CN1827806A - Method for extracting tungsten and other rare metals from waste hard alloy - Google Patents
Method for extracting tungsten and other rare metals from waste hard alloy Download PDFInfo
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- CN1827806A CN1827806A CNA2006100125727A CN200610012572A CN1827806A CN 1827806 A CN1827806 A CN 1827806A CN A2006100125727 A CNA2006100125727 A CN A2006100125727A CN 200610012572 A CN200610012572 A CN 200610012572A CN 1827806 A CN1827806 A CN 1827806A
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Abstract
The invention relates the method of extracting tungsten and other rare metals from waste and old carbide alloy, belonging to waste and old carbide alloy reclamation and utilization technology field. The method comprises the following steps: melting the waste and old carbide alloy with sodium acid carbonate or sodium carbonate in water, forming ammonium tungstate solution and precipitum containing other rare metals, separating them, heating the tungstate solution, then crystallization, drying, calcining, and adding hydrogen gas to deacidize, get tungsten powder; and mixing the precipitum with sulfuric acid and ammonium oxalate to extract cobalt powder, nickel powder, tantalum and niobium. The method has the advantages of low cost and great economy value.
Description
Technical field
The invention belongs to the recycling technical field of scrap hard alloy, relate in particular to a kind of method of from scrap hard alloy, extracting tungsten and other rare metals.
Background technology
Along with rapid development of economy, industries such as machinofacture, geology and mine, building, electronics and chemical industry are to Wimet, and particularly the demand of tungsten material is increasing.And the various metallic elements that constitute Hardmetal materials nearly all are rare elements, and contain a large amount of tungstens.Under the situation that storage capacity is fewer and feweri in the ore deposit of rare metals such as tungsten, exploitation is also more and more difficult, the approach that extracts tungsten and other rare metals from scrap hard alloy more and more seems important.
At present, the utilization again of scrap hard alloy is meant the powder that forms after the scrap hard alloy that will reclaim is by classification, fragmentation, ball milling, electrolysis, after chemically examining, add required metallic element according to needs, repressed again moulding and sintering are finished the regeneration of Wimet.
As the patent No. be 98112022.9, Granted publication number is the patent of CN1064716C, the technology that disclosed " scrap hard alloy reclaim and regeneration treating method " adopted is: waste alloy is directly strengthened after just broken wet-milling fragmentation, drying, then send into calcining furnace through pyroprocessing to remove the excessive levels of impurities in the powder, again behind analysis of components as raw material powder, the production technique of Wimet is made alloy product routinely.
And for example number of patent application is 200310104868.8, publication number is the patent application of CN1609279A, the technology that disclosed " scrap hard alloy is produced the method for hard metal article powder stock " adopted is: give up back Wimet classification, the cleaning that will reclaim, the dynamic electrolytic electromechanics of directly packing into is separated processing, separates and makes powdered alloy.
Utilize foregoing invention or technology that application for a patent for invention provided, extract the rare metal in the Wimet, because will be through Wimet being carried out fragmentation, utilizing the technologies such as powder, calcined oxide, extraction or process electrolysis that ball mill is processed into more than 300 orders various METAL EXTRACTION in the Wimet could to be gone out, therefore, these processing methodes all exist the defective of complete processing complexity, energy consumption height (the tungsten extraction cost is about 20,000 yuan/ton):
The content of invention
Purpose of the present invention just provides that a kind of technology is simple, energy consumption is low, and the various rare metals in the scrap hard alloy especially tungsten can be extracted, can directly utilize the directly synthetic method of from scrap hard alloy, extracting tungsten and other rare metals that reaches the Wimet of standard of various rare metal powder that this extracted.
