CN101863472B - Method for recovering tungsten carbide from discarded hard alloy - Google Patents
Method for recovering tungsten carbide from discarded hard alloy Download PDFInfo
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- CN101863472B CN101863472B CN2010102100203A CN201010210020A CN101863472B CN 101863472 B CN101863472 B CN 101863472B CN 2010102100203 A CN2010102100203 A CN 2010102100203A CN 201010210020 A CN201010210020 A CN 201010210020A CN 101863472 B CN101863472 B CN 101863472B
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- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 230000002829 reductive effect Effects 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 238000007885 magnetic separation Methods 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 65
- 239000012074 organic phase Substances 0.000 claims description 50
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 34
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- 239000002253 acid Substances 0.000 claims description 8
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- 238000007789 sealing Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
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- 239000001301 oxygen Substances 0.000 claims description 7
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- 150000001412 amines Chemical class 0.000 claims description 4
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Abstract
The invention relates to a method for recovering tungsten carbide from discarded hard alloy. In the method, the discarded hard alloy is put into electrolyte and dissolved in the electrolyte, so that tungsten carbide granules are separated out, and then, preprocessing, i.e. magnetic separation and breaking, is carried out. The method is characterized in that the method also includes the following steps that: the preprocessed tungsten carbide is decarburized, dissolved in alkali, ammoniated, calcined, reduced and carburized, so that the tungsten carbide is produced. The method can produce recycled tungsten carbide powder with an excellent grain structure and less micro-inclusions, and meanwhile, the method has high recovery efficiency.
Description
Technical field
The present invention relates to a kind of recovery and utilization technology of waste metal product, more particularly, relate to a kind of method that reclaims wolfram varbide from discarded hard alloy.
Background technology
Along with the national economy high speed development; Departments such as the energy, machinofacture, traffic, geological prospecting, mine/oil production, construction and decoration come big more to the demand of high firmness instrument; Except artificially synthesizing diamond; Wimet has high temperature resistant, antioxidant, excellent specific property such as shock-resistant, corrosion-resistant because of it, and its consumption, output all grow at top speed.And wolfram varbide is an important source material of making wimet, is the wimet of main preparation high-voltage contact of can be used for making the miniature brill of producing surface-mounted integrated circuit, oil bit, machining tool, weapon component, diamond composition instrument, automatic watch pendulum, telecommunication ticker, aircraft balanced plate, anti-x ray, alpha-ray, gamma ray protecting sheet, electrical alloy or the like by wolfram varbide.And wherein; The tungsten that accounts for exhausted vast scale has played conclusive effect again: the hardness of tungsten itself is high; Ductility is strong, does not receive the erosion of air under the normal temperature, and fusing point becomes infusible metal about up to 3410 ℃; Because these characteristics that tungsten has, therefore become a kind of material of important and tool strategic importance day by day.Reality shows with trend prediction: the consumption of tungsten on the domestic and international market, price will day by day it rises, and only enough 50 years of its proven reserve estimation on earth.
Along with the rapid growth of wimet consumption, the quantity of discarded hard alloy product also increases considerably thereupon.In view of the resource of primary tungsten is deficient day by day, if can utilize again with the recovery of discarded hard alloy product and through after the manipulation of regeneration, no matter be from development and national economy, still from abundant efficent use of resources aspect, all have very significant meaning.
For this reason, generally take both at home and abroad to reclaim the approach that discarded hard alloy carries out manipulation of regeneration and solve the deficient day by day contradiction of tungsten resource.At present, reclaim the technology that discarded hard alloy carries out manipulation of regeneration both at home and abroad and mainly contain three kinds, be i.e. mechanical crushing method, the molten method of zinc and electrodissolution method:
Wherein comparatively traditional mechanical crushing method recovery processing technique is to adopt manual work and mechanical disintegration to combine; Put into hard alloy scraps the crusher of inwall embedding wimet liner plate and large size sintered carbide ball; Be ground into powder through rolling to grind with rolling impact; And then after wet-milling becomes compound, process hart metal product by common process at last.This method exists and is prone to sneak into other impurity in the material; The oxygen level of compound is higher, and the alloy quality product is had the shortcoming that has a strong impact on, and the normal temperature crushing efficiency is extremely low in addition; Generally need roll and grind about 500 hours; And the power consumption of high temperature, cryogenic pulverization is too high, and also the fineness of inaccessible requirement far can not reach the modern production standard-required.
