CN103266231A - High-efficiency and clean tungsten smelting method - Google Patents
High-efficiency and clean tungsten smelting method Download PDFInfo
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- CN103266231A CN103266231A CN2013101953433A CN201310195343A CN103266231A CN 103266231 A CN103266231 A CN 103266231A CN 2013101953433 A CN2013101953433 A CN 2013101953433A CN 201310195343 A CN201310195343 A CN 201310195343A CN 103266231 A CN103266231 A CN 103266231A
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Abstract
The invention provides a high-efficiency and clean tungsten smelting method. The method comprises the steps of: carrying out electrolysis on an NaCl solution to obtain NaOH and H2 from a cathode chamber and obtain Cl2 from an anode chamber; leaching a tungsten mineral raw material by the NaOH solution obtained by electrolysis to prepare a sodium tungstate solution; treating and transforming the obtained sodium tungstate solution by the existing technology to obtain a ammonium tungstate solution; oxidizing and removing ammonia nitrogen in waste smelting water by the Cl2 obtained by electrolysis; and reducing a tungsten oxide by the H2 obtained by electrolysis, thereby preparing tungsten powder. The method can be used for efficiently treating the tungsten mineral raw material to prepare the tungsten powder; and the method can save cost and no ammonia-nitrogen waste water is discharged.
Description
Technical field
The present invention relates to rare metal and extract the technological method that field of metallurgy, particularly tungsten are smelted.
Background technology
The NaOH decomposition method is because strong to adaptability to raw material, and rate of decomposition is high and become the main flow technology of existing processing tungsten mineral material.But in the real tungsten smelting process, obtain high tungsten leaching yield, the consumption of NaOH is very big.For example, when handling wolframite, in the time of obtaining 99% leaching yield, the consumption of NaOH is 1.5～2 times of theoretical amount; And when handling white tungsten fine ore, NaOH consumption even reached 3～4 times of theoretical amount.
As everyone knows, NaOH obtains by electrolysis NaCl in the chlorine industry.Cathode compartment produces NaOH and H in the NaCl electrolytic process
2, the anolyte compartment produces Cl
2Directly being obtained by electrolysis is that concentration is about 30% NaOH solution, and this can be used for Decomposition of Tungsten, but accumulating for convenience also needs by evaporative crystallization NaOH to be made solid caustic soda.Because the NaOH hydration heat is big, evaporative process need consume lot of energy; In addition because industrial big to the NaOH demand, and H
2And Cl
2Market demand less relatively, cause the NaOH substantial appreciation of prices, in fact H
2And Cl
2Production cost is also transferred on the NaOH product directly or indirectly.
NaOH holds at high price, and causes the tungsten smelting cost to rise.Therefore press for the comprehensive lifting by Technology, reduce cost, enhance the competitiveness.
Existing tungsten smelting process is to obtain sodium tungstate solution by the NaOH decomposition of tungsten mineral raw material, again through ion exchange method or solvent extration absorption or extraction tungsten, use ammonia solution to carry out desorb then or back extraction obtains ammonium tungstate solution, final evaporation crystallization ammonium tungstate solution obtains APT.Though whole technology is an extremely successful and ripe technology, but because used ammonia in the transformation process, inevitably can produce the waste water (China is very strict to ammonia nitrogen concentration restriction in the discharge of wastewater, and national grade one discharge standard is less than 15mg/L) that big volume low-concentration contains ammonia nitrogen.Yet the low-concentration ammonia-nitrogen waste water that produces in the tungsten smelting process does not still have effective treatment process at present.For this reason, some enterprise only does preliminary treatment for reducing cost and does not even handle direct discharging, seriously causes water pollution.
In fact the break point chlorination method can be efficiently with the NH in the solution
4 +Be oxidized to N
2, can reach the purpose of ammonia nitrogen in the thorough removing waste water, in sanitary sewage disposal, be used widely.But owing to buy Cl on the one hand specially
2Need additional cost again, even if on the other hand in the tungsten smelting wastewater of " lower concentration " ammonia nitrogen content cause Cl again also far above sanitary sewage (tens of times)
2Consumption rises violently and is difficult to bear, so nobody considered to handle the tungsten smelting wastewater by chlorine oxidation so far.Obviously how to obtain Cl cheaply
2Be crucial.
