CN104372169B - Method of extracting tungsten from high-barium tungsten ore - Google Patents
Method of extracting tungsten from high-barium tungsten ore Download PDFInfo
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- CN104372169B CN104372169B CN201410734362.3A CN201410734362A CN104372169B CN 104372169 B CN104372169 B CN 104372169B CN 201410734362 A CN201410734362 A CN 201410734362A CN 104372169 B CN104372169 B CN 104372169B
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- tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method of extracting tungsten from high-barium tungsten ore. The method includes: mixing the high-barium tungsten ore and a certain amount of SiO2 and Na2CO3 to obtain mixture, roasting the mixture at the high temperature, and leaching roasting slag with Na2CO3 to obtain tungsten. By roasting the Na2CO3 and SiO2, the structure of the high-barium tungsten ore is fully broken to obtain stable (Ba or Ca)2SiO4 slag which is leached with high-concentration Na2CO3, water-soluble calcium and barium ions in roasting material are deposited, deposition of tungsten ions is prevented, leaching rate of the tungsten is greatly increased, reaching greater than 95%, and the problem that the high-tension alkaline leaching methods of the prior art fail to break the barite structure, leading to low leaching rate, is solved. The method according to the technical scheme is simple to operate, raw materials are cheap, processing can be performed with traditional equipment, and the method fully satisfies industrial production.
Description
Technical field
The present invention relates to a kind of method extracting tungsten from high barium tungsten ore, belong to tungsten ore technical field of smelting.
Background technology
The main raw materials for metallurgy of tungsten is wolframite and scheelite, but the exploitation year by year with tungsten resource, it presents grade
Reduce, group sub-agencies complicated and with other metal associations etc. so that the ore dressing of tungsten resource and smelting cost raise.
Process now wolframite and the common method of scheelite is soaked for high pressure base, this technique is in high-alkali, high-temperature and high-pressure conditions
Under, tungsten ore can be made to be decomposed, and make W content in slag be reduced to less than 1～3%, but needed for this technique, condition and equipment are severe
Carve, and this technique can not destroy barite structure, be not suitable with to containing high barium tungsten ore.
Similarly for sour decomposition method, due to BaSO4Insoluble in acid, and part barite and white tungsten composition dispersion exist,
Even if therefore the heteropoly acid processing method mentioned in patent is also inapplicable.
And the common processing method containing high barium material, then the method adopting pyrocarbon reduction, by BaSO4Reduction generates molten
BaS or BaCl in water2(adding chlorinating agent in reduction), thus destroying barite structure, reaches the extraction of object element.
Content of the invention
The defect existing for the technology extracting tungsten in prior art from high barium tungsten ore, the purpose of the present invention is to be to carry
High barium tungsten ore structure can effectively be destroyed for one kind, the method efficiently leaching tungsten ore, the method is simple to operate, and low cost meets work
Industry production requirement.
The invention provides a kind of from high barium tungsten ore extract tungsten method, the method be by high barium tungsten ore pulverize after, with
Silicate and/or SiO2, and Na2CO3Mix homogeneously, after carrying out roasting under conditions of temperature is 800～1000 DEG C, roasting
Slag is not less than the Na of 8g/L using concentration2CO3Solution leaches, and obtains sodium tungstate solution；Wherein, silicate and/or SiO2Quality
With SiO2Measure 5～20% for high barium tungsten ore quality；Na2CO3Mole be 2～4 times of tungsten mole in high barium tungsten ore.
The method extracting tungsten from high barium tungsten ore of the present invention also includes following preferred version：
Preferably in scheme, roasting time is 2～3h.
Preferably in scheme, high barium tungsten ore is crushed to granularity in 74～200 μ m.
Preferably leach in scheme is to carry out under conditions of temperature is 20～90 DEG C；Most preferably in 50～90 DEG C of bar
Carry out under part.
Preferably in scheme, extraction time is 0.5～3h；Most preferably 0.5～1h.Extraction time is more than 1h, tungsten leaching rate
Almost unchanged.
Preferably in scheme, fired slags adopt Na2CO3Solution is crushed to granularity in the range of 0.1mm～1mm before leaching.This
A large amount of gases can be produced, fired slags are in cellular, therefore fired slags only need to be crushed to 0.1mm～1mm is in the roasting process of invention
Can reach good leaching effect.
Preferably in scheme, sodium tungstate solution passes through ion exchange or extracting process extracts tungsten.
Described high barium tungsten ore contains higher barite composition, and the dispersion of barite composition exists in tungsten ore or parcel tungsten
Ore deposit.
Silicate and/or SiO preferably in scheme2Addition made according to the number of actual silicone content in high barium tungsten ore
Suitably adjust.