The molten method of zinc is under 900 ℃ of left and right sides temperature, adds zinc and makes cobalt and zinc in the discarded hard alloy form the zinc cobalt-base alloy, dezincifies through vacuum distilling at a certain temperature and handles; Form spongy alloy block; Broken then, batching grinds to form raw material powder, produces hart metal product by common process at last.This method shortcoming exists facility investment big, and productive expense and energy consumption are high, and is difficult to thoroughly remove dezincify, causes quality product, unstable properties; Because used molten powder zinc has certain harm to environment, also there is problem of environmental pollution in addition.
The electrodissolution rule is to adopt suitable leaching liquid; Under electric field action, the cementing metal cobalt in the discarded hard alloy is dissolved in the leaching liquid; Reclaim cobalt powder and will after cleaning and crushing is ground, be obtained the tungsten-carbide powder of regenerating through electrochemical method, utilize the regenerated tungsten-carbide powder to process new hart metal product again by the waste alloy material piece of molten debanding agent.This method is because regenerate crystals of tungsten carbide process series of physical, chemical process; Crystal microscopic structure exists to be out of shape, to damage, is mingled with; Make the quality of the fresh tungsten carbide powder that the aspects such as crystalline-granular texture, purity of regeneration tungsten-carbide powder still can't obtain with primary tungsten ore production compare favourably, thereby have influence on the popularization of range of application with the wolfram varbide recovery industry of regeneration tungsten-carbide powder.
In addition, other reclaim the method for wolfram varbide raw material to also have some.But present traditional recovery method common shortcoming is that regeneration tungsten carbide crystal grain structure and size-grade distribution are unstable, purity is low.
On the other hand, existing industry is had higher requirement to the wolfram varbide quality, and the wimet of original micron order wolfram varbide preparation can not adapt to current requirement at physical and chemical indexs such as intensity, hardness; In the world; With the superfine tungsten carbide is the wimet that raw material is processed, and its hardness and intensity can significantly improve, and can overcome the contradiction that micron order carboloy intensity and hardness can not improve simultaneously fully; Superfine tungsten carbide is becoming the renewal substitute products of traditional micron order tungsten carbide powder; In the market, the price of high-performance superfine tungsten carbide is about the several times of common micron order tungsten carbide powder, and this situation has the aggravation Development Trend.
Hart metal product by the regeneration wolfram varbide of traditional method recovery is made is of poor quality, performance is low; So that the regeneration wolfram varbide that reclaims becomes the synonym of low-quality wolfram varbide; Can't be with comparing by the primary wolfram varbide of ore preparation; More can not adapt to the hart metal product quality and promote the needs that increase fast with market, in other words, the method for recycling discarded hard alloy has traditionally faced the prospect of dead end.
Summary of the invention
Above-mentioned shortcoming to prior art; The objective of the invention is to provide a kind of novel method from discarded hard alloy recovery high-quality wolfram varbide; This recovery method has following advantage: can make excellent grain structure, microcosmic is mingled with low regeneration tungsten-carbide powder; The regeneration tungsten-carbide powder performance mineral that can match in excellence or beauty make primary wolfram varbide, and have high recovery efficiency.
For this reason; Technical solution of the present invention is to place electrolytic solution to dissolve to separate through electricity discarded hard alloy to obtain the wolfram varbide pellet; Carry out magnetic separation, fragmentation then; The invention is characterized in, also comprise the steps: with the wolfram varbide after magnetic separation, the fragmentation more successively through decarburization, alkali dissolve, ammonification, calcining, reduction and carburization step make the high-quality wolfram varbide.
Described decarbonation process is carried out in kiln, makes the Tungsten oxide 99.999 pellet.Wherein, kiln temperature is controlled at 500～1600 ℃, maintains the circulation of air in the decarbonation process or feeds the oxygen of 0.5～1.0atm.
