the adsorbent is 0.2 (mol) to 1.1 (mol) with respect to 1 (mol) of the metal component of the tungsten compound. Add in proportion. As a result, a large amount of tungsten compound can be adsorbed with a small amount of adsorbent.
  • the total added amount of the salt of the first amino acid is, for example, 10 (g/l) to 300 (g/l) with respect to the tungsten compound solution.
  • the viscosity of the solution does not increase, and the recovery efficiency of the metal compound is less likely to decrease.
  • the adsorbent consists of an amino acid salt, the viscosity of the solution is less likely to increase, resulting in good workability.
  • the temperature may be adjusted according to the activity of free amino acids, and usually room temperature is fine.
  • the tungsten compound solution to which the adsorbent has been added may be adjusted using hydrochloric acid or the like so that the zeta potential of free amino acids is positive. This allows the adsorbent to adsorb tungsten compound ions, which are anions.
  • the pH of the solution may be less than 7 (acidic).
  • the free amino acid is glutamic acid, the preferred pH is 1.5 or less.
  • Potassium has a higher tendency to ionize than sodium. Therefore, when the solution is acidic, potassium is easier to ionize than sodium. That is, sodium is relatively difficult to ionize and is difficult to be removed in the step of washing the adsorbent, which will be described later.
  • the sodium concentration in the powder can be higher than the potassium concentration for the reasons described above.
  • the recovery rate of the tungsten compound can be increased by the above steps. Either the step of adjusting the pH of the solution or the step of adding the adsorbent to the solution containing the metal compound may be performed first.
  • the sodium concentration in the powder can be made higher than the potassium concentration. is possible.
  • the recovery efficiency of the adsorbent is higher if the adsorption reaction is within 1 hour. That is, when the adsorption reaction exceeds 1 hour, part of the adsorbed metal compound may be desorbed from the free amino acid.
  • the adsorbent with the tungsten compound ions adsorbed was dehydrated by centrifugation or other means. Then, if necessary, the adsorbent is washed in the order of acid washing and pure water washing. Instead of acid cleaning, hot water of 40 (° C.) or more may be used for cleaning. Impurities were removed by washing with pure water until the electric conductivity of the washing filtrate became 500 ( ⁇ S/m) or less. As a result, the tungsten compound can be highly graded and recovered.
  • the adsorbent with the tungsten compound ions adsorbed thereon was incinerated, for example, at a temperature of 300 (° C.) or higher in the atmosphere to oxidize the tungsten compound and remove organic components including the adsorbent.
  • a tungsten oxide powder (WO 3 ) according to the embodiment was obtained.
  • the obtained tungsten oxide powder is heat-treated at a temperature of 800 (° C.) to 950 (° C.) in a reducing atmosphere (eg, hydrogen gas atmosphere) to reduce the tungsten oxide compound.
  • a reducing atmosphere eg, hydrogen gas atmosphere
  • metallic tungsten (W) can be obtained.
  • tungsten carbide (WC) By carbonizing the obtained metal tungsten, it is possible to obtain tungsten carbide (WC) as a raw material of cemented carbide.
  • FIG. 2 is a flow chart showing an example of a procedure for producing tungsten oxide powder and tungsten carbide in a reference example.
  • a procedure for producing tungsten oxide powder and tungsten carbide in a reference example in the step of producing tungsten oxide powder and tungsten carbide in the reference example, first, cemented carbide scrap was prepared. Moreover, the scrap in the reference example also contains sodium and potassium, like the scrap in the example.
  • the prepared cemented carbide scrap was then oxidatively roasted to obtain a mixture of tungsten oxide (WO 3 ) and cobalt tungstate (CoWO 4 ).
  • a tungsten compound solution containing sodium tungstate (Na 2 WO 4 ) was obtained by extracting the resulting mixture with an aqueous sodium hydroxide (NaOH) solution. Since each process up to this point is the same as the above-described embodiment, detailed description thereof is omitted.
  • the resulting tungsten compound solution was ion-exchanged with an ion exchange resin or the like to produce an aqueous solution of ammonium tungstate ((NH 4 ) 2 WO 4 ). Then, the resulting aqueous solution was heated and concentrated to crystallize the tungsten compound as ammonium paratungstate (APT). At this time, since the aqueous solution of ammonium tungstate used in the comparative example is not an acidic solution, a large amount of sodium is removed in the step of crystallizing APT, and the content ratio of potassium to sodium tends to increase.
  • metal tungsten (W) can be obtained by heat-treating the obtained tungsten oxide powder in a reducing atmosphere to reduce the tungsten oxide compound.
  • tungsten carbide (WC) By carbonizing the obtained metal tungsten, it is possible to obtain tungsten carbide (WC) as a raw material of cemented carbide.
  • the obtained tungsten oxide powders of the embodiment and reference example were analyzed by ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry). Specifically, the depth distribution of sodium and potassium in the tungsten oxide powders of the embodiment and reference example was measured by ToF-SIMS.
  • the measurement conditions for ToF-SIMS are as follows.
  • the tungsten oxide powders of the embodiment and reference example were fixed, and the powder surface was measured at 100 ( ⁇ m) square.
  • the measuring device is TOF.
  • SIMS5 was used, Bi (bismuth) was selected as the primary ion source, and elemental analysis in the depth direction was measured.
  • FIG. 3 is a diagram showing the depth direction distribution of sodium and potassium in the tungsten oxide powder according to the embodiment.
  • FIG. 4 is a diagram showing the depth direction distribution of sodium and potassium in the tungsten oxide powder in the reference example.
  • the sodium concentration is higher than the potassium concentration throughout the depth direction.
  • the tungsten oxide crystal grains contained in the tungsten oxide powder according to the embodiment had a particle size of about several tens to several hundred (nm). Therefore, by measuring the depth distribution up to 500 (nm) as shown in FIG. 3, it can be estimated that the sodium concentration is higher than the potassium concentration throughout the depth direction.
  • tungsten carbide can be efficiently produced from the tungsten oxide powder as described above. Specifically, the processing temperature can be lowered by about 5% to 10%, thereby reducing the energy required during manufacturing by about 5% to 20%.
  • a region having a higher sodium concentration than the inside of the tungsten oxide crystal grain is formed on the surface of the tungsten oxide crystal grain to a depth of about 100 (nm) from the surface.
  • tungsten carbide can be more efficiently produced from tungsten oxide powder.
  • the sodium content of the obtained tungsten oxide powder according to the embodiment was evaluated by an ICP (Inductively Coupled Plasma) emission spectrometer. As a result, it was found that the tungsten oxide crystal grains contained in the tungsten oxide powder according to the embodiment had 5 (ppm) to 100 (ppm) of sodium.
  • ICP Inductively Coupled Plasma
  • tungsten carbide can be more efficiently produced from tungsten oxide powder.
  • the present invention is not limited to the above embodiments, and various modifications are possible without departing from the spirit of the present invention.
  • the above embodiment shows the case of producing (recycling) tungsten oxide powder and tungsten carbide from cemented carbide scrap, but the present disclosure is not limited to such examples, and tungsten oxide powder and tungsten carbide are produced from ore. It can also be applied when generating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/JP2023/001031 2022-01-28 2023-01-16 酸化タングステン粉末 WO2023145520A1 (ja)

