CN1314818C - Method for extracting rare metal from waste and old carbide alloy - Google Patents
Method for extracting rare metal from waste and old carbide alloy Download PDFInfo
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- CN1314818C CN1314818C CNB200510012779XA CN200510012779A CN1314818C CN 1314818 C CN1314818 C CN 1314818C CN B200510012779X A CNB200510012779X A CN B200510012779XA CN 200510012779 A CN200510012779 A CN 200510012779A CN 1314818 C CN1314818 C CN 1314818C
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Abstract
The present invention belongs to the technical field of the recovery and the reutilization of waste and old hard alloys, more specifically to a method for extracting rare metal from the waste and old hard alloys. The technique comprises the following steps: the waste and old hard alloys are ground to be powder and are calcined after being crushed, the powder carry out reactions in a sodium hydroxide solution, sulphuric acid is added to the obtained sodium tungstate solution, and an ammonium tungstate solution is generated by the extraction and the back extraction of ammonia water. The ammonium tungstate solution is evaporated by heating, crystallized, dried, caclined once again and reduced to be metal tungsten powder by added hydrogen gas, and cobalt powder, nickel powder, metal tantalum and metal niobium are extracted from the solid substances by sulphuric acid and ammonium oxalate. Metal tungsten, metal cobalt, metal nickel, the metal tantalum and the metal niobium are extracted from the waste and old hard alloys by the processes, and the utilization value of the waste and old hard alloys is increased. The metal elements extracted by the technique are made into new hard alloys as required, and the quality requirements of products can be easily achieved. The technique has great 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 rare metal.
Background technology
Along with rapid development of economy, industries such as machinofacture, geology and mine, building, electronics and chemical industry are increasing to the demand of Wimet and former tungsten material.And the various metallic elements that constitute Hardmetal materials almost all are rare elements, its ore deposit storage capacity seldom, exploitation rare metal ore deposit is more and more difficult.Therefore, the utilization again to scrap hard alloy more and more comes into one's own.
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, discloses a kind of " scrap hard alloy reclaims and regeneration treating method ".The disclosed method of this patent 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, discloses a kind of " scrap hard alloy is produced the method for hard metal article powder stock ".The disclosed method of this patent application is: the Wimet classification of giving up back that will reclaim, clean, 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, the cemented carbide powder of production or hart metal product exist following defective:
---the contained metallic element that exceeds standard can not effectively be removed in the impurity of sneaking in process of manufacture and the former surplus or excess alloy;
---Wimet has the thousands of kinds of trades mark, and composition has nothing in common with each other, and the chemical examination time error is very big;
---quality product is difficult for improving, and product specification is lower;
---course of processing equipment complexity, loss are big.
The content of invention
Purpose of the present invention just provides a kind of various rare metals in the scrap hard alloy can be extracted, and can directly utilize the directly synthetic method of extracting rare metal from scrap hard alloy 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 rare metal, comprise the following steps:
The first step, the processing of scrap hard alloy
With the scrap hard alloy fragmentation, clay into power, aerobic calcining, the powder after will calcining again is presented in the sodium hydroxide solution and reacts, generation contains the reaction solution and the throw out of sodium wolframate, after filtration the two is separated into sodium tungstate solution and solids;
In second step, utilize obtained sodium tungstate solution to extract tungsten
Get described sodium tungstate solution, add sulphuric acid soln and carry out acid adjustment, its pH value is controlled between 2.0--3.5, generate ammonium tungstate solution through extraction and the back extraction of adding ammoniacal liquor again, make the ammonium tungstate crystallization separate out this solution heating evaporation, the formation Tungsten oxide 99.999 is calcined in it oven dry once more, added hydrogen reducing again and become metal tungsten powder;
In the 3rd 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, remove iron contamination, after extraction process will contain cobalt liquid and nickeliferous liquid separation; 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.
