CN1219896C - Method of producing sodium tungstate solution using scheelite powder as raw material - Google Patents
Method of producing sodium tungstate solution using scheelite powder as raw material Download PDFInfo
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- CN1219896C CN1219896C CNB031178685A CN03117868A CN1219896C CN 1219896 C CN1219896 C CN 1219896C CN B031178685 A CNB031178685 A CN B031178685A CN 03117868 A CN03117868 A CN 03117868A CN 1219896 C CN1219896 C CN 1219896C
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- CN
- China
- Prior art keywords
- raw material
- sodium tungstate
- slip
- powder
- tungstate solution
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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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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a method for producing sodium tungstate solutions by using calcic tungsten mineral powder as a raw material. In the method, NaOH and H3PO4 in a low time amount of the Ca content in WO3 and CaWO4 of raw material mineral powder and a certain amount of Al2O3 and NaNO3 are added to be prepared into slurry; under the conditions of 0.4 to 0.9MPa and 140 to 180 DEG C, the slurry is stirred for decomposition treatment for 2 to 3 hours, and then through filtration for separation and washing for residue filtration, the target sodium tungstate solution is obtained. Since the present invention treats the raw material mineral powder by low-pressure and low-basicity thermal decomposition, the present invention has the advantages of scientific and accurate compounding, wide adaptive norm and high utilization rate of the raw materials, low slurry basicity, easy filtration and separation, high efficiency, good product quality, long service life of equipment, low production cost, favorable environmental protection, etc.; the present invention overcomes the defects of low background art decomposition rate and utilization rate, high slurry basicity, difficult filtration, easy corrosion of equipment, high product basic content, serious influence on the subsequent job, etc.
Description
Technical field
The invention belongs to a kind of production method of producing sodium tungstate solution from contain the scheelite powder, particularly a kind of low pressure, low alkali, thermal degradation of adopting is to produce the method for sodium tungstate solution.This method especially is suitable for from sheelite, and black, white tungsten mixings ore deposit and high seyrigite are raw material, produce sodium tungstate solution, for further production tungsten product provides intermediates.
Background technology
At publication number is CN1361296A, name is called in the patent documentation of " high calcium tungsten mineral is pressed and boiled decomposition method ", disclose a kind of tungsten minerals (powder) that contains high calcium under the condition that adds high concentration alkali, the method that pressurization, heating (soda boiling of promptly pressurizeing) are decomposed is to realize sheelite (CaWO
4) wait the decomposition of calcic tungsten minerals.Though this method has overcome the existing disadvantage of traditional hydrochloric acid decomposition method (being acid decomposition), but since this method be adopt to add high concentration alkali (NaOH concentration＞300g/l) and breeze under the pressure of 130～200 ℃ and 0.15～1.0MPa (pressure is boiled) decompose, and under high density free alkali (NaOH＞100g/l)) and 100 ℃ of left and right sides temperature timely filtering separation Na
2WO
4Thereby this technology exists white tungsten fine ore rate of decomposition and utilization of resources rate low again, slip basicity height, big, the filtration difficulty of viscosity, WO in the slag
3Content exceeds 1～12 times of raw material ore deposit grade up to 1.5～2.5%, and the erosion resistance of equipment is had relatively high expectations, work-ing life is shorter, production cost height and Na
2WO
4Free alkali concn height has a strong impact on the disadvantage such as carry out smoothly of subsequent job again in the solution.
Summary of the invention
The objective of the invention is defective at the background technology existence, it is a kind of to contain the method that the scheelite powder is the raw material production sodium tungstate solution to improve design, to improve the utilization ratio of decomposition efficiency and resource, the work-ing life of prolongation equipment, wide to the grade and the kind adaptation of mineral, filtering separation efficient height, and purpose such as boost productivity, reduce production costs.
Solution of the present invention is with raw material breeze and NaOH and H
3PO
4Mixing the back decomposes under the temperature and pressure that requires.Its principal reaction process is:
For the white tungsten (CaWO in the former fine ore powder
4):
For [(Fe, the Mn) WO of the black tungsten in the raw material breeze
4]:
In above-mentioned reaction process, be the SiO in the inhibition raw material ore deposit
2Leaching and promote the leaching of tungsten in the tungsten sulfide, add the Al of respective amount again
2O
3And NaNO
3Therefore, production method of the present invention comprises:
A, batching: behind calcareous raw material tungsten ore grinding fine tuning slurry, under whipped state, press WO in the raw material breeze
31.4～1.6 of theoretical consumption extraordinarily goes into NaOH, by CaWO
41.02～1.10 of the theoretical consumption of middle calcium contents is extraordinarily gone into H
3PO
4, and add Al respectively by 1～6% and 0.5～1.2% amount of raw material breeze weight
2O
3And NaNO
3And with the density of slip be adjusted into 1.55～1.60, basicity adjusts to 90～110g/l;
B, disaggregating treatment: in above-mentioned deployed slip input reactor, stir process is 2～3 hours under 0.4～0.9MPa pressure and 140～180 ℃ of conditions;
C, filtering separation: will import filter through the slip that disaggregating treatment finishes, and get sodium tungstate solution after filtration; Filter residue is then through no Ca
2+Water washing, filtration, its washings are incorporated slip filtrate into and are the object of the invention thing.
