CN1952187A - Process for extracting tungsten metal and other rare metal from waste and old hard alloy - Google Patents
Process for extracting tungsten metal and other rare metal from waste and old hard alloy Download PDFInfo
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Abstract
The invention belongs to the technical field of recovery and salvage of scrap metal carbide, specifically disclosing a method of extracting tungsten and other rare metals from scrap metal carbide. Its process includes the following steps: melting the scrap metal carbide and sodii bicarbonas or natrium carbonicum and introducing into water to obtain ammonium tungstate solution and sediments containing other rare metals, separating, heating ammonium tungstate solution for evaporation, crystallizing, drying, calcining by adding hydrogen for the reduction of tungsten powder, mixing the sediments with sulfuric acid, ammonium oxalate for the extraction of cobalt powder, nickel powder, tantalum and niobium. The method has the advantages of simple operation and low production cost. Extracting cobalt, nickel, tantalum and niobium through the use of the above processes from scrap metal carbide increases the use value of scrap metal carbide and has tremendous economic significance.
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 fusing;
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
Get described solids and join the hydrochloric acid soln reaction that concentration is 10--30%, 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 process extraction and the extraction conditions that adds in the ammoniacal liquor back extraction generation ammonium tungstate solution operation are: extraction liquid is that 260# solvent oil, the reverse-extraction agent of secondary octanol+80 weight parts of the N235+10 weight part of 10 weight parts is ammoniacal liquor;
When utilizing obtained sodium tungstate solution to extract tungsten, at first, promptly in this solution, add sulfuric acid to described sodium tungstate solution removal of impurities, the pH value of regulator solution makes silicon ion generate the water glass precipitation between 2.0--3.5;
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 ℃, and the time is 3--8 hour;
When utilizing obtained sodium tungstate solution to extract tungsten, be that 80--104 ℃, time are 4--7 hour with the temperature of the ammonium tungstate crystallization oven dry of heating evaporation gained;
When utilizing described solids to extract other metals, described incinerating temperature is 700--750 ℃, and the required incinerating time is 1.5--3 hour;
When utilizing described solids to extract other metals, the described employed extraction liquid of extraction process that contains cobalt liquid and nickeliferous liquid separation is made of the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts;
Use the temperature of the extraction liquid extraction that the 260# solvent oil by the P507 of 20 weight parts and 80 weight parts constitutes to be 40--50 ℃;
When utilizing described solids to extract other metals, described metal tantalum and the employed extraction liquid of the isolating extraction process of metal niobium are made of the hydrofluoric acid of 8--12 weight part, the secondary octanol of 7--15 weight part and the kerosene of 60--90 weight part.
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 weight parts of the N235+10 weight part of 10 weight parts 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 the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts 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, via the hydrofluoric acid of 8 weight parts, the secondary octanol of 15 weight parts and the extraction liquid extraction that 60 weight part kerosene constitute, 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 weight parts of the N235+25 weight part of 15 weight parts 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 the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts 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, with it again after calcining fusion in 2.5 hours under 700 ℃ of temperature, be presented in the water and dissolve, the extraction liquid extraction that constitutes via the hydrofluoric acid of 10 weight parts, 10 weight part octanols and 80 weight part kerosene 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 weight parts of the N235+10 weight part of 20 weight parts 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 the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts 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, with it again after calcining fusion in 2 hours under 750 ℃ of temperature, be presented in the water and dissolve, the extraction liquid extraction that constitutes via the kerosene of the secondary octanol of 12 weight part hydrofluoric acid, 7 weight parts and 90 weight parts 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 weight parts of the N235+15 weight part of 10 weight parts 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 the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts 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 constitutes via the kerosene of the hydrofluoric acid of 9 weight parts, the secondary octanol of 12 weight parts and 70 weight parts 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 weight parts of the N235+10 weight part of 5 weight parts 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 the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts 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, with it again after calcining fusion in 3 hours under 720 ℃ of temperature, be presented in the water and dissolve, the extraction liquid extraction that constitutes via the kerosene of the secondary octanol of the hydrofluoric acid of 11 weight parts, 8 weight parts and 85 weight parts 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 fusing;
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
Get described solids and join the hydrochloric acid soln reaction that concentration is 10--30%, 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 process extraction and the extraction conditions that adds in the ammoniacal liquor back extraction generation ammonium tungstate solution operation are: extraction liquid is that 260# solvent oil, the reverse-extraction agent of secondary octanol+80 weight parts of the N235+10 weight part of 10 weight parts 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 of regulator solution makes silicon ion generate the water glass precipitation between 2.0--3.5.