Realize that the technical scheme that above-mentioned purpose of the present invention adopted is:
From scrap hard alloy, extract the method for tungsten and other rare metals, comprise the following steps:
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and adds sodium bicarbonate or yellow soda ash is heated to 800---1200 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, is generated the reaction solution and the throw out that contain sodium wolframate, after filtration the two is separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
Get described sodium tungstate solution, generate ammonium tungstate solution, make the ammonium tungstate crystallization separate out this solution heating evaporation, it oven dry calcining is formed Tungsten oxide 99.999, add hydrogen reducing again and become metal tungsten powder through extraction and the back extraction of adding ammoniacal liquor;
In the 4th step, utilize described solids to extract other metals
Getting described solids and joining concentration is 10---the reaction of 30% hydrochloric acid soln, generate throw out, after filtration with liquid object and precipitate and separate and handle:
---get liquid object, behind the removal iron contamination, will contain cobalt liquid and nickeliferous liquid separation through extraction process; After in containing cobalt liquid and nickeliferous liquid, adding ammonium oxalate solution reaction respectively, and respectively through precipitate, filter, evaporate, dry cobalt oxalate and nickelous oxalate solids, again it is reduced into cobalt powder and nickel powder;
---get precipitation, it is carried out the igneous fusion second time again after, be presented in the water and dissolve, through extraction process metal tantalum and metal niobium are extracted respectively.
In addition:
Described through extraction with add the extraction conditions that the ammoniacal liquor back extraction generates in the ammonium tungstate solution operation and be: extraction liquid is that 260# solvent oil, the reverse-extraction agent of secondary octanol+80% of 10% N235+10% is ammoniacal liquor;
When utilizing obtained sodium tungstate solution to extract tungsten, at first, promptly in this solution, add sulfuric acid, the pH value to 2.0 of regulator solution to described sodium tungstate solution removal of impurities---3.5, make silicon ion generate the water glass precipitation;
Pour the hard metal mixtures of described fusing into the back forms in the water throw out and carry out wet-milling;
When utilizing obtained sodium tungstate solution to extract tungsten, the temperature of described ammonium tungstate solution heating evaporation is 80---95 ℃, the time is 3---8 hours;
When utilizing obtained sodium tungstate solution to extract tungsten, be 80 with the temperature of the ammonium tungstate crystallization oven dry of heating evaporation gained---104 ℃, time be 4---7 hours;
When utilizing described solids to extract other metals, described incinerating temperature is 700---750 ℃, the required incinerating time is 1.5---and 3 hours;
When utilizing described solids to extract other metals, with the described employed extraction liquid of extraction process that contains cobalt liquid and nickeliferous liquid separation by 1:0.8---1.2 20% P507 and 80% 260# solvent oil constitute;
Use is by 1:0.8---temperature of the extraction liquid extraction that 1.2 20% P507 and 80% 260# solvent oil constitute is 40---50 ℃;
When utilizing described solids to extract other metals,---12% hydrofluoric acid, 7---15% secondary octanol and 60---, 90% kerosene constitutes by 8 with described metal tantalum and the employed extraction liquid of the isolating extraction process of metal niobium.
The processing method of extracting tungsten and other rare metals from scrap hard alloy provided by the present invention compared with prior art, have the following advantages: one, because this technology is directly scrap hard alloy to be inserted the smelting of heating in the smelting furnace, again the Wimet under the molten state directly is prepared into the aqueous solution, carry out the extraction of tungsten, saved fragmentation of the prior art, utilize ball mill to be processed into the above powder of 300 orders and the operation of calcined oxide, therefore has the technology characteristic of simple, the more important thing is that the cost that utilizes this technology to extract tungsten and other rare metals reduces by 50% (reducing to below 10000 yuan/ton) at least; They are two years old, utilize this technology that the various element extraction in the scrap hard alloy are come out, make new Wimet more on request, be easy to reach the specification of quality of product, therefore, improve the utility value of scrap hard alloy, the various rare metals that are contained in the Wimet have been separated purify, increased the approach that utilizes.