The technological difficulties that the present invention solves：The technique that inventor extracts tungsten to high barium tungsten ore makes substantial amounts of experimentation,
Research finds to add appropriate Na in high barium tungsten ore roasting process2CO3And SiO2(or silicate), can effectively destroy former height
The structure (original structure is that barite by tungsten ore parcel or is dispersed in tungsten ore) of barium tungsten ore, makes Ba, the Ca in high barium tungsten ore
Form more stable (Ba, Ca) with Si2SiO4, adopt the sodium carbonate liquor of high concentration to leach simultaneously, can effectively prevent CaSiO3
Deng dissolving, and suppression tungsten precipitation further, substantially increase the leaching rate of tungsten.Technical scheme efficiently solves existing
There is high barium tungsten ore structure in technology to be difficult to destroy, lead to the low problem of tungsten leaching rate.
The beneficial effect that the hinge structure present invention brings：1st, fully achieve the low-grade high barium tungsten ore being difficult by
The high efficiency extraction of middle tungsten；2nd, the adjuvant additive adopting is cheap, and process is simple can be processed using legacy equipment, completely
Meet industrialization production requirements.
Brief description
【Fig. 1】For the XRD figure of leached mud in embodiment 1, wherein, B is Ba1.55CaO0.45SiO4, W is BaWO4, P is W2O3
(PO4)2.
【Fig. 2】XRD figure for leached mud in embodiment 2.
【Fig. 3】XRD figure for leached mud in comparative example 1.
【Fig. 4】XRD figure for leached mud in comparative example 2.
Specific embodiment
Further illustrate with reference to example, following instance is intended to further illustrate the present invention and not enters one to invent
Step limits.
Embodiment 1
Take a certain high barium tungsten ore 500g (its component analysis such as table 1), be crushed to granularity in 74～200 μ m, with
270gNa2CO3And 40gSiO2After mix homogeneously, put into corundum crucible, in 850 DEG C of Muffle kiln roasting 3h.Calcining is cooled,
Be crushed to granularity be 0.1mm～1mm after, with 10g/L NaCO3Solution, liquid-solid ratio controls in 5mL/g, 60 DEG C leaching 1h.Institute
Obtain sodium tungstate solution and pass through ion exchange or extracting process extraction tungsten.
Composition/the % of the high barium white tungsten concentrate of table 1
After leaching, analyze the W content in leachate and leached mud, ammonium acetate therein such as table 2, tungsten leaching rate is
95.96%, leached mud XRD figure such as Fig. 1.Roasting process Ca, Ba, Si form relatively stable (Ca, Ba)2SiO4, leached mud XRD
Figure such as Fig. 1, the formation of this material directly illustrates that the method can destroy BaSO4Structure, during can reducing turnover simultaneously
The W that white tungsten precipitation causes is lost high problem.
Table 2 ammonium acetate is analyzed
Embodiment 2
Take a certain high barium tungsten ore 500g (its component analysis such as table 1), be crushed to granularity in 74～200 μ m, with
270gNa2CO3And 70gSiO2After mix homogeneously, put into corundum crucible, in 950 DEG C of Muffle kiln roasting 2h.Calcining is cooled,
Be crushed to granularity be 0.1mm～1mm after, with 20g/LNaCO3Solution, liquid-solid ratio controls in 4mL/g, 60 DEG C leaching 1h.Leach
Afterwards, analyze the W content in leachate and leached mud, the leaching rate obtaining is 96.76%, and its leached mud XRD figure such as Fig. 2.Institute
Obtain sodium tungstate solution and pass through ion exchange or extracting process extraction tungsten.
Comparative example 1
And when sintering temperature is less than 800 DEG C, as follows using the method Roasting And Leaching tungsten result：
Take a certain high barium tungsten ore 50g (its component analysis such as table 1), be crushed to granularity in 74～200 μ m, with
27gNa2CO3And 5gSiO2After mix homogeneously, put into corundum crucible, in 700 DEG C of Muffle kiln roasting 3h.Calcining is cooled, breaks
Be broken to granularity be 0.1mm～1mm after, in NaCO3In 10g/L solution, liquid-solid ratio controls in 5mL/g, leaches 1h at 60 DEG C.Leach
Afterwards, analyze the W content in leachate and leached mud, the leaching rate obtaining is 65.61%, and its leached mud XRD figure such as Fig. 3.Institute
Obtain sodium tungstate solution and pass through ion exchange or extracting process extraction tungsten.
