CN103266231B - A kind of Tungsten smelting method of high-efficiency cleaning - Google Patents
A kind of Tungsten smelting method of high-efficiency cleaning Download PDFInfo
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Abstract
The invention provides a kind of Tungsten smelting method of high-efficiency cleaning, by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, anolyte compartment obtains Cl
2; The NaOH solution that electrolysis obtains prepares sodium tungstate solution for leaching tungsten mineral material; Obtain sodium tungstate solution and obtain ammonium tungstate solution transition through existing art breading again; The Cl that electrolysis obtains
2the ammonia nitrogen be used in oxidation removal Tungsten smelting waste water; The H that electrolysis produces
2tungsten powder is prepared for restoring tungsten oxide.The present invention can realize efficiently processing tungsten mineral material and prepare tungsten powder, provides cost savings, and discharges without ammonia nitrogen waste water.
Description
Technical field
The present invention relates to the technological method in rare metal Extraction metallurgy field, particularly Tungsten smelting.
Background technology
NaOH decomposition method is due to strong to adaptability to raw material, and rate of decomposition is high and become the prevailing technology of existing process tungsten mineral material.But in real tungsten smelting process, obtain high tungsten leaching yield, the consumption of NaOH is very large.Such as, during process wolframite, when obtain the leaching yield of 99%, the consumption of NaOH is 1.5 ~ 2 times of theoretical amount; And when processing white tungsten fine ore, NaOH consumption even reaches 3 ~ 4 times of theoretical amount.
As everyone knows, NaOH is obtained by electrolysis NaCl in chlorine industry.In NaCl electrolytic process, cathode compartment produces NaOH and H
2, anolyte compartment produces Cl
2.Directly obtained being concentration by electrolysis be about 30% NaOH solution, this may be used for Decomposition of Tungsten, but conveniently accumulating, also needs, by evaporative crystallization, NaOH is made solid caustic soda.Because NaOH hydration heat is large, evaporative process needs to consume a large amount of energy; In addition due to industrial large to NaOH demand, and H
2and Cl
2market demand relatively little, cause NaOH substantial appreciation of prices, in fact H
2and Cl
2production cost is also transferred on NaOH product directly or indirectly.
NaOH holds at high price, and causes Tungsten smelting cost increase.Therefore in the urgent need to the comprehensive lifting by Technology, reduce costs, enhance the competitiveness.
Existing tungsten smelting process obtains sodium tungstate solution by NaOH decomposition of tungsten mineral raw material, adsorb or extraction tungsten through ion exchange method or solvent extration again, then use ammonia solution to carry out desorb or back extraction obtains ammonium tungstate solution, final evaporation crystallization ammonium tungstate solution obtains APT.Although whole technique is an extremely successful and ripe technique, but because employ ammonia in transformation process, inevitably produce the waste water (China in discharge of wastewater ammonia nitrogen concentration restriction very strict, national grade one discharge standard for be less than 15mg/L) of large volume low-concentration containing ammonia nitrogen.But the Low Concentration Ammonia Containing Wastewater produced in tungsten smelting process there is no effective treatment process at present.For this reason, some enterprise only does preliminary treatment even do not process direct discharge for reducing costs, and seriously causes water pollution.
In fact break point chlorination method can efficiently by the NH in solution
4 +be oxidized to N
2, the object thoroughly removing ammonia nitrogen in waste water can be reached, be used widely in sanitary sewage disposal.But owing to buying Cl specially on the one hand
2need additional cost again, even if the content of ammonia nitrogen, also far above sanitary sewage (decades of times), causes Cl again in the Tungsten smelting waste water of another aspect " lower concentration "
2consumption rises violently and is difficult to bear, and considers to process Tungsten smelting waste water by chlorine oxidation so unmanned so far.Obviously how the acquisition Cl of low cost
2crucial.
In addition, ammonium tungstate solution crystallization obtains APT(ammonium paratungstate) become Tungsten oxide 99.999 through calcining again, also need through H
2reduction just can make tungsten powder.The approach of traditional acquisition hydrogen passes through water electrolysis exactly.Therefore in order to obtain H
2, Tungsten smelting factory also needs to build complicated water electrolysis hydrogen production system, and be again the electrowinning process of one power consumption, production cost is high.Therefore, the acquisition H of how low cost
2that another is crucial.
By above analysis, be limited to different operation in the past and mutually split the limitation considered a problem, cause cost to remain high.And if tungsten metallurgy integrally can be considered, then can simplify literary writing by leaving out superfluous words, reduce costs.