In addition, the ammonium tungstate solution crystallization gets the APT(ammonium paratungstate) become Tungsten oxide 99.999 through calcining again, also need through H
2Reduction just can be made tungsten powder.Traditional approach that obtains hydrogen passes through water electrolysis exactly.Therefore in order to obtain H
2, the tungsten smeltery also needs to build complicated water electrolysis hydrogen production system, is again the electrowinning process of one power consumption, and production cost is high.Therefore, how to obtain H cheaply
2It is another key.
By above analysis, be limited to different operations in the past and cut apart the limitation that considers a problem mutually, cause cost high.And if tungsten metallurgy can be considered as a whole synthesis, then can simplify literary writing by leaving out superfluous words, reduce cost.
If can obtain NaOH solution at the on-the-spot electrolysis NaCl of tungsten smelting shop, be directly used in the leaching tungsten mineral material, then NaOH needn't pass through irrational high energy consumption process of " to solid caustic soda, being mixed with solution more again by solution " again, and the Cl that produces
2Also can be directly used in the oxide treatment ammonia nitrogen waste water, produced simultaneously H
2Can also be used for reduction preparation tungsten powder, then whole tungsten smelting technology process just can realize clean and effective production.
Summary of the invention
The tungsten smelting process that the purpose of this invention is to provide a kind of high-efficiency cleaning.
A kind of tungsten smelting process of high-efficiency cleaning may further comprise the steps:
(1) earlier by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, the anolyte compartment obtains Cl
2
(2) the NaOH solution that again step (1) electrolysis is obtained is used for leaching tungsten mineral material and prepares sodium tungstate solution;
(3) step (2) is obtained the sodium tungstate solution treated ammonium tungstate solution that obtains again;
(4) Cl that step (1) electrolysis is obtained
2Be used for ammonia nitrogen in the oxidation removal tungsten smelting wastewater;
(5) H that step (1) electrolysis is produced
2Be used for reduction-oxidation tungsten and prepare tungsten powder.
The NaOH strength of solution that described electrolysis obtains is 20%～40%, is directly used in the leaching tungsten mineral material.
Described tungsten mineral material comprises wolframite, white tungsten fine ore, and Scheelite-Wolframite Mixed Mine, black tungsten ore or white tungsten ore, tungsten minerals contains WO
3Be 10%～76%.
Described sodium tungstate solution is handled the mode that obtains ammonium tungstate solution and is comprised ion exchange method or solvent extration.
Described tungsten smelting wastewater comprises liquid and washings after the ion-exchange, one or more in raffinate and the washings.
Adopt in the aforesaid method before ion exchange method or the solvent extration, adopt the hcl acidifying sodium tungstate solution, liquid or raffinate are NaCl solution after the ion-exchange; Through Cl
2Behind the oxidation removal ammonia nitrogen, after returning or concentrate, part returns the electrowinning process of step (1).
Described H
2Be used for reduction-oxidation tungsten after drying and prepare tungsten powder.
Described Tungsten oxide 99.999 is to obtain by calcining APT.
Described APT obtains by the ammonium tungstate solution evaporative crystallization, the NH that evaporation produces
3Desorb or back extraction when after absorbing, returning for step (3) preparation ammonium tungstate solution; Or feed Cl again after earlier ammonium tungstate solution being evaporated part solution
2Perhaps do not evaporate direct feeding Cl
2Gas is oxidized to N with ammonia nitrogen
2Time neutralization crystallization obtains APT.
The tungsten smelting process of the high-efficiency cleaning that the present invention proposes, its particular content is as follows:
(1) between the built-in vertical lathe of tungsten hydrometallurgy factory, produces NaOH, H
2And Cl
2, concrete: by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, the anolyte compartment obtains Cl
2
(2) the NaOH solution that obtains of electrolysis is directly used in and leaches tungsten mineral material and prepare sodium tungstate solution.The NaOH strength of solution that described electrolysis obtains is 20%～40%, can be directly used in the leaching tungsten mineral material.Described tungsten mineral material comprises wolframite, white tungsten fine ore, and Scheelite-Wolframite Mixed Mine, black tungsten ore, white tungsten ore etc., tungsten minerals contains WO
3Be 10%～76%.Leaching obtains sodium tungstate solution WO
3Concentration is 80g/L～250g/L.Obtain sodium tungstate solution and obtain ammonium tungstate solution through ion exchange method or solvent extration processing again; Ion exchange method can contact absorption with sodium tungstate solution dilution back with strongly basic anion exchange resin; Perhaps can adopt and to contact absorption or extraction tungsten after the direct acidifying of sodium tungstate solution with ion exchange resin or extraction agent.The acid that acidifying is adopted is hydrochloric acid, sulfuric acid or nitric acid; Ion exchange resin comprises macroporous strong basic resin and macroreticular weakly base resin; Described extraction agent is the weakly alkaline extraction agent.
