WO2017164898A1 - Procédé de traitement d'acide tungstique non raffiné pour produire du tungstène pour alliage destiné à être utilisé dans des aciers contenant du tungstène et des superalliages à base de nickel - Google Patents

Procédé de traitement d'acide tungstique non raffiné pour produire du tungstène pour alliage destiné à être utilisé dans des aciers contenant du tungstène et des superalliages à base de nickel Download PDF

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Publication number
WO2017164898A1
WO2017164898A1 PCT/US2016/034058 US2016034058W WO2017164898A1 WO 2017164898 A1 WO2017164898 A1 WO 2017164898A1 US 2016034058 W US2016034058 W US 2016034058W WO 2017164898 A1 WO2017164898 A1 WO 2017164898A1
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WIPO (PCT)
Prior art keywords
tungsten
roasting
tungstic acid
unrefined
hours
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PCT/US2016/034058
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English (en)
Inventor
James Edward HOULDEN
Xiaoying Song
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Aeroalloys LLC
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Aeroalloys LLC
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Publication of WO2017164898A1 publication Critical patent/WO2017164898A1/fr
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    • 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
    • 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
    • C22B1/02—Roasting 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • This invention relates to methods of treating unrefined tungstic acid to produce a semi-refined anhydrous tungsten trioxide.
  • the anhydrous tungsten trioxide can be used as an input raw material for the manufacture of both tungsten bearing steels and nickel based superalloys.
  • tungsten in metallurgical applications has been widely recognized since the mid 1800's.
  • Tungsten was regarded as one of the first alloying elements used to improve steel properties such as hardness and wear resistance.
  • tungsten forms tungsten carbides or complexes with other elements such as chromium, molybdenum, vanadium, or iron.
  • This carbide formation increases the amount of undissolved and excess carbide in the hardened steel, causing precipitation of fine or very fine grained carbides evenly distributed in the steel matrix.
  • the formation of stable carbides can increase the hardness of the steel, particularly at high temperatures.
  • tungsten-alloyed steels were made by the simple addition of pure tungsten powder or a purified tungsten ore to the steel melt.
  • the more current practice involves adding tungsten to the steel melt in the form of tungsten scrap, as a tungsten-rich prealloy known as ferro-tungsten, or as natural or synthetic scheelite ore concentrates.
  • the tungsten scrap, ferro-tungsten, or scheelite concentrates can be added directly to the arc furnace to produce a base melt which can then be further refined, such as in an argon oxygen decarburization (AOD) or vacuum oxygen decarburization (VOD) converter.
  • AOD argon oxygen decarburization
  • VOD vacuum oxygen decarburization
  • Standard ferro- tungsten is available in different grades having varying carbon content and the tungsten amount is typically between 75 and 80 wt%.
  • Scheelite is a calcium tungstate material having the chemical formula CaW0 4 . Scheelite can be subject to extraction techniques to recover a concentrated amount of tungsten trioxide (WO3).
  • WO3 tungsten trioxide
  • Unrefined, hydrated tungstic acid is roasted in an oxidizing atmosphere to reduce the water and sulfur content.
  • the roasting process produces a semi-refined anhydrous tungsten trioxide. Once roasted, this material can be melted with an iron base or nickel base material to form iron-tungsten or nickel-tungsten alloys of varying tungsten concentrations.
  • described is a process of treating unrefined tungstic acid to produce anhydrous tungsten trioxide through roasting of the unrefined tungstic acid at a roasting temperature and for a roasting time period sufficient to remove the moisture from the unrefined tungstic acid.
  • the roasting temperature is between 300°C and 1200°C, such as between 300°C and 900°C.
  • the roasting time period is between 1 hour and 6 hours, such as between 1 hour and 5 hours.
  • the roasting temperature is between 600°C and 900°C and the roasting time period is between 3 hours and 5 hours.
  • a sulfur content of the anhydrous tungsten trioxide is reduced to 0.03 wt% or less, such as between 0.01 wt% and 0.03 wt , through the roasting process.
  • roasting the unrefined tungstic acid reduces a sulfur content of the unrefined tungstic acid by greater than 95 wt%.
  • roasting the unrefined tungstic acid reduces the weight of the unrefined tungstic acid by between 20 and 70 wt%.
  • the process can further include sintering the anhydrous tungsten trioxide at a temperature of 1600°C or more for between 2 hours and 4 hours.
  • anhydrous tungsten trioxide material prepared by roasting unrefined tungstic acid according to the process described above.
  • a process of producing a tungsten- bearing material includes melting a base material in the presence of an anhydrous tungsten trioxide material prepared according to the process described above.
  • the base material is an iron base material.
  • the base material is a nickel base material.
  • the starting material for this process is unrefined hydrated tungstic acid.
  • Tungstic acid refers to the hydrated form of tungsten trioxide and, for purposes of this disclosure, includes all hydrates thereof, including the monohydrate and di-hydrate. Hydrated tungstic acid is commercially available from a variety of sources and may be available in different physical forms.
  • the hydrated tungstic acid is roasted to prepare the material for addition, including by direct addition, to a melting furnace in subsequent operations.
  • the roasting process removes moisture contained therein.
