CN106868321A - It is a kind of to process the method that scheelite extracts tungsten - Google Patents
It is a kind of to process the method that scheelite extracts tungsten Download PDFInfo
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- CN106868321A CN106868321A CN201710171219.1A CN201710171219A CN106868321A CN 106868321 A CN106868321 A CN 106868321A CN 201710171219 A CN201710171219 A CN 201710171219A CN 106868321 A CN106868321 A CN 106868321A
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- China
- Prior art keywords
- scheelite
- tungsten
- naoh
- roasting
- extracts
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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
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The method that scheelite extracts tungsten is processed the invention discloses a kind of, and in particular to a kind of method that NaOH joint silica roasting scheelite extracts tungsten, comprise the following steps:Step one, scheelite granularity is ground to less than 200 mesh；Step 2, by the scheelite after grinding and solid NaOH and SiO2It is well mixed；Step 3, high temperature kiln roasting is placed in by the mixture that step 2 is obtained；Step 4, the calcining matter obtained to step 3 carries out water logging and obtains sodium tungstate solution.The method that NaOH of the present invention carries tungsten with silica mixed decomposition scheelite, overcome existing process and use the autoclave production intermittently operated for existing, the problem for having certain potential safety hazard, simultaneously, compared with the sodium carbonate sintering process Decomposition of Tungsten of early stage, reaction temperature is low nearly 200 DEG C, tungsten recovery rate improves about 5%, greatly reduces energy consumption and improves the utilization rate of valuable tungsten resource.
Description
Technical field
The present invention relates to mineral manufacture field, more particularly to a kind of method that tungsten is extracted from scheelite.
Background technology
The tungsten resource in the whole world nearly 70% is made up of scheelite.At present, with the continuous exhaustion of wolframite resource, scheelite is
Become the main raw material of industry.
Past, the conventional method for decomposing scheelite mainly has soda pressuring cooking method, hydrochloric acid leaching process and soda sintered method, by
In there is respective deficiency, it has been eliminated.The eighties in 20th century, ground as Central South University professor Li Honggui develops alkali hot-bulb
Technique, changes the view of " can not possibly process scheelite with NaOH decomposition methods in industrial conditions ", and caustic digestion scheelite
Theoretical and technique is progressively ripe and progressive, scheelite basic pressure digestion technique is progressively turned into the prevailing technology of Tungsten smelting industry, at present,
The Tungsten smelting enterprise in the whole nation nearly more than 95% uses the production breakdown scheelite.But the equipment that the method is used is autoclave, is still belonged to
High-tension apparatus, needs just to can guarantee that the decomposition of scheelite with 8-15 kilograms of pressure, there is certain potential safety hazard, meanwhile, production
Process is operated for intermittent one-pot, and the scale and efficiency of production are subject to certain restriction.Therefore, be badly in need of the new safety of exploitation,
Continuously, efficient tungsten ore decomposition technique.
In fact, China's first generation Tungsten smelting production technology-sodium carbonate sintering process, can be in 800-900 DEG C of condition of sintering temperature
Lower continuous decomposition scheelite, just can meet above-mentioned requirements in form, but several crucial problems need to solve.It is well known that
Sodium carbonate sintering process is used for smelting wolframite earliest, is also applied for processing scheelite, but when scheelite is processed, reaction generation
Calcium silicates and energy and Na2WO4Carry out secondary response and generate CaWO4, it is only 95% or so to cause tungsten ore resolution ratio, and can be produced big
The CO of amount2Greenhouse gases（《Non-ferrous extractive metallurgy handbook》Editorial board non-ferrous extractive metallurgies handbook-rare high-melting-point
Metal（On）[M] Beijing：Metallurgical industry publishing house, 2005:88-95）, therefore, decomposing scheelite using roasting method needs further
The resolution ratio of tungsten ore is improved, while solving CO2The generation of gas.
The content of the invention
Wide using scope it is an object of the invention to provide one kind, energy consumption is low, and resolution ratio is high, the hydrogen-oxygen of low production cost
Change the method that sodium carries tungsten with silica mixed decomposition scheelite.