(3) when adopting ion exchange method and solvent extration, behind the hcl acidifying sodium tungstate solution, liquid or raffinate are NaCl solution after the ion-exchange, again through Cl
2Behind the oxidation removal ammonia nitrogen, part is returned electrowinning process after returning or concentrating.
(4) Cl that obtains of electrolysis
2Be used for ammonia nitrogen in the oxidation removal tungsten smelting wastewater.The ammonia nitrogen waste water that produces in the described tungsten smelting process comprises liquid and washings, raffinate and washings after the ion-exchange.
(5) the ammonium tungstate solution evaporative crystallization is obtained APT, the NH that evaporation produces
3After absorbing, return for desorb or back extraction.Feed Cl again after perhaps earlier ammonium tungstate solution being evaporated part solution
2Perhaps do not evaporate direct feeding Cl
2Gas is oxidized to N with ammonia nitrogen
2Time neutralization crystallization obtains APT.To obtain obtaining Tungsten oxide 99.999 after the APT calcining.H with the electrolysis generation
2Be used for reduction-oxidation tungsten after drying and prepare tungsten powder.
Technical superiority of the present invention
Advantage of the present invention mainly embodies chlorine industry and tungsten smelting technology is organically combined, by producing in real time and the method for using, with the NaOH solution that chloralkali process is produced, Cl
2And H
2The tungsten minerals leaching, the ammonia nitrogen waste water that are directly used in the tungsten smelting process are administered and reduction preparation tungsten powder, and main advantage is embodied in:
(1) the NaOH solution (do not need first evaporative crystallization to make solid caustic soda, transport on-the-spot obtain solution again to) of electrolysis generation can be directly used in the tungsten ore leaching, greatly reduces the cost of NaOH, has reduced the cost that tungsten ore leaches;
(2) Cl of by-product
2Be used for the thorough processing of ammonia nitrogen waste water, the low-cost zero release that realizes ammonia nitrogen;
(3) ad hoc hydrogen generating system again adopts the H of by-product
2, reduce the cost that reduction prepares tungsten powder.
Cost relatively calculates
Produce 1 ton of APT and need consume NaOH and be about 0.6 ton, produce nitrogen-containing wastewater 80m
3(53m
3), containing ammonia nitrogen is 300mg/L; Also 1 ton of tungsten powder of original production consumes hydrogen 31.6Kg.Only compare two kinds of operations that the method cost there are differences in the computation process, comprise that mainly NaOH consumes, ammonia nitrogen is administered and reduction tungsten powder hydrogen consumption cost.
(1) by traditional method:
The price of buying 1 ton of solid NaOH is 3000 yuan, buys the 45 yuan/Kg of price of hydrogen, and the ammonia nitrogen treatment cost is 20 yuan/m
3(can't reach discharging standards 15mg/L).
Produce alkali and the ammonia nitrogen treatment cost=0.6 * 3000+80 * 20=3400 unit of 1 ton of APT
1 ton of APT is sintered into consumption hydrogen cost=22.1 * 45=995 unit of making 0.7 ton of tungsten powder behind the Tungsten oxide 99.999
Amount to: 4395 yuan
(2) by this processing method:
In chlorine industry, calculate to produce 1 ton of 100%NaOH finished product
2NaCl+2H
2O→2NaOH+H
2+Cl
2
Producing 1 ton of 100%NaOH can make the weight of chlorine, hydrogen and consume sodium-chlor and the weight of water is respectively: chlorine 887.5kg, hydrogen 25kg, consumption salt 1462.5kg, water consumption 450kg.Power consumption by 1 ton of solid caustic soda of chloralkali process production be 2250Kwh(comprising steam consumption, need to consume steam be 3.26 tons and produce 1 ton of solid caustic soda).Therefore, cost 1 ton of NaOH(liquid) is (comprising that 3.3 tons of concentration are liquid caustic soda+0.888 ton chlorine+25Kg hydrogen of 30%)=2250Kwh * 0.75 yuan/kwh(1 ton solid caustic soda)-3.26 * 120 yuan of/ton yuan/ton (water)=1882, yuan/ton (NaCl)+0.45 * 1.2, (steam)+1.463 * 400 yuan.