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CN202380016519.6A CN118613446A (zh) 2022-01-28 2023-01-16 氧化钨粉末

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4402737A (en) * 1982-09-01 1983-09-06 Gte Products Corporation Method of producing tungsten and tungsten carbide powder
JP2004508461A (ja) * 2000-09-06 2004-03-18 ハー　ツェー　シュタルク　ゲゼルシャフト　ミット　ベシュレンクテル　ハフツング 超粗粒の単結晶の炭化タングステン及びその製造方法及びそれから製造される硬質合金
CN108046326A (zh) * 2017-12-07 2018-05-18 崇义章源钨业股份有限公司 制备仲钨酸铵的方法
JP2018119197A (ja) * 2017-01-27 2018-08-02 京セラ株式会社 タングステン化合物の回収方法
CN108529628A (zh) * 2018-05-28 2018-09-14 株洲硬质合金集团有限公司 一种粗晶碳化钨粉的制备方法
CN111940753A (zh) * 2020-08-27 2020-11-17 崇义章源钨业股份有限公司 制备超粗钨粉的系统及方法
CN114436263A (zh) * 2022-02-14 2022-05-06 崇义章源钨业股份有限公司 一种超粗均匀碳化钨粉的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4402737A (en) * 1982-09-01 1983-09-06 Gte Products Corporation Method of producing tungsten and tungsten carbide powder
JP2004508461A (ja) * 2000-09-06 2004-03-18 ハー　ツェー　シュタルク　ゲゼルシャフト　ミット　ベシュレンクテル　ハフツング 超粗粒の単結晶の炭化タングステン及びその製造方法及びそれから製造される硬質合金
JP2018119197A (ja) * 2017-01-27 2018-08-02 京セラ株式会社 タングステン化合物の回収方法
CN108046326A (zh) * 2017-12-07 2018-05-18 崇义章源钨业股份有限公司 制备仲钨酸铵的方法
CN108529628A (zh) * 2018-05-28 2018-09-14 株洲硬质合金集团有限公司 一种粗晶碳化钨粉的制备方法
CN111940753A (zh) * 2020-08-27 2020-11-17 崇义章源钨业股份有限公司 制备超粗钨粉的系统及方法
CN114436263A (zh) * 2022-02-14 2022-05-06 崇义章源钨业股份有限公司 一种超粗均匀碳化钨粉的制备方法

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