If can obtain NaOH solution at Tungsten smelting plant site electrolysis NaCl, be directly used in leaching tungsten mineral material, then NaOH need not pass through irrational high energy consumption process of " by solution to solid caustic soda, then being mixed with solution again " again, and the Cl produced
2also oxide treatment ammonia nitrogen waste water can be directly used in, the H simultaneously produced
2can also be used for reduction and prepare tungsten powder, then whole Tungsten smelting technological process just can realize clean and effective production.
Summary of the invention
The object of this invention is to provide a kind of Tungsten smelting method of high-efficiency cleaning.
A Tungsten smelting method for high-efficiency cleaning, comprises the following steps:
(1) first by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, anolyte compartment obtains Cl
2;
(2) again the NaOH solution that step (1) electrolysis obtains is prepared sodium tungstate solution for leaching tungsten mineral material;
(3) step (2) is obtained sodium tungstate solution is treated again obtains ammonium tungstate solution;
(4) by Cl that step (1) electrolysis obtains
2the ammonia nitrogen be used in oxidation removal Tungsten smelting waste water;
(5) by the H of step (1) electrolysis generation
2tungsten powder is prepared for restoring tungsten oxide.
The NaOH solution concentration that described electrolysis obtains is 20% ~ 40%, is directly used in leaching tungsten mineral material.
Described tungsten mineral material comprises wolframite, white tungsten fine ore, Scheelite-Wolframite Mixed Mine, black tungsten ore or scheelite middling, and tungsten minerals is containing WO
3be 10% ~ 76%.
The mode that described sodium tungstate solution process obtains ammonium tungstate solution comprises ion exchange method or solvent extration.
Described Tungsten smelting waste water comprises liquid and washings after ion-exchange, one or more in raffinate and washings.
Before adopting ion exchange method or solvent extration in aforesaid method, adopt hcl acidifying sodium tungstate solution, after ion-exchange, liquid or raffinate are NaCl solution; Through Cl
2after oxidation removal ammonia nitrogen, part returns the electrowinning process of step (1) after returning or concentrating.
Described H
2tungsten powder is prepared after drying for restoring tungsten oxide.
Described Tungsten oxide 99.999 is obtained by calcining APT.
Described APT is obtained by ammonium tungstate solution evaporative crystallization, the NH that evaporation produces
3desorb when preparing ammonium tungstate solution for step (3) or back extraction is returned after absorbing; Or pass into Cl again after first ammonium tungstate solution being evaporated part solution
2or do not evaporate and directly pass into Cl
2gas, becomes N by ammonium oxidation
2while in and crystallization obtain APT.
The Tungsten smelting method of the high-efficiency cleaning that the present invention proposes, its particular content is as follows:
(1) in tungsten hydrometallurgy factory, set up workshop, produce NaOH, H
2and Cl
2, concrete: by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, anolyte compartment obtains Cl
2;
(2) NaOH solution that electrolysis obtains is directly used in leaching tungsten mineral material and prepares sodium tungstate solution.The NaOH solution concentration that described electrolysis obtains is 20% ~ 40%, can be directly used in leaching tungsten mineral material.Described tungsten mineral material comprises wolframite, white tungsten fine ore, Scheelite-Wolframite Mixed Mine, black tungsten ore, scheelite middling etc., and tungsten minerals is containing 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 process again; Ion exchange method can by rear for sodium tungstate solution dilution and strongly basic anion exchange resin Contact-sorption; Or can adopt by after direct for sodium tungstate solution acidifying with ion exchange resin or extraction agent Contact-sorption or extract tungsten.The acid that acidifying adopts 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 weakly alkaline extraction agent.
(3) when adopting ion exchange method and solvent extration, after hcl acidifying sodium tungstate solution, after ion-exchange, liquid or raffinate are NaCl solution, then through Cl
2after oxidation removal ammonia nitrogen, part returns electrowinning process after returning or concentrating.
(4) Cl that obtains of electrolysis
2the ammonia nitrogen be used in oxidation removal Tungsten smelting waste water.The ammonia nitrogen waste water produced in described tungsten smelting process comprises liquid and washings, raffinate and washings after ion-exchange.
(5) ammonium tungstate solution evaporative crystallization is obtained APT, the NH that evaporation produces
3return for desorb or back extraction after absorbing.Or pass into Cl again after first ammonium tungstate solution being evaporated part solution
2or do not evaporate and directly pass into Cl
2gas, becomes N by ammonium oxidation
2while in and crystallization obtain APT.Tungsten oxide 99.999 will be obtained after obtaining APT calcining.By the H that electrolysis produces
2tungsten powder is prepared after drying for restoring tungsten oxide.