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 ℃, and the time is 3--8 hour.
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 that 80--104 ℃, time are 4--7 hour the temperature of the ammonium tungstate crystallization oven dry of heating evaporation gained.
7, the method for extracting rare metal from scrap hard alloy as claimed in claim 1, it is characterized in that: when utilizing described solids to extract other metals, described incinerating temperature is 700--750 ℃, and the required incinerating time is 1.5--3 hour.
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, the described employed extraction liquid of extraction process that contains cobalt liquid and nickeliferous liquid separation is made of the P507 of 20 weight parts and the 260# solvent oil of 80 weight parts.
9, the method for extracting rare metal from scrap hard alloy as claimed in claim 8 is characterized in that: the temperature that the extraction liquid that uses the 260# solvent oil by the P507 of 20 weight parts and 80 weight parts to constitute extracts 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, described metal tantalum and the employed extraction liquid of the isolating extraction process of metal niobium are made of the hydrofluoric acid of 8--12 weight part, the secondary octanol of 7--15 weight part and the kerosene of 60--90 weight part.
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| CNA2006101370177A CN1952187A (en) | 2006-04-10 | 2006-10-13 | Process for extracting tungsten metal and other rare metal from waste and old hard alloy |
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| 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 |
| CN200610012572.7 | 2006-04-10 | ||
| CNA2006101370177A CN1952187A (en) | 2006-04-10 | 2006-10-13 | Process for extracting tungsten metal and other rare metal from waste and old hard alloy |
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| CN1952187A true CN1952187A (en) | 2007-04-25 |
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| CNA2006101370177A Pending CN1952187A (en) | 2006-04-10 | 2006-10-13 | Process for extracting tungsten metal and other rare metal from waste and old hard alloy |
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Cited By (5)
| 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 |
| CN103495736A (en) * | 2013-10-28 | 2014-01-08 | 成都名钨科技有限责任公司 | Method for recycling hard alloy green body |
| CN108728657A (en) * | 2018-07-15 | 2018-11-02 | 安化县众旺钨业有限公司 | A method of recycling tungsten, cobalt, silver, copper and tantalum from hard-alloy grinding waste material |
| CN114045396A (en) * | 2021-10-13 | 2022-02-15 | 湖北和兴环境材料科技有限公司 | Process for recycling rare metals from solid waste and iron oxide heating roasting furnace |
| CN116940698A (en) * | 2021-03-15 | 2023-10-24 | 学校法人福冈工业大学 | Liquefaction treatment method for niobium and tantalum, niobium solution, and method for producing tantalum solution |
-
2006
- 2006-10-13 CN CNA2006101370177A patent/CN1952187A/en active Pending
Cited By (6)
| 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 |
| CN103495736A (en) * | 2013-10-28 | 2014-01-08 | 成都名钨科技有限责任公司 | Method for recycling hard alloy green body |
| CN108728657A (en) * | 2018-07-15 | 2018-11-02 | 安化县众旺钨业有限公司 | A method of recycling tungsten, cobalt, silver, copper and tantalum from hard-alloy grinding waste material |
| CN116940698A (en) * | 2021-03-15 | 2023-10-24 | 学校法人福冈工业大学 | Liquefaction treatment method for niobium and tantalum, niobium solution, and method for producing tantalum solution |
| CN116940698B (en) * | 2021-03-15 | 2024-03-12 | 学校法人福冈工业大学 | Liquefaction treatment method for niobium and tantalum, niobium solution, and method for producing tantalum solution |
| CN114045396A (en) * | 2021-10-13 | 2022-02-15 | 湖北和兴环境材料科技有限公司 | Process for recycling rare metals from solid waste and iron oxide heating roasting furnace |
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