Comparative example 2
And roasting is when being not added with silicon, take a certain high barium tungsten ore 50g (its component analysis such as table 1), be crushed to granularity 74～
200 μ m, with 27g Na2CO3After mix homogeneously, put into corundum crucible, in 850 DEG C of Muffle kiln roasting 3h.Calcining is through cold
But, be crushed to granularity be 0.1mm～1mm after, in NaCO3In the solution of 10g/L, liquid-solid ratio controls in 5mL/g, leaches at 60 DEG C
1h.After leaching, analyze the W content in leachate and leached mud, the leaching rate obtaining is 55.72%, and its leached mud XRD figure is as schemed
4.Gained sodium tungstate solution passes through ion exchange or extracting process extracts tungsten.
Comparative example 3
During leaching, directly gone out with water logging, it is as follows that tungsten leaches result：
Take a certain high barium tungsten ore 50g (its component analysis such as table 1), be crushed to granularity in 74～200 μ m, with
27gNa2CO3And 5gSiO2After mix homogeneously, put into corundum crucible, in 850 DEG C of Muffle kiln roasting 3h.Calcining is cooled, breaks
It is broken to granularity for, after 0.1mm～1mm, liquid-solid ratio controls in 5mL/g, 60 DEG C of water leaches 1h.After leaching, analysis leachate and
W content in leached mud, the leaching rate obtaining is 89.56%.Gained sodium tungstate solution is carried by ion exchange or extracting process
Take tungsten.
Claims (6)
1. a kind of from high barium tungsten ore extract tungsten method it is characterised in that by high barium tungsten ore pulverize after, with silicate and/or
SiO2, and Na2CO3Mix homogeneously, after carrying out roasting under conditions of temperature is 800～1000 DEG C, fired slags adopt concentration not
Na less than 8g/L2CO3Solution leaches, and obtains sodium tungstate solution；Wherein, silicate and/or SiO2Quality with SiO2Measure and be
The 5～20% of high barium tungsten ore quality；Na2CO3Mole be 2～4 times of tungsten mole in high barium tungsten ore.
2. method according to claim 1 is it is characterised in that described roasting time is 2～3h.
3. method according to claim 1 is it is characterised in that described high barium tungsten ore is crushed to granularity at 74～200 μm
In the range of.
4. method according to claim 1 is it is characterised in that described leaching is under conditions of temperature is 20～90 DEG C
Carry out.
5. method according to claim 1 is it is characterised in that fired slags adopt Na2CO3Solution is crushed to granularity before leaching
In the range of 0.1mm～1mm.
6. the method according to any one of Claims 1 to 5 is it is characterised in that described sodium tungstate solution is handed over by ion
Change or extracting process extracts tungsten.
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| CN201410734362.3A CN104372169B (en) | 2014-12-04 | 2014-12-04 | Method of extracting tungsten from high-barium tungsten ore |
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| CN201410734362.3A CN104372169B (en) | 2014-12-04 | 2014-12-04 | Method of extracting tungsten from high-barium tungsten ore |
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| CN104372169B true CN104372169B (en) | 2017-02-22 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293556B (en) * | 2015-10-12 | 2017-03-01 | 中南大学 | Tungsten and the method comprehensively utilizing liquid after extraction is extracted from tungstenic sodium carbonate liquor |
| CN105296749A (en) * | 2015-10-29 | 2016-02-03 | 江西稀有稀土金属钨业集团有限公司 | Method and system for dissolving barium-containing tungsten ores |
| CN106011504B (en) * | 2016-07-05 | 2018-01-02 | 江西理工大学 | A kind of method for decomposing scheelite |
| CN107641724A (en) * | 2017-08-25 | 2018-01-30 | 洛阳栾川钼业集团股份有限公司 | One kind improves WO in scheelite3The method of leaching rate |
| CN109468453B (en) * | 2018-12-14 | 2020-09-11 | 中南大学 | Method for extracting tungsten from tungsten-containing raw material by using waste glass |
| JP7206009B2 (en) * | 2019-02-25 | 2023-01-17 | 三菱マテリアル株式会社 | How to recover tungsten |
| CN111057880A (en) * | 2019-12-27 | 2020-04-24 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
| CN114381618A (en) * | 2022-01-17 | 2022-04-22 | 江西理工大学 | Method for smelting tungsten ore |
| CN115072927B (en) * | 2022-08-01 | 2023-06-09 | 中南大学 | Method for recycling tungsten from tungsten smelting wastewater |
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2014
- 2014-12-04 CN CN201410734362.3A patent/CN104372169B/en not_active Expired - Fee Related
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| "用纯碱焙烧-浸出法从白钨精矿中提取钨";R.K.Paramguru等;《湿法冶金》;19921231(第2期);第33-37页 * |
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Granted publication date: 20170222 Termination date: 20211204 |