0.6 ton of 1 ton of APT alkaline consumption, ammonia nitrogen are administered consumption chlorine 240Kg(and are administered the back ammonia nitrogen concentration far below discharging standards 15mg/L), be sintered into Tungsten oxide 99.999 after reduction can get 0.7 ton of tungsten powder, need hydrogen 22.1Kg.The chlorine that produces by electrolysis just satisfies 1 ton of APT processing of production ammonia nitrogen waste water.0.27 ton of NaOH of output and 6.76Kg hydrogen also need 0.43 ton of NaOH of outsourcing and 15.34Kg hydrogen simultaneously.
Produce 1 ton of APT alkali and ammonia nitrogen treatment cost=0.27 * 1882+0.43 * 3000=1798 unit,
1 ton of APT is sintered into consumption hydrogen cost=15.34 * 45=690 unit of making 0.7 ton of tungsten powder behind the Tungsten oxide 99.999
Amount to: 2488 yuan
(3) two method costs compare:
Administer and produce 0.7 ton of tungsten powder cost and can reduce=4395-2488=1907 unit by 1 ton of APT of this explained hereafter and ammonia nitrogen
Description of drawings
Fig. 1 is high-efficiency cleaning tungsten smelting technology schema of the present invention.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Being that 26% NaCl solution carries out electrolysis with mass concentration, obtaining concentration and be 30% NaOH solution, is 60% wolframite reaction by 1.5 times of theoretical consumptions and grade, liquid-solid ratio 0.9:1, temperature of reaction is controlled at 160 ℃, and the reaction times is 2.0 hours, leaching yield reaches 99.2%, obtains the Na of 180g/L
2WO
4Solution.To 25g/L, use 201 * 7 resins to adsorb solution dilution, after the washing fully, use 5mol/LNH again
4Cl+2mol/LNH
3H
2O carries out desorb, and obtaining concentration is the 256g/L ammonium tungstate solution.Liquid and resin washings are pressed Cl by the break point chlorination method after the ion-exchange
2With ammonia mol ratio in the solution be that 1.02 amount feeds Cl
2Oxidation makes ammonia nitrogen be transformed into N
2Remove, ammonia nitrogen concentration is 0.3mg/L in the relief liquor.Ammonium tungstate solution is through evaporative crystallization, and the crystallization control rate is 95% to obtain APT, and APT reaches national 0 grade standard after testing.The APT calcining obtains WO
3, the H that produces with electrolysis again
2Reduction prepares tungsten powder after drying.
Embodiment 2
Being that 26% NaCl solution carries out electrolysis with mass concentration, obtaining concentration and be 28% NaOH solution, is 58% sheelite reaction by 3.5 times of theoretical consumptions and grade, and solid-to-liquid ratio is 1:1, and temperature of reaction is controlled at 200 ℃, and leaching yield reaches 98.5%, obtains the Na of 220g/L
2WO
4Solution.Solution uses HCl to regulate pH value to 4.5, uses the D301 resin to adsorb, and after the washing fully, carries out desorb with 25% ammoniacal liquor again, and acquisition concentration is the 256g/L ammonium tungstate solution.Liquid and resin washings are pressed Cl by the break point chlorination method after the ion-exchange
2With ammonia mol ratio in the solution be that 1.03 amount feeds Cl
2Oxidation makes ammonia nitrogen be transformed into N
2Remove.After reaction was finished, liquid was that concentration is the NaCl of 112g/L after the ion-exchange, is evaporated to saturated returning again for electrolysis; Ammonia nitrogen concentration is 0.2mg/L in the washings, directly the discharging of neutralization back.Ammonium tungstate solution feeds Cl again after evaporating part water
2, crystallization obtains APT when reoxidizing ammonia nitrogen, and percent crystallization in massecuite is 96%, reaches national 0 grade standard after testing.The APT calcining obtains WO
3, the H that produces with electrolysis again
2Reduction prepares tungsten powder after drying.