It is that the Tungsten oxide 99.999 pellet that makes is joined mass concentration is in 30%～50% the sodium hydroxide solution that described alkali dissolves step, and under 130～180 ℃ of liquid temperature, stirs, soaks and obtain coarse sodium tungstate, and precipitate and separate is removed Co simultaneously
2+, Ni
2+, Fe
2+, Mn
2+Deng foreign ion.
Described alkali dissolve and the ammonification step between also can further comprise following purification step: in coarse sodium tungstate, add acid solution and be acidified to certain pH value; Then add the organic phase that contains extraction agent and further separate foreign ions such as removing molybdenum, iron, zinc, calcium, aluminium, copper, thereby obtain highly purified sodium tungstate solution.Described organic extractant is P204 (two-(2-ethylhexyl) SULPHOSUCCINIC ACID ESTERs) or P507 (the own ester of 2-ethylhexyl phosphonic acid single 2-ethyl); Wherein, Saidly be acidified to certain pH value, be meant that the pH value of solution value is 1～4.5 when adopting the P204 extraction, the pH value of solution value more preferably 1～3.5 when adopting the P204 extraction; Extraction solution pH value is 1～6 when adopting P507.
Also can further remove the sodium ion in the solution to above-mentioned sodium tungstate solution: regulate earlier pH value to 2.5～3.0 of sodium tungstate solution, add then and contain TOA (positive trioctylamine) or the organic phase of TIOA (tri-iso-octylamine) or N235 (trialkylamine) extracts sodium tungstate solution, wherein; Liquid phase and organic phase volume ratio are 1: 1～2; Tungsten ion just is extracted to organic phase, and sodium ion is just still stayed liquid phase, separates liquid phase; Keep organic phase then, organic phase is carried out the processing of ammonification step.
Described ammonification step is in the tungstenic organic phase, to add ammoniacal liquor to stir, and evaporates then, concentrates, and obtains the crystallization of highly purified para-tungstic acid ammonia.
Described calcining step is the crystallization of para-tungstic acid ammonia to be calcined obtain the Tungsten oxide 99.999 powder, and wherein calcining temperature is 650～750 ℃.
Described reduction step is to adopt reductive agent to reduce in the Tungsten oxide 99.999 powder, obtains tungsten powder.
Said reductive agent be organic amine reductive agent, hydrogen, reduction carbon atmosphere wherein one or more.
Described carburization step is carried out in the sealing case hardening box, and the temperature of case hardening box is controlled at 650～1100 ℃, and carburizing time was controlled at 50～150 minutes.
Traditional technology is taked multiple tracks process step miscellaneous to handle and is reclaimed different, the assorted old discarded hard alloy product of component; Can know through analysis: the regeneration tungsten carbide powder grain that the multiple tracks process step of these traditional technologys obtains after separating, dispeling impurity; It is the crystals of tungsten carbide that has experienced varied processing course; Its common characteristic be to regenerate microcosmic crystal of wolfram varbide is succession body but not the new formation of discarded hard alloy product, and these wolfram varbides of inheriting bodies exist in the microcosmic crystal inevitably or the vestige between crystal pollutes, the vestige of crystalline-granular texture changes.Become for the micron order tungsten-carbide powder even this vestige pollutes, vestige is brilliant, also had influence on the quality of reconstituted product, and, just become flagrant defective more for the nano-stage tungsten carbide powder end of rising day by day.In addition, the wolfram varbide product of traditional technology acquisition tends to introduce new impurity (the molten method introducing of zinc Zn impurity; Mechanical process is introduced Fe impurity) or removal of impurities not thorough, this has also caused the quality of regeneration wolfram varbide can't reach the level of the wolfram varbide of primary ore preparation.To the above-mentioned shortcoming of traditional technology, method of the present invention adopts the electrodissolution method to obtain the wolfram varbide of preliminary purification, can reach and reclaim quality product effect relatively preferably; Under the high temperature aerobic conditions, carry out decarburization then to inheriting wolfram varbide; Crystal that make to inherit wolfram varbide disintegrates fully, new life becomes the Tungsten oxide 99.999 that state is given birth in the ore deposit, and then newborn Tungsten oxide 99.999 is carried out a series of processing such as decarburization, alkali are dissolved, ammonification, and final regeneration obtains the tungsten carbide powder that state is given birth in the ore deposit; Succession crystalline vestige pollutes and vestige is brilliant becomes because the finished product of technology of the present invention have been eliminated; It is low that thereby the excellent grain structure, the microcosmic that have guaranteed the regeneration wolfram varbide are mingled with, and makes the primary wolfram varbide that can match in excellence or beauty regeneration tungsten-carbide powder performance mineral make, and; The combination of process steps of technology of the present invention is reasonable, therefore has high recovery efficiency.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 2 recovery methods.