Technical superiority of the present invention
Chlorine industry and Tungsten smelting technique organically combine by advantage major embodiment of the present invention, by the method produced in real time with use, by the NaOH solution that chloralkali process is produced, and Cl
2and H
2be directly used in the tungsten minerals leaching in tungsten smelting process, Ammonia Wastewater Treatment and reduction and prepare tungsten powder, main advantage is embodied in:
(1) NaOH solution (do not need first evaporative crystallization to make solid caustic soda, then transport extemporaneous preparation solution to) that electrolysis produces can be directly used in tungsten ore and leach, and greatly reduces the cost of NaOH, reduces the cost that tungsten ore leaches;
(2) Cl of by-product
2for the thorough process of ammonia nitrogen waste water, low cost realizes the zero release of ammonia nitrogen;
(3) can ad hoc hydrogen generating system again, adopt the H of by-product
2, reduce the cost that tungsten powder is prepared in reduction.
Cost compare calculates
Producing 1 ton of APT needs consumption NaOH to be about 0.6 ton, produces nitrogen-containing wastewater 80m
3(53m
3), be 300mg/L containing ammonia nitrogen; Also original production 1 ton of tungsten powder consumes hydrogen 31.6Kg.Only compare the operation that two kinds of method costs there are differences in computation process, mainly comprise NaOH consumption, tungsten powder hydrogen consumption cost is administered and reduced to ammonia nitrogen.
(1) traditionally:
The price buying 1 ton of solid NaOH is 3000 yuan, and buy the price 45 yuan/Kg of hydrogen, ammonia nitrogen treatment cost is 20 yuan/m
3(can't discharging standards 15mg/L be reached).
Produce alkali and ammonia nitrogen treatment cost=0.6 × 3000+80 × 20=3400 unit of 1 ton of APT
The consumption hydrogen cost=22.1 × 45=995 unit of 0.7 ton of tungsten powder is made after 1 ton of APT is sintered into 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
Produce 1 ton of 100%NaOH can obtain chlorine, the weight of hydrogen and the weight that consumes sodium-chlor and water and be respectively: chlorine 887.5kg, hydrogen 25kg, consumption salt 1462.5kg, water consumption 450kg.The power consumption producing 1 ton of solid caustic soda by chloralkali process be 2250Kwh(comprising steam consumption, and producing 1 ton of solid caustic soda, need to consume steam be 3.26 tons).Therefore, 1 ton of NaOH(liquid) cost be (comprising liquid caustic soda+0.888 ton of chlorine+25Kg hydrogen that 3.3 tons of concentration are 30%)=2250Kwh × 0.75 yuan/kwh(1 ton solid caustic soda)-3.26 × 120 yuan/ton of (steam)+1.463 × 400 yuan/ton (NaCl)+0.45 × 1.2 yuan/ton of (water)=1882 yuan.
1 ton of APT alkaline consumption 0.6 ton, ammonia nitrogen administer consumption chlorine 240Kg(administer after ammonia nitrogen concentration far below discharging standards 15mg/L), after being sintered into Tungsten oxide 99.999, reduction can obtain 0.7 ton of tungsten powder, needs hydrogen 22.1Kg.The chlorine produced by electrolysis just meets production 1 ton of APT process ammonia nitrogen waste water.Output 0.27 ton of NaOH and 6.76Kg hydrogen, also needs outsourcing 0.43 ton of NaOH and 15.34Kg hydrogen simultaneously.
Produce 1 ton of APT alkali and ammonia nitrogen treatment cost=0.27 × 1882+0.43 × 3000=1798 unit,
The consumption hydrogen cost=15.34 × 45=690 unit of 0.7 ton of tungsten powder is made after 1 ton of APT is sintered into Tungsten oxide 99.999
Amount to: 2488 yuan
(3) two method cost compares:
Administer and produce 0.7 ton of tungsten powder cost by this explained hereafter 1 ton of APT and ammonia nitrogen and can reduce=4395-2488=1907 unit
Accompanying drawing explanation
Fig. 1 is high-efficiency cleaning Tungsten smelting process flow sheet of the present invention.
Embodiment
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
By mass concentration be 26% NaCl solution carry out electrolysis, obtain the NaOH solution that concentration is 30%, the wolframite being doubly 60% with grade by theoretical consumption 1.5 reacts, liquid-solid ratio 0.9:1, temperature of reaction controls at 160 DEG C, and the reaction times is 2.0 hours, leaching yield reaches 99.2%, obtains the Na of 180g/L
2wO
4solution.By solution dilution to 25g/L, use 201 × 7 resins to adsorb, after washing completely, then use 5mol/LNH
4cl+2mol/LNH
3h
2o carries out desorb, and obtaining concentration is 256g/L ammonium tungstate solution.After ion-exchange, liquid and resin washings press Cl by break point chlorination method
2the amount being 1.02 with ammonia mol ratio in solution passes into Cl
2oxidation, makes ammonia nitrogen be transformed into N
2removing, in relief liquor, ammonia nitrogen concentration is 0.3mg/L.Ammonium tungstate solution is through evaporative crystallization, and crystallization control rate is 95% obtain APT, and APT reaches national 0 grade standard after testing.APT calcining obtains WO
3, then with electrolysis produce H
2reduction prepares tungsten powder after drying.