Embodiment 3
Being that 26% NaCl solution carries out electrolysis with mass concentration, obtaining concentration and be 28% NaOH solution, is 61% sheelite reaction by 4.0 times of theoretical consumptions and grade, solid-to-liquid ratio is 1.1:1, temperature of reaction control is at 180 ℃, and leaching yield reaches 98.7%, obtains the Na of 215g/L
2WO
4Solution.Solution uses H
2SO
4Regulate pH value to 4.2, use the D314 resin to adsorb, after the washing fully, carry out desorb with 25% ammoniacal liquor again, acquisition concentration is the 256g/L ammonium tungstate solution.Resin uses H
2SO
4Make the transition the back for absorption tungsten.Liquid after the ion-exchange, resin washings and the back liquid that makes the transition are pressed Cl by the break point chlorination method
2With ammonia mol ratio in the solution be that 1.1 amount feeds Cl
2Oxidation makes ammonia nitrogen be transformed into N
2Remove.After reaction is finished, hand over back liquid, ammonia nitrogen concentration is 0mg/L in washings and the back liquid that makes the transition, directly neutralization back discharging.Ammonium tungstate solution directly feeds Cl
2, obtaining APT in oxidation except crystallization in the ammonia nitrogen, percent crystallization in massecuite is 95.8%, reaches national 0 grade standard after testing.The APT calcining obtains WO
3, the H that produces with electrolysis again
2Reduction prepares tungsten powder after drying.
Embodiment 4
Being that 26.5% NaCl solution carries out electrolysis with mass concentration, obtaining concentration and be 33% NaOH solution, is 45% Scheelite-Wolframite Mixed Mine reaction by 3.8 times of theoretical consumptions and grade, solid-to-liquid ratio is 1.2:1, temperature of reaction control is at 200 ℃, and leaching yield reaches 99.1%, obtains the Na of 215g/L
2WO
4Solution.Solution uses HCl to regulate pH value to 3.9, uses the weakly alkaline extraction agent to extract, and after the washing fully, carries out desorb with 25% ammoniacal liquor again, and acquisition concentration is the 249g/L ammonium tungstate solution.Resin uses HCl to make the transition the back for absorption tungsten.Raffinate, washings and the back liquid that makes the transition are pressed Cl by the break point chlorination method
2With ammonia mol ratio in the solution be that 1.25 amount feeds Cl
2Oxidation makes ammonia nitrogen be transformed into N
2Remove, ammonia nitrogen concentration is reduced to 0.22mg/L in the solution, discharging after neutralizing.Ammonium tungstate solution directly feeds Cl
2, obtaining APT in oxidation except crystallization in the ammonia nitrogen, percent crystallization in massecuite is 94.9%, reaches national 0 grade standard after testing; Crystalline mother solution returns the evaporative crystallization operation after removing impurity such as Pb, As Si.The APT calcining obtains WO
2.9, the H that produces with electrolysis again
2Reduction prepares tungsten powder after drying.
Embodiment 5
Being that 26.5% NaCl solution carries out electrolysis with mass concentration, obtaining concentration and be 33% NaOH solution, is 25% black tungsten ore reaction by 3.8 times of theoretical consumptions and grade, and leaching yield reaches 97.8%, obtains the Na of 120g/L
2WO
4Solution.Solution uses HCl to regulate pH value to 4.2, uses the macroporous strong basic resin to adsorb, and after the washing fully, carries out desorb with ammoniacal liquor again, and obtaining concentration is the 220g/L ammonium tungstate solution.Resin uses HCl to make the transition the back for absorption tungsten.Liquid after the ion-exchange, resin washings and back liquid use transition Cl
2Oxidation makes ammonia nitrogen be transformed into N
2Remove.After reaction was finished, liquid was that concentration is the NaCl solution of 98g/L after the ion-exchange, returns after the evaporation concentration for electrolysis; Ammonia nitrogen concentration is 0mg/L in washings and the back liquid that makes the transition, and part is returned the adjusting pH value for sodium tungstate solution, and directly discharge all the other neutralization backs.Directly with Cl
2Be passed in the ammonium tungstate solution, obtain APT in oxidation except crystallization in the ammonia nitrogen, crystalline mother solution returns the evaporative crystallization operation after removing impurity such as Pb, As Si.The APT calcining obtains WO
2.72, the H that produces with electrolysis again
2Reduction prepares ultrafine tungsten powder after drying.
Embodiment 6
The Cl that electrolysis is obtained
2Being passed into the waste water that ammonia nitrogen concentration is 3.5g/L (from tungsten smelting process) and ammonia nitrogen concentration is in the waste water (from the rare-earth smelting process) of 13g/L, Cl
2The feeding amount is 1.02 times of theoretical amount, makes ammonia nitrogen be transformed into N
2Remove.After reaction was finished, ammonia nitrogen concentration was reduced to 0.82mg/L and 13.26mg/L respectively in the solution, gained acidic solution qualified discharge after neutralizing.