Fig. 2 is that traditional electrical is dissolved process flow sheet.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
The present invention comprises the steps: from the method embodiment that discarded hard alloy reclaims wolfram varbide
An amount of discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 1000 ℃; And maintain the circulation of air and carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 35% mass concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 160 ℃, alkali dissolved 4 to 6 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～3.5; Then the P204 that adds by 20% (volume(tric)fraction) further extracts impurity such as separating removal molybdenum, iron, zinc, calcium, aluminium, copper one by one with the organic phase that 80% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 2.5 earlier; Then add the organic phase of being made up of 10%TOA (positive trioctylamine) and 90% kerosene sodium tungstate solution is extracted, wherein, liquid phase and organic phase volume ratio are 1; Tungsten ion just is extracted to organic phase; Sodium ion is just still stayed liquid phase, separates liquid phase, keeps organic phase then.Then organic phase is added ammoniacal liquor and stir, evaporate, concentrate, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt the organic amine reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 1000 ℃, and carburizing time was controlled at 100 minutes, finally made the high-quality tungsten-carbide powder.
Through experimental test, the physicochemical property of this high-quality tungsten-carbide powder such as following table:
The mass percent of each this substances content of numeric representation in the form; Like the quality percentage composition of Co 0.008 expression Co in products obtained therefrom is 0.008%; By visible in the table; The tungsten-carbide powder that technology of the present invention makes, its excellent grain structure, microcosmic are mingled with low, and tungsten-carbide powder performance and primary tungsten-carbide powder performance can match in excellence or beauty.
Embodiment 2
Contrast for ease, Figure of description of the present invention provide process flow sheet and traditional electrical of the present invention to dissolve process flow sheet.Fig. 1 is the process flow sheet of the embodiment of the invention 2 recovery methods, and Fig. 2 is that traditional electrical is dissolved process flow sheet.
The discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 800 ℃; And maintain the circulation of air and carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 30% concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 180 ℃, alkali dissolved 5 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～3; Then the P204 that adds by 20% (volume(tric)fraction) further separates impurity such as removing molybdenum, iron, zinc, calcium, aluminium, copper with the organic phase that 80% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 3.0 earlier; Then add the organic phase of being made up of 10%TOA and 90% kerosene sodium tungstate solution is extracted, wherein, liquid phase and organic phase volume ratio are 1; Tungsten ion just is extracted to organic phase; Sodium ion is just still stayed liquid phase, separates liquid phase, keeps organic phase then.Then organic phase is added ammoniacal liquor and stir, evaporate, concentrate, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt hydrogen to make reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 850 ℃, and carburizing time was controlled at 120 minutes, finally made the high-quality tungsten-carbide powder.
The process experimental test: the physicochemical property of this high-quality tungsten-carbide powder is tabulated as follows:
The mass percent of each this substances content of numeric representation in the form is 0.009% like the quality percentage composition of Co 0.009 expression Co in products obtained therefrom.By visible in the table, the tungsten-carbide powder that technology of the present invention makes, its excellent grain structure, microcosmic are mingled with low, and tungsten-carbide powder performance and primary tungsten-carbide powder performance can match in excellence or beauty.