Embodiment 2
By mass concentration be 26% NaCl solution carry out electrolysis, obtain the NaOH solution that concentration is 28%, the sheelite being doubly 58% with grade by theoretical consumption 3.5 reacts, and solid-to-liquid ratio is 1:1, and temperature of reaction controls at 200 DEG C, and leaching yield reaches 98.5%, obtains the Na of 220g/L
2wO
4solution.Solution uses HCl adjust ph to 4.5, and use D301 resin to adsorb, after washing completely, then carry out desorb with the ammoniacal liquor of 25%, obtaining concentration is 256g/L ammonium tungstate solution.After ion-exchange, liquid and resin washings press Cl by break point chlorination method
2the amount being 1.03 with ammonia mol ratio in solution passes into Cl
2oxidation, makes ammonia nitrogen be transformed into N
2removing.After having reacted, after ion-exchange, the NaCl of liquid to be concentration be 112g/L, is evaporated to saturated returning again for electrolysis; In washings, ammonia nitrogen concentration is 0.2mg/L, directly discharge after neutralization.Ammonium tungstate solution after evaporating part water, then passes into Cl
2, while reoxidizing ammonia nitrogen, crystallization obtains APT, and percent crystallization in massecuite is 96%, reaches national 0 grade standard after testing.APT calcining obtains WO
3, then with electrolysis produce H
2reduction prepares tungsten powder after drying.
Embodiment 3
By mass concentration be 26% NaCl solution carry out electrolysis, obtain the NaOH solution that concentration is 28%, the sheelite being doubly 61% with grade by theoretical consumption 4.0 reacts, solid-to-liquid ratio is 1.1:1, temperature of reaction controls at 180 DEG C, and leaching yield reaches 98.7%, obtains the Na of 215g/L
2wO
4solution.Solution uses H
2sO
4adjust ph is to 4.2, and use D314 resin to adsorb, after washing completely, then carry out desorb with the ammoniacal liquor of 25%, obtaining concentration is 256g/L ammonium tungstate solution.Resin uses H
2sO
4for adsorbing tungsten after making the transition.Liquid after ion-exchange, resin washings and the rear liquid that makes the transition press Cl by break point chlorination method
2the amount being 1.1 with ammonia mol ratio in solution passes into Cl
2oxidation, makes ammonia nitrogen be transformed into N
2removing.After having reacted, liquid after handing over, washings is 0mg/L with ammonia nitrogen concentration in the rear liquid that makes the transition, and directly discharges after neutralization.Ammonium tungstate solution directly passes into Cl
2, while oxidation is except ammonia nitrogen, crystallization obtains APT, and percent crystallization in massecuite is 95.8%, reaches national 0 grade standard after testing.APT calcining obtains WO
3, then with electrolysis produce H
2reduction prepares tungsten powder after drying.
Embodiment 4
By mass concentration be 26.5% NaCl solution carry out electrolysis, obtain the NaOH solution that concentration is 33%, the Scheelite-Wolframite Mixed Mine being doubly 45% with grade by theoretical consumption 3.8 reacts, solid-to-liquid ratio is 1.2:1, temperature of reaction controls at 200 DEG C, and leaching yield reaches 99.1%, obtains the Na of 215g/L
2wO
4solution.Solution uses HCl adjust ph to 3.9, and use weakly alkaline extraction agent to extract, after washing completely, then carry out desorb with the ammoniacal liquor of 25%, obtaining concentration is 249g/L ammonium tungstate solution.For adsorbing tungsten after resin uses HCl to make the transition.Raffinate, washings and the rear liquid that makes the transition press Cl by break point chlorination method
2the amount being 1.25 with ammonia mol ratio in solution passes into Cl
2oxidation, makes ammonia nitrogen be transformed into N
2removing, ammonia nitrogen in solution concentration reduces to 0.22mg/L, discharge after neutralization.Ammonium tungstate solution directly passes into Cl
2, while oxidation is except ammonia nitrogen, crystallization obtains APT, and percent crystallization in massecuite is 94.9%, reaches national 0 grade standard after testing; Evaporative crystallization operation is returned after the impurity such as crystalline mother solution removing Pb, As Si.APT calcining obtains WO
2.9, then with electrolysis produce H
2reduction prepares tungsten powder after drying.