Embodiment
Below in conjunction with the embodiments the processing method of extracting tungsten and other rare metals from scrap hard alloy provided by the present invention being described in further detail:
Embodiment 1
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and the adding sodium bicarbonate is heated to 800 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, generation contains the reaction solution of sodium wolframate and contains the throw out of multiple metals such as cobalt, nickel, titanium, tantalum, with this throw out through the wet-milling operation, make tungsten can fully react the formation sodium wolframate, after filtration the two be separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
1, the sodium tungstate solution to gained carries out removal of impurities
Get the sodium tungstate solution of gained, the limit adds the stirring of vitriol oil limit therein, makes the pH value of solution adjust to 2.0, forms water glass jelly precipitation, and removes this precipitation to such an extent that be sodium tungstate solution;
2, adding through over-richness in 1: 1 ratio in the sodium tungstate solution of having removed silicon ion is that the extraction liquid (during extraction, the concentration of feed liquid is for containing Tungsten oxide 99.999 400 grams per liters) that the 260# solvent oil by secondary octanol+80% of 10% N235+10% of 0.5mol/L vitriolization constitutes reacts the generation sodium salt; Ratio in 2: 1 in the sodium salt liquid that has extracted adds the ammoniacal liquor reaction that concentration is 3.5mol/L, generates secondary tungsten acid ammonium solution;
To be heated to 90 ℃ in this solution, kept 5 hours, evaporation makes ammonium para-tungstate crystal separate out;
3, taking out this crystallization is 7 hours with it drying time under 80 ℃ of temperature, gets the ammonium paratungstate powder;
4, getting above-mentioned ammonium paratungstate powder is 600 ℃ through excess temperature once more, and the time is that 3 hours calcining forms Tungsten oxide 99.999;
5, will calcine the Tungsten oxide 99.999 that forms is presented to and feeds hydrogen reducing in the reduction furnace and promptly get metal tungsten powder.
In the 4th step, utilize solids obtained in the first step to extract other metals
1, gets solids and to join concentration be to be heated to 250 ℃ of reactions in 10% the hydrochloric acid soln, generate and contain the solution of cobalt, nickel and contain tantalum and the throw out bits of niobium, after filtration cobalt, nickel solution thing and precipitation bits are separated;
2, getting the solution that contains cobalt, nickel, is that 30% hydrogen peroxide adds wherein fully reaction with concentration, adds the PH to 4.0 of ammoniacal liquor conditioned reaction liquid again, and reaction forms ferric hydroxide precipitate, has removed iron contamination.Constitute extraction liquid with 1: 0.8 20% P507 and 80% 260# solvent oil after the deironing,, under 40 ℃ of temperature, will contain cobalt liquid and nickeliferous liquid separation through extraction process in putting into wherein with 1: 1 ratio of reaction solution; In containing cobalt liquid and nickeliferous liquid, add the ammonium oxalate solution reaction respectively and generate cobalt oxalate and nickelous oxalate feed liquid, and get cobalt oxalate and nickelous oxalate solids through precipitation, filtration, sedimentary evaporation and baking operation respectively, by hydrogen it is reduced into cobalt powder and nickel powder through reduction furnace again;
3, get the precipitation bits, it is calcined under 600 ℃ of temperature about 3 hours after the fusion again, be presented in the water and dissolve, the extraction liquid extraction that the hydrofluoric acid via 8%, 15% secondary octanol and 60% kerosene constitute is with the solution separating of metal tantalum and metal niobium; Solution after separating is extracted metal tantalum and metal niobium through crystallization and cooling baking operation.
By above operation, can from scrap hard alloy, propose containing tungsten, cobalt, nickel, tantalum, niobium, make full use of again.
Embodiment 2
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and adding yellow soda ash is heated to 1200 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, is generated reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum, after filtration the two is separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
1, the sodium tungstate solution to gained carries out removal of impurities
Get the sodium tungstate solution of gained, the limit adds the stirring of vitriol oil limit therein, makes the pH value of solution adjust to 3.5, form water glass jelly precipitation, through the wet-milling operation, make tungsten can fully react the formation sodium wolframate this throw out, and will precipitate and remove to such an extent that be sodium tungstate solution;
2, adding through over-richness in 1: 0.8 ratio in the sodium tungstate solution of having removed silicon ion is that the extraction liquid (during extraction, the concentration of feed liquid is for containing Tungsten oxide 99.999 350 grams per liters) that the 260# solvent oil by secondary octanol+60% of 15% N235+25% of 0.4mol/L vitriolization constitutes reacts the generation sodium salt; Ratio in 1.5: 1 in the sodium salt liquid that has extracted adds the ammoniacal liquor reaction that concentration is 3.5mol/L, generates secondary tungsten acid ammonium solution;
To be heated to 80 ℃ in this solution, kept 8 hours, evaporation makes ammonium para-tungstate crystal separate out;
3, taking out this crystallization is 5 hours with it drying time under 100 ℃ of temperature, gets the ammonium paratungstate powder;
4, getting above-mentioned ammonium paratungstate powder is 700 ℃ through excess temperature once more, and the time is that 2 hours calcining forms Tungsten oxide 99.999;
5, will calcine the Tungsten oxide 99.999 that forms is presented to and feeds hydrogen reducing in the reduction furnace and promptly get metal tungsten powder.