Embodiment 3
The discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 1600 ℃; And keep the oxygen of feeding 0.5atm to carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 50% concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 180 ℃, alkali dissolved 6 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～6; Then the P507 that adds by 25% (volume(tric)fraction) further separates impurity such as removing molybdenum, iron, zinc, calcium, copper, magnesium with the organic phase that 75% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 2.9 earlier; Then add the organic phase of being made up of 10%N235 and 90% kerosene sodium tungstate solution is extracted, wherein, liquid phase and organic phase volume ratio are 1: 1.5; Tungsten ion just is extracted to organic phase; Sodium ion is just still stayed liquid phase, separates liquid phase, keeps organic phase then.Then organic phase is added ammoniacal liquor, evaporation, concentrates, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt reduction carbon to make reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 1100 ℃, and carburizing time was controlled at 60 minutes, finally made the high-quality tungsten-carbide powder.
Process experimental test: the physicochemical property of this high-quality tungsten-carbide powder such as following table:
The mass percent of each this substances content of numeric representation in the form is 0.009% like the quality percentage composition of Co 0.009 expression Co in products obtained therefrom.By visible in the table, the tungsten-carbide powder that technology of the present invention makes, its excellent grain structure, microcosmic are mingled with low, and tungsten-carbide powder performance and primary tungsten-carbide powder performance can match in excellence or beauty.
Can know from the detected result of top embodiment; Compare with the electrodissolution method with existing mechanical crush method, the molten method of zinc; The various impurity that method of the present invention is removed are more, and the wolfram varbide purity that purification is come out is higher, and the performance also wolfram varbide performance with the primary ore preparation is suitable; The wolfram varbide of complete alternative primary ore preparation uses, and the saving of resource is had very important significance.
Embodiment 4
The discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 1000 ℃; And keep the oxygen of feeding 0.8atm to carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 40% mass concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 150 ℃, alkali dissolved 4 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～4.5; Then the P204 that is added with by 25% (volume(tric)fraction) further separates impurity such as removing molybdenum, iron, zinc, calcium, aluminium, copper with the organic phase that 75% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 2.8 earlier, then adds the organic phase of being made up of 10%TOA and 90% kerosene sodium tungstate solution is extracted, wherein; Liquid phase and organic phase volume ratio are 1: 2, and tungsten ion just is extracted to organic phase, and sodium ion is just still stayed liquid phase; Separate liquid phase; Keep organic phase then, then organic phase is added ammoniacal liquor and stir, evaporate, concentrate, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt organic amine as reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 900 ℃, and carburizing time was controlled at 110 minutes, finally made the high-quality tungsten-carbide powder.
Through detecting, the tungsten-carbide powder of present embodiment gained, each physicochemical property reach the specification of quality of the tungsten-carbide powder of primary ore preparation preferably.
Embodiment 5
The discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 500 ℃; And keep the oxygen of logical 1.0atm to carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 35% mass concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 130 ℃, alkali dissolved 4 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～3.5; Then the P204 that adds by 25% (volume(tric)fraction) further separates impurity such as removing molybdenum, iron, zinc, calcium, aluminium, copper with the organic phase that 75% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 2.7 earlier, then adds the organic phase of being made up of 10%TIOA and 90% kerosene sodium tungstate solution is extracted, wherein; Liquid phase and organic phase volume ratio are 1, and tungsten ion just is extracted to organic phase, and sodium ion is just still stayed liquid phase; Separate liquid phase; Keep organic phase then, then organic phase is added ammoniacal liquor and stir, evaporate, concentrate, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt reduction carbon as reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 650 ℃, and carburizing time was controlled at 150 minutes, finally made the high-quality tungsten-carbide powder.
Through detection, the tungsten-carbide powder of present embodiment gained, the tungsten-carbide powder of each physicochemical property and primary ore preparation is suitable.