Claims (10)
1. the tungsten smelting process of a high-efficiency cleaning is characterized in that, may further comprise the steps:
(1) earlier by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, the anolyte compartment obtains Cl
2
(2) the NaOH solution that again step (1) electrolysis is obtained is used for leaching tungsten mineral material and prepares sodium tungstate solution;
(3) step (2) is obtained the sodium tungstate solution treated ammonium tungstate solution that obtains again;
(4) Cl that step (1) electrolysis is obtained
2Be used for ammonia nitrogen in the oxidation removal tungsten smelting wastewater;
(5) H that step (1) electrolysis is produced
2Be used for reduction-oxidation tungsten and prepare tungsten powder.
2. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 1, it is characterized in that: the NaOH strength of solution that described electrolysis obtains is 20%～40%, is directly used in the leaching tungsten mineral material.
3. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 1 and 2, it is characterized in that: described tungsten mineral material comprises wolframite, white tungsten fine ore, Scheelite-Wolframite Mixed Mine, black tungsten ore or white tungsten ore, tungsten minerals contains WO
3Be 10%～76%.
4. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 1 is characterized in that: described sodium tungstate solution is handled the mode that obtains ammonium tungstate solution and is comprised ion exchange method or solvent extration.
5. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 4 is characterized in that: described tungsten smelting wastewater comprises liquid and washings after the ion-exchange, one or more in raffinate and the washings.
6. according to the tungsten smelting process of claim 1 or 4 or 5 described a kind of high-efficiency cleanings, it is characterized in that: adopt before ion exchange method or the solvent extration, adopt the hcl acidifying sodium tungstate solution, liquid or raffinate are NaCl solution after the ion-exchange; Through Cl
2Behind the oxidation removal ammonia nitrogen, after returning or concentrate, part returns the electrowinning process of step (1).
7. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 1 is characterized in that: described H
2Be used for reduction-oxidation tungsten after drying and prepare tungsten powder.
8. according to the tungsten smelting process of claim 1 or 7 described a kind of high-efficiency cleanings, it is characterized in that: described Tungsten oxide 99.999 is to obtain by calcining APT.
9. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 8 is characterized in that: described APT obtains by the ammonium tungstate solution evaporative crystallization, the NH that evaporation produces
3Desorb or back extraction when after absorbing, returning for step (3) preparation ammonium tungstate solution.
10. the tungsten smelting process of a kind of high-efficiency cleaning according to claim 8 is characterized in that: described APT feeds Cl after earlier ammonium tungstate solution being evaporated part solution again
2Perhaps do not evaporate direct feeding Cl
2Gas is oxidized to N with ammonia nitrogen
2Time neutralization crystallization obtains APT.
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| CN104046800A (en) * | 2014-07-11 | 2014-09-17 | 谭春波 | Process of extracting white tungsten concentrate from tungstenic iron ores or tungstenic waste residues |
| CN104263976A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process |
| CN104263971A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero pollution |
| CN104263974A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero waste water discharge |
| CN104263972A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | Metallurgy system with multiple closed cycles for tungsten mineral raw materials |
| CN104263975A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Metallurgical technology with multiple closed cycles for tungsten mineral raw materials |
| CN104263973A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops |
| CN104829008A (en) * | 2015-05-08 | 2015-08-12 | 哈尔滨工业大学 | Water treatment method for removing ammonia nitrogen |
| JP2018119197A (en) * | 2017-01-27 | 2018-08-02 | 京セラ株式会社 | Method of recovering tungsten compound |
| CN109250758A (en) * | 2018-12-01 | 2019-01-22 | 湖南懋天世纪新材料有限公司 | A kind of comprehensive utilization process of useless WC production APT byproduct in process object |
| CN109850948A (en) * | 2019-03-14 | 2019-06-07 | 东北大学 | It is a kind of to adulterate WO with white tungsten fine ore synthesis Au3The methods and applications of nanometer sheet |
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| CN104263976B (en) * | 2014-10-09 | 2016-07-27 | 江西稀有金属钨业控股集团有限公司 | The tungsten mineral material metallurgical technology of omnidistance non-pollution discharge |
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| CN104263976A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process |
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| CN109250758A (en) * | 2018-12-01 | 2019-01-22 | 湖南懋天世纪新材料有限公司 | A kind of comprehensive utilization process of useless WC production APT byproduct in process object |
| CN109850948A (en) * | 2019-03-14 | 2019-06-07 | 东北大学 | It is a kind of to adulterate WO with white tungsten fine ore synthesis Au3The methods and applications of nanometer sheet |
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