To achieve the above object, the method that scheelite extracts tungsten is processed the invention provides a kind of, is comprised the following steps.
Step one, scheelite granularity is ground to less than 200 mesh.
Step 2, by the scheelite after grinding and solid NaOH and SiO2It is well mixed.
Step 3, high temperature kiln roasting is placed in by the mixture that step 2 is obtained.
Step 4, the calcining matter obtained to step 3 carries out water logging and obtains sodium tungstate solution.
Further, with WO3Meter, in the scheelite 30~70wt. of tungstenic %, NaOH consumptions for theoretical amount 1.0~
3.0 times, SiO2Consumption is 1.0-1.5 times of theoretical amount.
Further, in the step 3, at 600 ~ 800 DEG C, roasting time is controlled 1.0 ~ 3.0 for sintering temperature control
Hour.
Further, in the step 4, the liquid-solid ratio of leaching is 2:1~5:1；Extraction temperature is controlled in room temperature to 95
DEG C, extraction time was controlled at 3.0 ~ 5.0 hours.
Further, extraction temperature control is at 50 ~ 80 DEG C.
The beneficial effects of the invention are as follows：NaOH of the present invention carries tungsten with silica mixed decomposition scheelite
Method, reacts by by scheelite and solid sodium hydroxide and the baking mixed realization of silica；Compared with the prior art, overcome
The production intermittently operated existed using autoclave, the problem for having certain potential safety hazard, meanwhile, the sodium carbonate sintering process with early stage
Decomposition of Tungsten is compared, and reaction temperature is low nearly 200 DEG C, and tungsten recovery rate improves about 5%, is greatly reduced energy consumption and is improve valuable tungsten
The utilization rate of resource.
Brief description of the drawings
The process chart of the method for the treatment scheelite extraction tungsten that Fig. 1 is provided for the present invention.
Fig. 2 is the XRD analysis detection figure of product of roasting in the present invention.
Specific embodiment
Classical theory --- the counterfeit ternary phase diagrams of scheelite is decomposed from NaOH, as long as the concentration foot of NaOH
Enough height, just can decompose scheelite under conditions of normal temperature and pressure, if the concentration of NaOH is improved to ultimate attainment, i.e. solid hydrogen
Sodium oxide molybdena, while mixing certain temperature, if equally decompose scheelite, forms the side of NaOH Roasting Decomposition scheelite
Method.Based on this imagination, after seminar is by white tungsten fine ore and NaOH batch mixing, it is placed in corundum crucible and is calcined, as a result sends out
Existing slag tungstenic is 3.88%, as a result unsatisfactory；And same dispensing is pressed, ceramic crucible is placed in, and roasted by same condition
During burning, slag tungstenic is only 0.25%, excellent.The difference of two experiments is only crucible material, by examination, two kinds of crucible materials
SiO in matter2Content ceramic crucible is far above corundum crucible.Therefore, according to identical white tungsten fine ore and NaOH charge ratio, together
When add a certain amount of SiO2, it is placed in corundum crucible, it is calcined under identical roasting condition, slag tungstenic is 0.28%, is further proved
SiO2Effect during NaOH Roasting Decomposition scheelite, product of roasting is detected as Na by XRD analysis2CaSiO4
（Na2O·CaO·SiO2）, be a kind of new ternary slag, rather than soda sintered method generation calcium silicates, thus, be inferred to this anti-
The equation answered is as follows.
CaWO4+4NaOH+SiO2=Na2WO4+Na2CaSiO4+2H2O
Found based on the studies above, the present invention proposes a kind of NaOH and carries the side of tungsten with silica mixed decomposition scheelite
Method, in order to more clearly state the present invention, is further described to the present invention below in conjunction with the accompanying drawings.
Refering to the method that Fig. 1, the NaOH that the present invention is provided carry tungsten with silica mixed decomposition scheelite, change
The technique for decomposing scheelite with NaOH solution in the prior art, uses NaOH solids and SiO instead2Solid roasting decomposes scheelite.