Its additional technical feature comprises:
The granularity of described scrap hard alloy fragmentation is the 1--5 millimeter;
Described powder size of claying into power with ball mill is the 2--10 micron;
Described incinerating temperature is 300--750 ℃;
The described incinerating time is 1.5--3 hour;
The concentration of described sodium hydroxide solution is 8--15%;
Inject hot steam when reacting in the sodium hydroxide solution in that powder is presented to, make reaction solution boiling 1.5--3 hour;
Described process extraction and the extraction conditions that adds in the ammoniacal liquor back extraction generation ammonium tungstate solution operation are: extraction liquid is the N235 of 10% weight, the secondary octanol of 10% weight and the 260# solvent oil of 80% weight, and reverse-extraction agent is an 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 silicic acid precipitation, and silicic acid is removed between 8.0--9.0;
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, the temperature that the ammonium tungstate crystallization of heating evaporation gained is dried is 80--104 ℃, and the time of oven dry is 4--7 hour;
When utilizing described solids to extract other metals, the described temperature of incinerating once more is 700--750 ℃, and the required incinerating time is 1.5--3 hour;
When utilizing described solids to extract other metals, contain in cobalt liquid and the nickeliferous liquid separation extraction process described, the ratio that contains cobalt liquid and nickeliferous liquid and the consumption of extraction liquid is 1: the 0.8--1.2 weight part, wherein extraction liquid is made of the P507 of 20% weight and the 260# solvent oil of 80% weight.
Use the temperature of the extraction liquid extraction that the 260# solvent oil by the P 507 of 20% weight and 80% weight 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 described third step that utilizes obtained sodium tungstate solution to extract second step of tungsten formation and utilize described solids to extract other metals formations is a step arranged side by side.
The processing method of extracting rare metal from scrap hard alloy provided by the present invention compared with prior art has the following advantages:
1, improves 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.
2, utilize this technology to separate the various rare metals of purifying, improved the technical benefits of product.One ton of waste and old benefit of former processing is about 20,000 yuan, and the economic benefit of new technology is more than 50,000 yuan.
3, 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.
Embodiment
Below the processing method of extracting rare metal from scrap hard alloy provided by the present invention in conjunction with the embodiments is described in further detail:
Embodiment 1
The first step, the treatment step of scrap hard alloy is:
1,, and utilize crusher that it is broken into the fragment of 3 millimeter with the scrap hard alloy washing;
2, the Wimet fragment after the fragmentation is put into the powder of wearing in the ball mill about 2 microns;
3, cemented carbide powder is taken out from ball mill, insert in the calcining furnace 300 ℃ temperature lower calcination 3 hours.This calcining is fired for aerobic, and the most handy oxygen hose replenishes an amount of oxygen in calcining furnace, makes the abundant oxidation of cemented carbide powder, to obtain metal oxide;
4, the incinerating metal oxide is cooled off, promptly but obtain the solubility micro mist, it is in 8% the sodium hydroxide solution that the solubility micro mist of getting gained is presented to concentration, and feed 110 ℃ heat steam ebuillition of heated reaction 4 hours, generate reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum;
5, operation becomes sodium tungstate solution and solids with above-mentioned reactants separate after filtration:
In second 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 8.0, 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 of the N235+10% weight of 10% weight 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 3rd 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 1: 0.8 weight 20% and the 260# solvent oil of 80% weight 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 constitutes via the kerosene of the secondary octanol of the hydrofluoric acid of 8 weight parts, 15 weight parts and 60 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.