In the 4th step, utilize solids obtained in the first step to extract other metals
1, gets solids and to join concentration be to be heated to 150 ℃ of reactions in 20% the hydrochloric acid soln, generate and contain the solution of cobalt, nickel and contain tantalum and the throw out bits of niobium, after filtration cobalt, nickel solution thing and precipitation bits are separated;
2, getting the solution that contains cobalt, nickel, is that 25% hydrogen peroxide adds wherein fully reaction with concentration, adds the PH to 5.0 of ammoniacal liquor conditioned reaction liquid again, and reaction forms ferric hydroxide precipitate, has removed iron contamination.Constitute extraction liquid with 1: 1 20% P507 and 80% 260# solvent oil after the deironing,, under 45 ℃ of temperature, will contain cobalt liquid and nickeliferous liquid separation through extraction process in putting into wherein with 1: 1 ratio of reaction solution; In containing cobalt liquid and nickeliferous liquid, add the ammonium oxalate solution reaction respectively and generate cobalt oxalate and nickelous oxalate feed liquid, and get cobalt oxalate and nickelous oxalate solids through precipitation, filtration, sedimentary evaporation and baking operation respectively, by hydrogen it is reduced into cobalt powder and nickel powder through reduction furnace again;
3, get the precipitation bits, it again after calcining fusion in 2.5 hours under 700 ℃ of temperature, is presented in the water and dissolves, the extraction liquid extraction that the hydrofluoric acid via 10%, 10% secondary octanol and 80% kerosene constitute is with the solution separating of metal tantalum and metal niobium; Solution after separating is extracted metal tantalum and metal niobium through crystallization and cooling baking operation.
By above operation, will contain tungsten, cobalt, nickel, tantalum, niobium and from scrap hard alloy, propose, make full use of again.
Embodiment 3
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and the adding sodium bicarbonate is heated to 1000 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, generation contains the reaction solution of sodium wolframate and contains the throw out of multiple metals such as cobalt, nickel, titanium, tantalum, with this throw out through the wet-milling operation, make tungsten can fully react the formation sodium wolframate, after filtration the two be separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
1, the sodium tungstate solution to gained carries out removal of impurities
Get the sodium tungstate solution of gained, the limit adds the stirring of vitriol oil limit therein, makes the pH value of solution adjust to 3.0, forms water glass jelly precipitation, and removes this precipitation to such an extent that be sodium tungstate solution;
2, adding through over-richness in 1: 0.9 ratio in the sodium tungstate solution of having removed silicon ion is that the extraction liquid (during extraction, the concentration of feed liquid is for containing Tungsten oxide 99.999 300 grams per liters) that the 260# solvent oil by secondary octanol+70% of 20% N235+10% of 0.6mol/L vitriolization constitutes reacts the generation sodium salt; Ratio in 2.5: 1 in the sodium salt liquid that has extracted adds the ammoniacal liquor reaction that concentration is 4.0mol/L, generates secondary tungsten acid ammonium solution;
To be heated to 95 ℃ in this solution, kept 3 hours, evaporation makes ammonium para-tungstate crystal separate out;
3, taking out this crystallization is 4 hours with it drying time under 110 ℃ of temperature, gets the ammonium paratungstate powder;
4, getting above-mentioned ammonium paratungstate powder is 750 ℃ through excess temperature once more, and the time is that 1.5 hours calcining forms Tungsten oxide 99.999;
5, will calcine the Tungsten oxide 99.999 that forms is presented to and feeds hydrogen reducing in the reduction furnace and promptly get metal tungsten powder.