Specifically, comprise the following steps.
Step one, scheelite granularity is ground to less than 200 mesh, with WO3Meter, 30~70wt. of tungstenic in the scheelite
%。
Step 2, by the scheelite after grinding and solid NaOH and SiO2Well mixed, NaOH consumptions are the 1.0 of theoretical amount
~3.0 times, SiO2Consumption is 1.0-1.5 times of theoretical amount.
Step 3, high temperature kiln roasting is placed in by the mixture that step 2 is obtained；Sintering temperature is controlled at 600 ~ 800 DEG C,
Roasting time was controlled at 1.0 ~ 3.0 hours.
Step 4, the calcining matter obtained to step 3 carries out water logging and obtains sodium tungstate solution, wherein, the liquid-solid ratio of leaching is
2:1~5:1；Extraction temperature control is controlled at 3.0 ~ 5.0 hours in room temperature to 95 DEG C, extraction time.It is preferred that the extraction temperature
Control is at 50 ~ 80 DEG C.
It is below more specifically embodiment.
Embodiment 1：Certain white tungsten fine ore contains 62.45%WO3, granularity is -200 mesh.Ore deposit weight 100g, 2.0 times of theory NaOH use
Amount, 1 times of theory SiO2Consumption, 700 DEG C of roasting 2.0h, product of roasting adds water leaching, liquid-solid ratio 5:1, temperature 70 C, insulation
3h, filtering, washing, drying contains insoluble WO in slag3It is 0.26%, resolution ratio is up to 99.78%.
Embodiment 2：Contain 46.77%WO in certain scheelite3, granularity is -250 mesh.Ore deposit weight 80g, 2.5 times of theory NaOH consumptions,
1.3 times of theory SiO2Consumption, 800 DEG C of roasting 3h, product of roasting adds water leaching, liquid-solid ratio 4:1, temperature 50 C is incubated 4h,
Filtering, washing, drying contains insoluble WO in slag3It is 0.21%, resolution ratio is up to 99.85%.
Embodiment 3：Contain 52.36%WO in certain scheelite3, granularity is -250 mesh.Take above-mentioned ore deposit 150g, 1.5 times of theory NaOH
Consumption, 1.2 times of theory SiO2Consumption, 600 DEG C of roasting 1h, product of roasting adds water leaching, liquid-solid ratio 2:1, temperature is room
Temperature, is incubated 3.5h, and filtering, washing, drying contains insoluble WO in slag3It is 8.48%, resolution ratio is up to 93.76%.
Embodiment 4：Contain 35.71%WO in certain scheelite3, granularity is -300 mesh.Ore deposit weight 200g, 1.3 times of theory NaOH use
Amount, 1.5 times of theory SiO2Consumption, 650 DEG C of roasting 3h, product of roasting adds water leaching, liquid-solid ratio 3:1,80 DEG C of temperature, insulation
5h, filtering, washing, drying contains insoluble WO in slag3It is 0.33%, resolution ratio is up to 98.64%.
Can be drawn from above-mentioned test data, NaOH of the invention carries tungsten with silica mixed decomposition scheelite
Method, can any scheelite of efficient-decomposition, compared with existing alkali decomposition process, overcome using autoclave exist production intermittently
The problem of certain potential safety hazard is operated, has, meanwhile, compared with the sodium carbonate sintering process Decomposition of Tungsten of early stage, reaction temperature is low near
200 DEG C, tungsten recovery rate improves about 5%, greatly reduces energy consumption and improves the utilization rate of valuable tungsten resource.
These are only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Say, on the premise of the technology of the present invention principle is not departed from, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (5)
1. it is a kind of to process the method that scheelite extracts tungsten, it is characterised in that to comprise the following steps:
Step one, scheelite granularity is ground to less than 200 mesh；
Step 2, by the scheelite after grinding and solid NaOH and SiO2It is well mixed；
Step 3, high temperature kiln roasting is placed in by the mixture that step 2 is obtained；
Step 4, the calcining matter obtained to step 3 carries out water logging and obtains sodium tungstate solution.