Embodiment 5
By mass concentration be 26.5% NaCl solution carry out electrolysis, obtain the NaOH solution that concentration is 33%, the black tungsten ore being doubly 25% with grade by theoretical consumption 3.8 reacts, and leaching yield reaches 97.8%, obtains the Na of 120g/L
2wO
4solution.Solution uses HCl adjust ph to 4.2, and use macroporous strong basic resin to adsorb, after washing completely, then carry out desorb with ammoniacal liquor, obtaining concentration is 220g/L ammonium tungstate solution.For adsorbing tungsten after resin uses HCl to make the transition.Liquid after ion-exchange, resin washings and liquid use Cl after transition
2oxidation, makes ammonia nitrogen be transformed into N
2removing.After having reacted, after ion-exchange, the NaCl solution of liquid to be concentration be 98g/L, returns after evaporation concentration for electrolysis; Washings is 0mg/L with ammonia nitrogen concentration in the rear liquid that makes the transition, and part returns the adjust ph for sodium tungstate solution, the rear directly discharge of all the other neutralizations.Directly by Cl
2evaporative crystallization operation is returned after the impurity such as be passed in ammonium tungstate solution, crystallization obtains APT while oxidation is except ammonia nitrogen, crystalline mother solution removing Pb, As Si.APT calcining obtains WO
2.72, then with electrolysis produce H
2reduction prepares ultrafine tungsten powder after drying.
Embodiment 6
The Cl that electrolysis is obtained
2be passed into waste water (from tungsten smelting process) that ammonia nitrogen concentration is 3.5g/L and ammonia nitrogen concentration is in the waste water (from rare-earth smelting process) of 13g/L, Cl
2intake is 1.02 times of theoretical amount, makes ammonia nitrogen be transformed into N
2removing.After having reacted, ammonia nitrogen in solution concentration reduces to 0.82mg/L and 13.26mg/L respectively, and gained acidic solution is qualified discharge after neutralization.
Claims (10)
1. a Tungsten smelting method for high-efficiency cleaning, is characterized in that, comprise the following steps:
(1) first by electrolysis NaCl solution, cathode compartment obtains NaOH and H
2, anolyte compartment obtains Cl
2;
(2) again the NaOH solution that step (1) electrolysis obtains is prepared sodium tungstate solution for leaching tungsten mineral material;
(3) step (2) is obtained sodium tungstate solution is treated again obtains ammonium tungstate solution;
(4) by Cl that step (1) electrolysis obtains
2the ammonia nitrogen be used in oxidation removal Tungsten smelting waste water;
(5) by the H of step (1) electrolysis generation
2tungsten powder is prepared for restoring tungsten oxide.
2. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 1, is characterized in that: the NaOH solution concentration that described electrolysis obtains is 20% ~ 40%, is directly used in leaching tungsten mineral material.
3. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 1 and 2, is characterized in that: described tungsten mineral material comprises wolframite, white tungsten fine ore, Scheelite-Wolframite Mixed Mine, black tungsten ore or scheelite middling, and tungsten minerals is containing WO
3be 10% ~ 76%.
4. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 1, is characterized in that: the mode that described sodium tungstate solution process obtains ammonium tungstate solution comprises ion exchange method or solvent extration.
5. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 4, is characterized in that: described Tungsten smelting waste water comprises liquid and washings after ion-exchange, one or more in raffinate and washings.
6. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 4 or 5, is characterized in that: before adopting ion exchange method or solvent extration, and adopt hcl acidifying sodium tungstate solution, after ion-exchange, liquid or raffinate are NaCl solution; Through Cl
2after oxidation removal ammonia nitrogen, part returns the electrowinning process of step (1) after returning or concentrating.
7. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 1, is characterized in that: described H
2tungsten powder is prepared after drying for restoring tungsten oxide.
8. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 1 or 7, is characterized in that: described Tungsten oxide 99.999 is obtained by calcining APT.
9. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 8, is characterized in that: described APT is obtained by ammonium tungstate solution evaporative crystallization, the NH that evaporation produces
3desorb when preparing ammonium tungstate solution for step (3) or back extraction is returned after absorbing.
10. the Tungsten smelting method of a kind of high-efficiency cleaning according to claim 8, is characterized in that: described APT passes into Cl after first ammonium tungstate solution being evaporated part solution again
2or do not evaporate and directly pass into Cl
2gas, becomes N by ammonium oxidation
2while in and crystallization obtain APT.
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