In the 4th step, utilize solids obtained in the first step to extract other metals
1, gets solids and to join concentration be to be heated to 100 ℃ of reactions in 30% the hydrochloric acid soln, generate and contain the solution of cobalt, nickel and contain tantalum and the throw out bits of niobium, after filtration cobalt, nickel solution thing and precipitation bits are separated;
2, getting the solution that contains cobalt, nickel, is that 20% hydrogen peroxide adds wherein fully reaction with concentration, adds the PH to 5.5 of ammoniacal liquor conditioned reaction liquid again, and reaction forms ferric hydroxide precipitate, has removed iron contamination.Constitute extraction liquid with 1: 1.2 20% P507 and 80% 260# solvent oil after the deironing,, under 50 ℃ of temperature, will contain cobalt liquid and nickeliferous liquid separation through extraction process in putting into wherein with 1: 1 ratio of reaction solution; In containing cobalt liquid and nickeliferous liquid, add the ammonium oxalate solution reaction respectively and generate cobalt oxalate and nickelous oxalate feed liquid, and get cobalt oxalate and nickelous oxalate solids through precipitation, filtration, sedimentary evaporation and baking operation respectively, by hydrogen it is reduced into cobalt powder and nickel powder through reduction furnace again;
3, get the precipitation bits, it again after calcining fusion in 2 hours under 750 ℃ of temperature, is presented in the water and dissolves, the extraction liquid extraction that the hydrofluoric acid via 12%, 7% secondary octanol and 90% kerosene constitute is with the solution separating of metal tantalum and metal niobium; Solution after separating is extracted metal tantalum and metal niobium through crystallization and cooling baking operation.
Embodiment 4
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and adding yellow soda ash is heated to 900 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, generation contains the reaction solution of sodium wolframate and contains the throw out of multiple metals such as cobalt, nickel, titanium, tantalum, with this throw out through the wet-milling operation, make tungsten can fully react the formation sodium wolframate, after filtration the two be separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
1, the sodium tungstate solution to gained carries out removal of impurities
Get the sodium tungstate solution of gained, the limit adds the stirring of vitriol oil limit therein, makes the pH value of solution adjust to 3.5, forms water glass jelly precipitation, and removes this precipitation to such an extent that be sodium tungstate solution;
2, adding through over-richness in 1: 1.1 ratio in the sodium tungstate solution of having removed silicon ion is that the extraction liquid (during extraction, the concentration of feed liquid is for containing Tungsten oxide 99.999 200 grams per liters) that the 260# solvent oil by secondary octanol+75% of 10% N235+15% of 0.5mol/L vitriolization constitutes reacts the generation sodium salt; Ratio in 2: 1 in the sodium salt liquid that has extracted adds the ammoniacal liquor reaction that concentration is 3.7mol/L, generates secondary tungsten acid ammonium solution;
To be heated to 85 ℃ in this solution, kept 6 hours, evaporation makes ammonium para-tungstate crystal separate out;
3, taking out this crystallization is 6 hours with it drying time under 90 ℃ of temperature, gets the ammonium paratungstate powder;
4, getting above-mentioned ammonium paratungstate powder is 650 ℃ through excess temperature once more, and the time is that 2.5 hours calcining forms Tungsten oxide 99.999;
5, will calcine the Tungsten oxide 99.999 that forms is presented to and feeds hydrogen reducing in the reduction furnace and promptly get metal tungsten powder.
In the 4th step, utilize solids obtained in the first step to extract other metals
1, gets solids and to join concentration be to be heated to 200 ℃ of reactions in 15% the hydrochloric acid soln, generate and contain the solution of cobalt, nickel and contain tantalum and the throw out bits of niobium, after filtration cobalt, nickel solution thing and precipitation bits are separated;
2, getting the solution that contains cobalt, nickel, is that 22% hydrogen peroxide adds wherein fully reaction with concentration, adds the PH to 4.5 of ammoniacal liquor conditioned reaction liquid again, and reaction forms ferric hydroxide precipitate, has removed iron contamination.Constitute extraction liquid with 1: 0.9 20% P507 and 80% 260# solvent oil after the deironing,, under 43 ℃ of temperature, will contain cobalt liquid and nickeliferous liquid separation through extraction process in putting into wherein with 1: 1 ratio of reaction solution; In containing cobalt liquid and nickeliferous liquid, add the ammonium oxalate solution reaction respectively and generate cobalt oxalate and nickelous oxalate feed liquid, and get cobalt oxalate and nickelous oxalate solids through precipitation, filtration, sedimentary evaporation and baking operation respectively, by hydrogen it is reduced into cobalt powder and nickel powder through reduction furnace again;
3, get the precipitation bits, it is calcined under 650 ℃ of temperature about 2.5 hours after the fusion again, be presented in the water and dissolve, the extraction liquid extraction that the hydrofluoric acid via 9%, 12% secondary octanol and 70% kerosene constitute is with the solution separating of metal tantalum and metal niobium; Solution after separating is extracted metal tantalum and metal niobium through crystallization and cooling baking operation.