Embodiment 6
The discarded hard alloy piece dissolved through electricity obtain the wolfram varbide pellet; Magnetic separation again, the broken tungsten carbide powder that obtains preliminary purification place kiln with tungsten carbide powder, and kiln temperature is set to 1200 ℃; And keep the oxygen of feeding 0.5atm to carry out high temperature oxidation, thereby obtain the Tungsten oxide 99.999 pellet.Adopt the sodium hydroxide solution of 45% mass concentration to soak the Tungsten oxide 99.999 pellet of gained then, and control the liquid temperature and also stir at 160 ℃, alkali dissolved 6 hours, obtained containing soluble tungsten ionic coarse sodium tungstate (Na
2WO
4) solution, and the alkali process of dissolving makes foreign ion generation hydrations depositions such as remaining Co, Ni, Fe, its reaction formula is:
FeWO
4+2NaOH→Na
2WO
4+Fe(OH)
2↓，
MnWO
4+2NaOH→Na
2WO
4+Mn(OH)
2↓，
Ni
2++2NaOH→Ni(OH)
2↓+2Na
+，
Co
3++3NaOH→Co(OH)
3↓+3Na
+…。
The throw out that separates in the alkaline solution is made subsequent disposal in addition.In through the coarse sodium tungstate after the precipitate and separate; Add acid solution and carry out acidifying; The pH value is adjusted to 1～4.5; Then the P204 that adds by 25% (volume(tric)fraction) further separates impurity such as removing molybdenum, iron, zinc, calcium, aluminium, copper with the organic phase that 75% sulfonated kerosene is formed, thereby obtains highly purified sodium tungstate solution.Remove the sodium ion in the solution then: the pH value with sodium tungstate solution is adjusted to 2.6 earlier, then adds the organic phase of being made up of 10%N235 and 90% kerosene sodium tungstate solution is extracted, wherein; Liquid phase and organic phase volume ratio are 1, and tungsten ion just is extracted to organic phase, and sodium ion is just still stayed liquid phase; Separate liquid phase; Keep organic phase then, then organic phase is added ammoniacal liquor and stir, evaporate, concentrate, obtain the crystallization of highly purified para-tungstic acid ammonia.Method for calcinating is adopted in para-tungstic acid ammonia crystallization to obtaining, obtains the Tungsten oxide 99.999 powder; Adopt acetylene as reductive agent, gained Tungsten oxide 99.999 powder is reduced, make metal tungsten powder; Place the sealing case hardening box to carry out carburizing treatment the metal tungsten powder that obtains at last, the temperature of case hardening box is controlled at 900 ℃, and carburizing time was controlled at 110 minutes, finally made the high-quality tungsten-carbide powder.
Through detecting, the tungsten-carbide powder of present embodiment gained, each physicochemical property are also suitable with primary tungsten-carbide powder.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. method that reclaims wolfram varbide from discarded hard alloy; This method is to place electrolytic solution to dissolve to separate through electricity discarded hard alloy to obtain the wolfram varbide pellet; Carry out magnetic separation, broken pre-treatment then; It is characterized in that, also comprise the steps: with pretreated wolfram varbide again through decarburization, alkali dissolve, ammonification, calcining, reduction and carburization step make wolfram varbide;
Wherein, described decarbonation process is carried out in kiln, makes the Tungsten oxide 99.999 pellet, and wherein, kiln temperature is controlled at 500～1600 ℃, and decarbonation process maintains the circulation of air or feeds the oxygen of 0.5～1.Oatm;
It is that the Tungsten oxide 99.999 pellet that makes in the decarbonation process is joined mass concentration is in 30%～50% the sodium hydroxide solution that described alkali dissolves step, and under 130～180 ℃ of liquid temperature, stirs, soaks and obtain coarse sodium tungstate, and precipitate and separate is removed Co simultaneously
2+, Ni
2+, Fe
2+, Mn
2+Deng foreign ion;
Alkali dissolve and the ammonification step between also comprise following purification step: after the precipitate and separate; In coarse sodium tungstate, add acid solution and be acidified to certain pH value; Then add the further extracting and separating of organic phase that contains extraction agent and remove impurity such as molybdenum, iron, zinc, calcium, aluminium, copper, thereby obtain highly purified sodium tungstate solution; And then to sodium tungstate solution further extraction remove the sodium ion in the solution, obtain the tungstenic organic phase;
Described ammonification step is in the tungstenic organic phase, to add ammoniacal liquor to stir, and evaporates then, concentrates, and obtains the crystallization of highly purified para-tungstic acid ammonia.
2. as claimed in claim 1ly a kind ofly reclaim the method for wolfram varbide from discarded hard alloy, it is characterized in that: described extraction agent is P204 or P507, saidly is acidified to certain pH value, is meant that the pH value of solution value is 1～4.5 when adopting P204 to extract; The pH value of solution value is 1～6 when adopting the P507 extraction.