  • Hydrated tungstic acid typically contains both free moisture and chemically combined water. Free moisture refers to the water molecules that are not chemically combined with the tungsten trioxide. Both the free moisture and the chemically combined water must be removed to produce anhydrous tungsten trioxide. Removal of the free moisture and chemically combined water will typically amount to an overall loss of weight in the hydrated tungstic acid of between 20 and 70 wt% based on the weight of the starting material due to total water removal (known as loss on ignition, or "LOI").
  • LOI loss on ignition
  • the sulfur content in the input material which is typically in the range of 0.5 wt , is too high for most end use melting applications.
  • the sulfur content can be reduced to less than 0.03 wt , such as between 0.01 wt and 0.03 wt , with a lower value being most preferred.
  • An overall sulfur reduction of 90% or more, such as 95% or more, can be achieved with the process described herein.
  • roasting occurs at a temperature and for a time period sufficient to remove all, or substantially all, of the free and combined water and to reduce the sulfur content to a more acceptable level, consistent with the principles discussed above.
  • roasting can occur at a temperature of between 300°C and 1200°C in an oxidizing atmosphere, such as in an unprotected atmosphere of air, with the roasting time varying based on the temperature selected.
  • the roasting time may be between one and six hours with higher roasting temperatures requiring roasting times nearer the bottom of this range.
  • Roasting for a period longer than six hours is also possible, though sufficient moisture removal can usually be accomplished in under six hours.
  • roasting occurs at a temperature of less than 900°C for a maximum of five hours, such as between 600°C and 900°C for between three and five hours, or about 700°C for about three hours.
  • Roasting can occur in an industrial multi-hearth roaster, or other suitable furnace (such as a rotary kiln), operating at or near atmospheric pressure.
  • Laboratory testing using a muffle furnace has confirmed that roasting at a temperature of less than 900°C for five hours or less in an air atmosphere can produce anhydrous tungsten trioxide with a resulting sulfur reduction greater than 95%.
  • the resulting anhydrous tungsten trioxide is suitable as a direct charge material to any air melting furnace (e.g., electric arc/AOD, or Air Induction Furnace).
  • any air melting furnace e.g., electric arc/AOD, or Air Induction Furnace.
  • Slitter scrap was used as a source of iron, and the roasted tungsten trioxide, prepared by roasting hydrated tungstic acid for three hours at a temperature of 700°C was added directly to the furnace, along with the slitter scrap, prior to powering up the furnace. Once power was applied, the tungsten trioxide began to melt first, followed shortly thereafter by the slitter scrap. No slag cover or flux was added to any of the melting trials.
  • tungsten trioxide melted before both the iron and nickel base materials. This provides an advantage over traditional sources of tungsten, such as tungsten/ferro-tungsten solids. Due to the low melting point of tungsten trioxide (approx. 1473°C), the tungsten will rapidly diffuse in its molten state. Tungsten, a high temperature refractory metal, is notoriously difficult to dissolve in a molten metal bath when present as a solid, such as a tungsten/ferro-tungsten solid. In conventional processes, if the addition of solid tungsten or ferro-tungsten is not carefully sized, it can often be found as an undissolved solid at the end of a melt.
  • tungsten trioxide will allow melters to reduce melting cycle time and ensure yields are not compromised due to any residual undissolved material.
  • the powdered tungsten trioxide produced from the roasting process described above can be pressed into a briquette (similar to a standard charcoal briquette) or pelletized, which process can be aided by including one or more commercially available binder agents.
  • the anhydrous tungsten trioxide prepared according to the roasting process was directly added to the furnace.
  • Initial laboratory testing has been performed which indicates additional processing of the anhydrous tungsten trioxide may prove beneficial.
  • the anhydrous tungsten trioxide may be subjected to a sintering process in which a high temperature reduction furnace, such as one operating at a temperature of 1600°C or more, is used to lower the oxygen content of the anhydrous tungsten trioxide and form a metallic diffusion bond between the fine particles of reduced tungsten.
  • the sintering can be accomplished by subjecting the anhydrous tungsten trioxide to a temperature of 1600°C for between two and four hours.
  • the diffusion bond that occurs between the fine particles of metallic tungsten may be sufficient to form a strong, sturdy porous "cake” with the strength of the cake varying depending on the extent of the oxygen reduction and the diffusion bonding. If sufficiently strong, the cake may act as a "briquette,” similar to a charcoal briquette, which can be added to the furnace.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de traitement d'acide tungstique non raffiné pour produire un trioxyde de tungstène anhydre semi-raffiné. Le procédé consiste à griller l'acide tungstique non raffiné à une température de grillage et pendant une durée de grillage suffisantes pour éliminer l'humidité de l'acide tungstique non raffiné. Le trioxyde de tungstène anhydre peut être utilisé comme matière première d'entrée pour la fabrication d'aciers contenant du tungstène et de superalliages à base de nickel.
PCT/US2016/034058 2016-03-23 2016-05-25 Procédé de traitement d'acide tungstique non raffiné pour produire du tungstène pour alliage destiné à être utilisé dans des aciers contenant du tungstène et des superalliages à base de nickel Ceased WO2017164898A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662312252P 2016-03-23 2016-03-23
US62/312,252 2016-03-23