By above operation, will contain tungsten, cobalt, nickel, tantalum, niobium and from scrap hard alloy, propose, make full use of again.
Embodiment 5
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and the adding sodium bicarbonate is heated to 1000 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, generation contains the reaction solution of sodium wolframate and contains the throw out of multiple metals such as cobalt, nickel, titanium, tantalum, with this throw out through the wet-milling operation, make tungsten can fully react the formation sodium wolframate, after filtration the two be separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
1, the sodium tungstate solution to gained carries out removal of impurities
Get the sodium tungstate solution of gained, the limit adds the stirring of vitriol oil limit therein, makes the pH value of solution adjust to 2.5, forms water glass jelly precipitation, and removes this precipitation to such an extent that be sodium tungstate solution;
2, adding through over-richness in 1: 1.2 ratio in the sodium tungstate solution of having removed silicon ion is that the extraction liquid (during extraction, the concentration of feed liquid is for containing Tungsten oxide 99.999 100 grams per liters) that the 260# solvent oil by secondary octanol+85% of 5% N235+10% of 0.6mol/L vitriolization constitutes reacts the generation sodium salt; Ratio in 1.8: 1 in the sodium salt liquid that has extracted adds the ammoniacal liquor reaction that concentration is 4.5mol/L, generates secondary tungsten acid ammonium solution;
To be heated to 90 ℃ in this solution, kept 4 hours, evaporation makes ammonium para-tungstate crystal separate out;
3, taking out this crystallization is 5 hours with it drying time under 105 ℃ of temperature, gets the ammonium paratungstate powder;
4, getting above-mentioned ammonium paratungstate powder is 700 ℃ through excess temperature once more, and the time is that 3 hours calcining forms Tungsten oxide 99.999;
5, will calcine the Tungsten oxide 99.999 that forms is presented to and feeds hydrogen reducing in the reduction furnace and promptly get metal tungsten powder.
In the 4th step, utilize solids obtained in the first step to extract other metals
1, gets solids and to join concentration be to be heated to 120 ℃ of reactions in 25% the hydrochloric acid soln, generate and contain the solution of cobalt, nickel and contain tantalum and the throw out bits of niobium, after filtration cobalt, nickel solution thing and precipitation bits are separated;
2, getting the solution that contains cobalt, nickel, is that 28% hydrogen peroxide adds wherein fully reaction with concentration, adds the PH to 5.0 of ammoniacal liquor conditioned reaction liquid again, and reaction forms ferric hydroxide precipitate, has removed iron contamination.Constitute extraction liquid with 1: 1 20% P507 and 80% 260# solvent oil after the deironing,, under 48 ℃ of temperature, will contain cobalt liquid and nickeliferous liquid separation through extraction process in putting into wherein with 1: 1 ratio of reaction solution; In containing cobalt liquid and nickeliferous liquid, add the ammonium oxalate solution reaction respectively and generate cobalt oxalate and nickelous oxalate feed liquid, and get cobalt oxalate and nickelous oxalate solids through precipitation, filtration, sedimentary evaporation and baking operation respectively, by hydrogen it is reduced into cobalt powder and nickel powder through reduction furnace again;
3, get the precipitation bits, it again after calcining fusion in 3 hours under 720 ℃ of temperature, is presented in the water and dissolves, the extraction liquid extraction that the hydrofluoric acid via 11%, 8% secondary octanol and 85% kerosene constitute is with the solution separating of metal tantalum and metal niobium; Solution after separating is extracted metal tantalum and metal niobium through crystallization and cooling baking operation.
By above operation, can from scrap hard alloy, propose containing tungsten, cobalt, nickel, tantalum, niobium, make full use of again.