2. the method that treatment scheelite according to claim 1 extracts tungsten, it is characterised in that with WO3Meter, the scheelite
Middle 30~70wt. of tungstenic %, NaOH consumption is 1.0~3.0 times of theoretical amount, SiO2Consumption is 1.0-1.5 times of theoretical amount.
3. the method that the treatment scheelite according to claim any one of 1-2 extracts tungsten, it is characterised in that in the step
In three, at 600 ~ 800 DEG C, roasting time was controlled at 1.0 ~ 3.0 hours for sintering temperature control.
4. the method that the treatment scheelite according to claim any one of 1-3 extracts tungsten, it is characterised in that in the step
In four, the liquid-solid ratio of leaching is 2:1~5:1；Extraction temperature control is in room temperature to 95 DEG C, and extraction time control is small 3.0 ~ 5.0
When.
5. the method that the treatment scheelite according to claim any one of 1-3 extracts tungsten, it is characterised in that in the step
In four, the liquid-solid ratio of leaching is 2:1~5:1；At 50 ~ 80 DEG C, extraction time was controlled at 3.0 ~ 5.0 hours for extraction temperature control.
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| CN201710171219.1A CN106868321B (en) | 2017-03-21 | 2017-03-21 | A method of processing scheelite extracts tungsten |
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| CN201710171219.1A CN106868321B (en) | 2017-03-21 | 2017-03-21 | A method of processing scheelite extracts tungsten |
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| CN106868321B CN106868321B (en) | 2018-11-02 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468453A (en) * | 2018-12-14 | 2019-03-15 | 中南大学 | A method of tungsten being extracted from tungstenic raw material using cullet |
| CN115353148A (en) * | 2022-08-31 | 2022-11-18 | 赣州有色冶金研究所有限公司 | Method for recovering sodium hydroxide from sodium tungstate alkali cooking liquor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011017A (en) * | 2010-11-19 | 2011-04-13 | 中南大学 | Method for extracting tungsten by decomposing tungsten minerals |
| CN104789772A (en) * | 2015-04-06 | 2015-07-22 | 桂林理工大学 | Energy-saving and consumption-reducing method for alkaline leaching of scheelite |
| CN105112691A (en) * | 2015-10-10 | 2015-12-02 | 江西理工大学 | Method for extracting tungsten from tungsten minerals through alkaline decomposition |
| CN105969977A (en) * | 2016-07-05 | 2016-09-28 | 江西理工大学 | Method for extracting tungsten from scheelite |
| CN106011504A (en) * | 2016-07-05 | 2016-10-12 | 江西理工大学 | Method for resolving scheelite |
-
2017
- 2017-03-21 CN CN201710171219.1A patent/CN106868321B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011017A (en) * | 2010-11-19 | 2011-04-13 | 中南大学 | Method for extracting tungsten by decomposing tungsten minerals |
| CN104789772A (en) * | 2015-04-06 | 2015-07-22 | 桂林理工大学 | Energy-saving and consumption-reducing method for alkaline leaching of scheelite |
| CN105112691A (en) * | 2015-10-10 | 2015-12-02 | 江西理工大学 | Method for extracting tungsten from tungsten minerals through alkaline decomposition |
| CN105969977A (en) * | 2016-07-05 | 2016-09-28 | 江西理工大学 | Method for extracting tungsten from scheelite |
| CN106011504A (en) * | 2016-07-05 | 2016-10-12 | 江西理工大学 | Method for resolving scheelite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468453A (en) * | 2018-12-14 | 2019-03-15 | 中南大学 | A method of tungsten being extracted from tungstenic raw material using cullet |
| CN115353148A (en) * | 2022-08-31 | 2022-11-18 | 赣州有色冶金研究所有限公司 | Method for recovering sodium hydroxide from sodium tungstate alkali cooking liquor |
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| CN106868321B (en) | 2018-11-02 |
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Granted publication date: 20181102 |