Embodiment 2
The first step, the treatment step of scrap hard alloy is:
1,, and utilize crusher that it is broken into the fragment of 4 millimeter with the scrap hard alloy washing;
2, the Wimet fragment after the fragmentation is put into the powder of wearing in the ball mill about 6 microns;
3, cemented carbide powder is taken out from ball mill, insert in the calcining furnace 500 ℃ temperature lower calcination 2 hours.This calcining is fired for aerobic, and the most handy oxygen hose replenishes an amount of oxygen in calcining furnace, makes the abundant oxidation of cemented carbide powder, to obtain metal oxide;
4, the incinerating metal oxide is cooled off, promptly but obtain the solubility micro mist, it is in 10% the sodium hydroxide solution that the solubility micro mist of getting gained is presented to concentration, and feed 120 ℃ heat steam ebuillition of heated reaction 2 hours, generate reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum;
5, operation becomes sodium tungstate solution and solids with above-mentioned reactants separate after filtration:
In second 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 8.5, 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: 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 of the N235+25% weight of 15% weight 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 3rd 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 1: 1 20% weight and the 260# solvent oil of 80% weight 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 kerosene of the secondary octanol of the hydrofluoric acid of 10 weight parts, 10 weight parts and 80 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 3
The first step, the treatment step of scrap hard alloy is:
1,, and utilize crusher that it is broken into the fragment of 5 millimeter with the scrap hard alloy washing;
2, the Wimet fragment after the fragmentation is put into the powder of wearing in the ball mill about 10 microns;
3, cemented carbide powder is taken out from ball mill, insert in the calcining furnace 750 ℃ temperature lower calcination 1.5 hours.This calcining is fired for aerobic, and the most handy oxygen hose replenishes an amount of oxygen in calcining furnace, makes the abundant oxidation of cemented carbide powder, to obtain metal oxide;
4, the incinerating metal oxide is cooled off, promptly but obtain the solubility micro mist, it is in 15% the sodium hydroxide solution that the solubility micro mist of getting gained is presented to concentration, and feed 150 ℃ heat steam ebuillition of heated reaction 1.5 hours, generate reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum;
5, operation becomes sodium tungstate solution and solids with above-mentioned reactants separate after filtration:
In second 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 9.0, 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 of the N235+10% weight of 20% weight 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 3rd 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 1: 1.2 20% weight and the 260# solvent oil of 80% weight 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 the hydrofluoric acid of 12 weight parts, 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 treatment step of scrap hard alloy is:
1,, and utilize crusher that it is broken into the fragment of 2 millimeter with the scrap hard alloy washing;
2, the Wimet fragment after the fragmentation is put into the powder of wearing in the ball mill about 4 microns;
3, cemented carbide powder is taken out from ball mill, insert in the calcining furnace 400 ℃ temperature lower calcination 2.5 hours.This calcining is fired for aerobic, and the most handy oxygen hose replenishes an amount of oxygen in calcining furnace, makes the abundant oxidation of cemented carbide powder, to obtain metal oxide;
4, the incinerating metal oxide is cooled off, promptly but obtain the solubility micro mist, it is in 9% the sodium hydroxide solution that the solubility micro mist of getting gained is presented to concentration, and feed 125 ℃ heat steam ebuillition of heated reaction 3 hours, generate reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum;
5, operation becomes sodium tungstate solution and solids with above-mentioned reactants separate after filtration:
In second 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 8.5, 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 of the N235+15% weight of 10% weight 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 3rd 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 1: 0.9 20% weight and the 260# solvent oil of 80% weight 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 secondary octanol of the hydrofluoric acid of 9 weight parts, 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 treatment step of scrap hard alloy is:
1,, and utilize crusher that it is broken into the fragment of 1 millimeter with the scrap hard alloy washing;
2, the Wimet fragment after the fragmentation is put into the powder of wearing in the ball mill about 8 microns;
3, cemented carbide powder is taken out from ball mill, insert in the calcining furnace 600 ℃ temperature lower calcination 2.5 hours.This calcining is fired for aerobic, and the most handy oxygen hose replenishes an amount of oxygen in calcining furnace, makes the abundant oxidation of cemented carbide powder, to obtain metal oxide;
4, the incinerating metal oxide is cooled off, promptly but obtain the solubility micro mist, it is in 12% the sodium hydroxide solution that the solubility micro mist of getting gained is presented to concentration, and feed 140 ℃ heat steam ebuillition of heated reaction 2.5 hours, generate reaction solution that contains sodium wolframate and the throw out that contains multiple metals such as cobalt, nickel, titanium, tantalum;
5, operation becomes sodium tungstate solution and solids with above-mentioned reactants separate after filtration:
In second 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 9.0, 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: 1.2 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 of the N235+10% weight of 5% weight 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 3rd 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 1: 1 20% weight and the 260# solvent oil of 80% weight 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 (16)
1, from scrap hard alloy, extracts the method for rare metal, it is characterized in that comprising the following steps:
The first step, the processing of scrap hard alloy
With the scrap hard alloy fragmentation, clay into power, aerobic calcining, the powder after will calcining again is presented in the sodium hydroxide solution and reacts, generation contains the reaction solution and the throw out of sodium wolframate, after filtration the two is separated into sodium tungstate solution and solids;
In second step, utilize obtained sodium tungstate solution to extract tungsten
Get described sodium tungstate solution, add sulphuric acid soln and carry out acid adjustment, make its pH value be controlled at 2.0---3.5, generate ammonium tungstate solution through extraction and the back extraction of adding ammoniacal liquor again, make the ammonium tungstate crystallization separate out this solution heating evaporation, the formation Tungsten oxide 99.999 is calcined in it oven dry once more, added hydrogen reducing again and become metal tungsten powder;
In the 3rd 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 from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: the granularity of described scrap hard alloy fragmentation is 1---5 millimeters.
3, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: described powder size of claying into power with ball mill is 2---10 microns.
4, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: described incinerating temperature is 300---750 ℃.
5, the method for from scrap hard alloy, extracting rare metal as claimed in claim 4, it is characterized in that: the described incinerating time is 1.5---3 hours.
6, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it is characterized in that: the concentration of described sodium hydroxide solution is 8---15%.
7, the method for extracting rare metal from scrap hard alloy as claimed in claim 1 is characterized in that: inject hot steam when reacting in the sodium hydroxide solution in that powder is presented to, make reaction solution boiling 1.5---3 hours.
8, the method for from scrap hard alloy, extracting rare metal as claimed in claim 1, it 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 the N235 of 10% weight, the secondary octanol of 10% weight and the 260# solvent oil of 80% weight, and reverse-extraction agent is an ammoniacal liquor.
9, 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 8.0 of regulator solution---9.0, make silicon ion generate the silicic acid precipitation.
10, 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.
11, 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.
12, 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 temperature of incinerating once more is 700---750 ℃, the required incinerating time is 1.5---and 3 hours.
13, 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, contain in cobalt liquid and the nickeliferous liquid separation extraction process described, the ratio that contains cobalt liquid and nickeliferous liquid and the consumption of extraction liquid is 1: 0.8---1.2 weight parts, wherein extraction liquid is made of the P507 of 20% weight and the 260# solvent oil of 80% weight.
14, the method for extracting rare metal from scrap hard alloy as claimed in claim 13 is characterized in that: using the temperature of the extraction liquid extraction that the 260# solvent oil by the P507 of 20% weight and 80% weight constitutes is 40---50 ℃.
15, 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,---kerosene of the hydrofluoric acid of 12 weight parts, 7---secondary octanols and 60 of 15 weight parts---90 weight parts constitutes by 8 with described metal tantalum and the employed extraction liquid of the isolating extraction process of metal niobium.
16, the method for extracting rare metal from scrap hard alloy as claimed in claim 1 is characterized in that: the described third step that utilizes obtained sodium tungstate solution to extract second step of tungsten formation and utilize described solids to extract other metals formations is a step arranged side by side.
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| CN101603125B (en) * | 2009-06-01 | 2011-04-06 | 邱致忠 | Method for purification and impurity removal of nickel liquid |
| CN101885070B (en) * | 2009-07-05 | 2011-12-14 | 张雪云 | Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap |
| CN103088217A (en) * | 2013-02-28 | 2013-05-08 | 江苏龙源催化剂有限公司 | Method for recovering tungsten component from selective catalytic reduction denitrification catalyst |
| CN106947865B (en) * | 2016-05-25 | 2018-08-24 | 江西理工大学 | A kind of energy-efficient method for oxidation of scrap hard alloy |
| CN106399691B (en) * | 2016-08-17 | 2018-08-17 | 湖南金源新材料股份有限公司 | The method that cobalt, tungsten, bismuth are detached from bismuth-containing tungsten-cobalt waste material |
| CN108439473A (en) * | 2018-04-08 | 2018-08-24 | 昆明理工大学 | A kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054270A (en) * | 1991-03-19 | 1991-09-04 | 国营自贡硬质合金厂 | The recovery and treatment method of waste hand alloy material |
| RU2110590C1 (en) * | 1996-07-11 | 1998-05-10 | Институт металлургии им.А.А.Байкова РАН | Method of processing carbide waste originated from solid alloys |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1054270A (en) * | 1991-03-19 | 1991-09-04 | 国营自贡硬质合金厂 | The recovery and treatment method of waste hand alloy material |
| RU2110590C1 (en) * | 1996-07-11 | 1998-05-10 | Институт металлургии им.А.А.Байкова РАН | Method of processing carbide waste originated from solid alloys |
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