Publications (1)

Publication Number Publication Date
WO2017164898A1 true WO2017164898A1 (fr) 2017-09-28

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PCT/US2016/034058 Ceased WO2017164898A1 (fr) 2016-03-23 2016-05-25 Procédé de traitement d'acide tungstique non raffiné pour produire du tungstène pour alliage destiné à être utilisé dans des aciers contenant du tungstène et des superalliages à base de nickel

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057882A (zh) * 2019-12-31 2020-04-24 厦门钨业股份有限公司 从镍钨基合金粉中回收钨的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902917A (en) * 1970-06-04 1975-09-02 Bosch Gmbh Robert Process for the production of tungsten carbide catalyst adapted for use in fuel cells
CN1485450A (zh) * 2003-04-11 2004-03-31 自贡硬质合金有限责任公司 用钨合金废料生产超细晶粒碳化钨——铁系复合粉的方法
US7591984B2 (en) * 2003-07-28 2009-09-22 Los Alamos National Security, Llc Preparation of tungsten oxide
US20140014875A1 (en) * 2011-03-30 2014-01-16 Chonghu Wu Preparation method of industrial purple nano-needle tungsten oxide
CN104591740A (zh) * 2015-01-12 2015-05-06 吴江佳亿电子科技有限公司 一种耐冲击陶瓷材料及其制备方法
CN104818416A (zh) * 2015-05-07 2015-08-05 柳州环山科技有限公司 一种农用浅松机
CN105349803A (zh) * 2015-10-22 2016-02-24 中南大学 一种从含钼的磷钨酸/磷钨酸盐溶液分离钨钼的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902917A (en) * 1970-06-04 1975-09-02 Bosch Gmbh Robert Process for the production of tungsten carbide catalyst adapted for use in fuel cells
CN1485450A (zh) * 2003-04-11 2004-03-31 自贡硬质合金有限责任公司 用钨合金废料生产超细晶粒碳化钨——铁系复合粉的方法
US7591984B2 (en) * 2003-07-28 2009-09-22 Los Alamos National Security, Llc Preparation of tungsten oxide
US20140014875A1 (en) * 2011-03-30 2014-01-16 Chonghu Wu Preparation method of industrial purple nano-needle tungsten oxide
CN104591740A (zh) * 2015-01-12 2015-05-06 吴江佳亿电子科技有限公司 一种耐冲击陶瓷材料及其制备方法
CN104818416A (zh) * 2015-05-07 2015-08-05 柳州环山科技有限公司 一种农用浅松机
CN105349803A (zh) * 2015-10-22 2016-02-24 中南大学 一种从含钼的磷钨酸/磷钨酸盐溶液分离钨钼的方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057882A (zh) * 2019-12-31 2020-04-24 厦门钨业股份有限公司 从镍钨基合金粉中回收钨的方法

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