Claims (10)
1, from scrap hard alloy, extracts the method for tungsten and other rare metals, it is characterized in that comprising the following steps:
The first step, the fusing of scrap hard alloy
Scrap hard alloy is presented in the smelting furnace, and adds sodium bicarbonate or yellow soda ash is heated to 800---1200 ℃ of fusings;
Second step, the producing of sodium tungstate solution
The hard metal mixtures of fusing is poured in the water, is generated the reaction solution and the throw out that contain sodium wolframate, after filtration the two is separated into sodium tungstate solution and solids:
In the 3rd step, utilize obtained sodium tungstate solution to extract tungsten
Get described sodium tungstate solution, generate ammonium tungstate solution, make the ammonium tungstate crystallization separate out this solution heating evaporation, it oven dry calcining is formed Tungsten oxide 99.999, add hydrogen reducing again and become metal tungsten powder through extraction and the back extraction of adding ammoniacal liquor;
In the 4th step, utilize described solids to extract other metals
Getting described solids and joining concentration is 10---the reaction of 30% hydrochloric acid soln, generate throw out, after filtration with liquid object and precipitate and separate and handle:
---get liquid object, behind the removal iron contamination, will contain cobalt liquid and nickeliferous liquid separation through extraction process; After in containing cobalt liquid and nickeliferous liquid, adding ammonium oxalate solution reaction respectively, and respectively through precipitate, filter, evaporate, dry cobalt oxalate and nickelous oxalate solids, again it is reduced into cobalt powder and nickel powder;
---get precipitation, it is carried out the igneous fusion second time again after, be presented in the water and dissolve, through extraction process metal tantalum and metal niobium are extracted respectively.
2, the method for extracting rare metal from scrap hard alloy as claimed in claim 1 is characterized in that: described through extraction with add the extraction conditions that the ammoniacal liquor back extraction generates in the ammonium tungstate solution operation and be: extraction liquid is that 260# solvent oil, the reverse-extraction agent of secondary octanol+80% of 10% N235+10% is ammoniacal liquor.
3, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing obtained sodium tungstate solution to extract tungsten, at first to described sodium tungstate solution removal of impurities, promptly in this solution, add sulfuric acid, the pH value to 2.0 of regulator solution---3.5, make silicon ion generate the water glass precipitation.
4, the method for extracting rare metal from scrap hard alloy as claimed in claim 1 is characterized in that: pour the hard metal mixtures of described fusing into the back forms in the water throw out and carry out wet-milling.
5, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing obtained sodium tungstate solution to extract tungsten, the temperature of described ammonium tungstate solution heating evaporation is 80---95 ℃, the time is 3---and 8 hours.
6, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing obtained sodium tungstate solution to extract tungsten, be 80---104 ℃, time be 4---7 hours with the temperature of the ammonium tungstate crystallization oven dry of heating evaporation gained.
7, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing described solids to extract other metals, described incinerating temperature is 700---750 ℃, the required incinerating time is 1.5---and 3 hours.
8, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing described solids to extract other metals, with the described employed extraction liquid of extraction process that contains cobalt liquid and nickeliferous liquid separation by 1: 0.8---1.2 20% P507 and 80% 260# solvent oil constitute.
9, the method for extracting rare metal from scrap hard alloy as claimed in claim 8 is characterized in that: use by 1: 0.8---temperature of the extraction liquid extraction that 1.2 20% P 507 and 80% 260# solvent oil constitute is 40---50 ℃.
10, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: when utilizing described solids to extract other metals,---12% hydrofluoric acid, 7---15% secondary octanol and 60---, 90% kerosene constitutes by 8 with described metal tantalum and the employed extraction liquid of the isolating extraction process of metal niobium.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100125727A CN1827806A (en) | 2006-04-10 | 2006-04-10 | Method for extracting tungsten and other rare metals from waste hard alloy |
| CNA2006101370177A CN1952187A (en) | 2006-04-10 | 2006-10-13 | Process for extracting tungsten metal and other rare metal from waste and old hard alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885070B (en) * | 2009-07-05 | 2011-12-14 | 张雪云 | Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap |
| CN103194604A (en) * | 2012-01-06 | 2013-07-10 | 深圳市格林美高新技术股份有限公司 | Method for recovering tantalum, silver and manganese in waste and old tantalum capacitor |
| CN103924092A (en) * | 2014-05-06 | 2014-07-16 | 厦门嘉鹭金属工业有限公司 | High-efficient recovery method of waste tungsten powder |
| CN106191455A (en) * | 2016-07-08 | 2016-12-07 | 大余县东宏锡制品有限公司 | A kind of tungsten essence artware preparation method refined from ammonium paratungstate solid slag |
| CN106947865A (en) * | 2016-05-25 | 2017-07-14 | 江西理工大学 | A kind of energy-efficient method for oxidation of scrap hard alloy |
| CN108441640A (en) * | 2018-04-03 | 2018-08-24 | 湖南工学院 | A kind of method that waste diamond abrasive material resource comprehensive utilization utilizes |
| CN108910966A (en) * | 2018-09-21 | 2018-11-30 | 湖南金雕能源科技有限公司 | A method of extracting tungsten carbide and cobalt from scrap hard alloy |
| CN109897962A (en) * | 2019-03-14 | 2019-06-18 | 厦门钨业股份有限公司 | A kind of method and apparatus using tungsten in oxidizing semlting method recycling tungsten waste |
| CN111041208A (en) * | 2019-11-30 | 2020-04-21 | 福达合金材料股份有限公司 | Method for efficiently recycling copper and tungsten in copper-tungsten alloy waste |
| CN115156545A (en) * | 2022-06-30 | 2022-10-11 | 赣州有色冶金研究所有限公司 | Ultra-coarse tungsten powder, ultra-coarse tungsten carbide powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101885070B (en) * | 2009-07-05 | 2011-12-14 | 张雪云 | Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap |
| CN103194604A (en) * | 2012-01-06 | 2013-07-10 | 深圳市格林美高新技术股份有限公司 | Method for recovering tantalum, silver and manganese in waste and old tantalum capacitor |
| CN103194604B (en) * | 2012-01-06 | 2014-09-17 | 深圳市格林美高新技术股份有限公司 | Method for recovering tantalum, silver and manganese in waste and old tantalum capacitor |
| CN103924092A (en) * | 2014-05-06 | 2014-07-16 | 厦门嘉鹭金属工业有限公司 | High-efficient recovery method of waste tungsten powder |
| CN103924092B (en) * | 2014-05-06 | 2016-03-23 | 厦门嘉鹭金属工业有限公司 | A kind of efficient recycling method of useless tungsten powder |
| CN106947865A (en) * | 2016-05-25 | 2017-07-14 | 江西理工大学 | A kind of energy-efficient method for oxidation of scrap hard alloy |
| CN106191455A (en) * | 2016-07-08 | 2016-12-07 | 大余县东宏锡制品有限公司 | A kind of tungsten essence artware preparation method refined from ammonium paratungstate solid slag |
| CN108441640B (en) * | 2018-04-03 | 2019-05-07 | 湖南工学院 | A kind of method that waste diamond abrasive material resource comprehensive utilization utilizes |
| CN108441640A (en) * | 2018-04-03 | 2018-08-24 | 湖南工学院 | A kind of method that waste diamond abrasive material resource comprehensive utilization utilizes |
| CN108910966A (en) * | 2018-09-21 | 2018-11-30 | 湖南金雕能源科技有限公司 | A method of extracting tungsten carbide and cobalt from scrap hard alloy |
| CN108910966B (en) * | 2018-09-21 | 2020-06-09 | 湖南金雕能源科技有限公司 | Method for extracting tungsten carbide and cobalt from waste hard alloy |
| CN109897962A (en) * | 2019-03-14 | 2019-06-18 | 厦门钨业股份有限公司 | A kind of method and apparatus using tungsten in oxidizing semlting method recycling tungsten waste |
| CN109897962B (en) * | 2019-03-14 | 2020-11-17 | 厦门钨业股份有限公司 | Method and device for recovering tungsten in tungsten-containing waste by adopting oxidation smelting method |
| CN111041208A (en) * | 2019-11-30 | 2020-04-21 | 福达合金材料股份有限公司 | Method for efficiently recycling copper and tungsten in copper-tungsten alloy waste |
| CN111041208B (en) * | 2019-11-30 | 2021-06-22 | 福达合金材料股份有限公司 | Method for efficiently recycling copper and tungsten in copper-tungsten alloy waste |
| CN115156545A (en) * | 2022-06-30 | 2022-10-11 | 赣州有色冶金研究所有限公司 | Ultra-coarse tungsten powder, ultra-coarse tungsten carbide powder and preparation method thereof |
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