3. a kind of method from discarded hard alloy recovery wolfram varbide as claimed in claim 2, it is characterized in that: the pH value of solution value is 1～3.5 when adopting the P204 extraction.
4. a kind of method that reclaims wolfram varbide from discarded hard alloy as claimed in claim 1; It is characterized in that: when the sodium ion in the solution is removed in further extraction to the sodium tungstate solution of gained, regulate pH value to 2.5～3.0 of sodium tungstate solution earlier, add the organic phase that contains TOA or TIOA or N235 then sodium tungstate solution is extracted; Wherein, Liquid phase and organic phase volume ratio are 1: 1～2, and tungsten ion just is extracted to organic phase, and sodium ion is just still stayed liquid phase; Separate liquid phase, keep organic phase then as the follow-up object that adds ammonia treating step.
5. a kind of method from discarded hard alloy recovery wolfram varbide as claimed in claim 1, it is characterized in that: described calcining step is the crystallization of para-tungstic acid ammonia to be calcined obtain the Tungsten oxide 99.999 powder, and wherein calcining temperature is 650～750 ℃.
6. like the described a kind of method that reclaims wolfram varbide from discarded hard alloy of the arbitrary claim of claim 1～5; It is characterized in that: described reduction step; Be to adopt reductive agent to reduce in the Tungsten oxide 99.999 powder; Obtain tungsten powder, said reductive agent be organic amine reductive agent, hydrogen, reduction carbon atmosphere wherein one or more.
7. like the described a kind of method that reclaims wolfram varbide from discarded hard alloy of the arbitrary claim of claim 1～5; It is characterized in that: described carburization step is carried out in the sealing case hardening box; The temperature of case hardening box is controlled at 650～1100 ℃, and carburizing time was controlled at 50～150 minutes.
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| CN102126025B (en) * | 2011-02-22 | 2012-12-05 | 中南大学 | Process for preparing surface decarbonized WC-Co gradient hard alloy preform |
| CN102329970B (en) * | 2011-08-31 | 2013-03-27 | 湖南力天世纪矿业有限公司 | Method for producing ferrotungsten with tungsten carbide obtained by tungsten-containing waste processing as raw material |
| WO2016158878A1 (en) * | 2015-03-31 | 2016-10-06 | Ｊｘ金属株式会社 | Tungsten carbide production method |
| US10940538B2 (en) * | 2017-08-11 | 2021-03-09 | Kennametal Inc. | Grade powders and sintered cemented carbide compositions |
| CN112209446B (en) * | 2020-09-04 | 2023-05-23 | 崇义章源钨业股份有限公司 | Method for recycling Cr-containing tungsten carbide waste and application thereof |
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|---|---|---|---|---|
| GB1329580A (en) * | 1970-12-23 | 1973-09-12 | Wickman Wimet Ltd | Tungsten carbide |
| US5384016A (en) * | 1993-11-10 | 1995-01-24 | National Science Council | Process for recovering tungsten carbide from cemented tungsten carbide scraps by selective electrolysis |
| CN1326424A (en) * | 1998-11-13 | 2001-12-12 | H·C·施塔克公司 | Method for producing wolfram carbides by gas-phase carburetion |
| EP1842589A1 (en) * | 2006-04-04 | 2007-10-10 | Postech Foundation | Nanoporous tungsten carbide catalyst and preparation method thereof |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1329580A (en) * | 1970-12-23 | 1973-09-12 | Wickman Wimet Ltd | Tungsten carbide |
| US5384016A (en) * | 1993-11-10 | 1995-01-24 | National Science Council | Process for recovering tungsten carbide from cemented tungsten carbide scraps by selective electrolysis |
| CN1326424A (en) * | 1998-11-13 | 2001-12-12 | H·C·施塔克公司 | Method for producing wolfram carbides by gas-phase carburetion |
| EP1842589A1 (en) * | 2006-04-04 | 2007-10-10 | Postech Foundation | Nanoporous tungsten carbide catalyst and preparation method thereof |
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