Above-mentioned calcareous raw material tungsten ore powder comprises white tungsten fine ore powder, middle grade sheelite powder, Scheelite-Wolframite Mixed Mine powder and high seyrigite powder; The granularity of various powders≤45 μ m.And in batching, also can directly adopt Na
3PO
4Replace H
3PO
4Add in the slip, the amount of its adding still is CaWO
4In 1.02～1.10 times of calcareous theoretical consumption; As Na with capacity
3PO
4Replace H
3PO
4Add fashionablely, the NaOH consumption that is added in the batching should be adjusted into by WO in the raw material breeze
30.3～0.6 times of theoretical consumption.And the described slip that finishes through disaggregating treatment, band is pressed output, heat filtering or is cooled to normal temperature and filters.
The present invention is owing to press WO in the raw material breeze in batching
3The NaOH and the CaWO of low times amount of content
4In the theoretical consumption of calcium contents (rather than with calcium contents in the raw material breeze) add H
3PO
4Or Na
3PO
4, when adding NaPO
4The time can turn down the consumption of NaOH according to its add-on.Thereby have batching science, accurate, raw material wide accommodation and effective rate of utilization height, basicity is low in the feed liquid; a little less than the corrodibility to equipment, filtering separation is easy, efficient is high; good product quality, service life of equipment is long, and production cost is lower and help characteristics such as environment protection.
Concrete real mode
Embodiment 1
Present embodiment is a raw material with the white tungsten fine ore powder:
A, batching:, wherein contain WO with granularity≤45 μ m
3: 70.61%, SiO
2: after 2.86% white tungsten fine ore 1500g sizes mixing, under whipped state, add NaOH:566g (WO
31.55 times of theoretical consumption), 85% H
3PO
4: 358g, granularity is the Al of 74 μ m
2O
3: 20g, NaNO
3: 15g, and pulp density transferred to 1.58, basicity 105g/l makes the slip of volume 3000ml;
B, disaggregating treatment: it is the reactor of 5000ml belt stirrer that above-mentioned slip is placed volume, under 165 ℃, 0.6MPa pressure, after 2 hours, is cooled to normal temperature with the rotating speed stirring reaction of 100r.p.m;
C, filtering separation: place vacuum filter to filter above-mentioned disaggregating treatment and the slip that is cooled to normal temperature, 2100mlNa
2WO
4Solution, WO in the solution
3Content 410g/l, free NaOH 42g/l, SiO
2: 0.12g/l, P:0.5g/l.Filter residue is washed through no calcium ion, and wash water is incorporated filtrate into, and slag is dried the 691g that weighs, insoluble WO in the slag
3Content 0.22%, rate of decomposition are 99.85%.This filter residue can be used as the fertile raw material of high-quality farming.
Embodiment 2:
It is raw material that present embodiment mixes the tungsten ore powder with the 1500g black and white, and wherein black tungsten accounts for 20%, white tungsten 80% (WO
3: 69.8%, SiO
2: 3.1%).
A, add WO in sizing mixing
3The H of the NaOH:523g:85% that theoretical consumption is 1.45 times
3PO
4: 288g, pulp density 1.60, basicity 158g/l, all the other and embodiment 1 get the 3000ml slip together;
B, disaggregating treatment temperature are 160 ℃, pressure 0.5MPa, treatment time 2.5 hours;
C, with above-mentioned slip band temperature, band press the input vacuum filter filter 2250mlNa
2WO
4Solution, WO in the solution
3Content 380g/l, free NaOH content 38g/l, SiO
2Content 0.14g/l, P content 0.25g/l; The heavy 668g of oven dry slag, insoluble WO in the slag
3Content 0.35%, rate of decomposition 99.8%.
Embodiment 3
Present embodiment is with grade sheelite powder (WO among the 1500g
3: SiO 45.0%,
2: 8%) be raw material, its processing parameter is:
Present embodiment is with grade sheelite powder (WO among the 1500g
3: SiO 45.0%,
2: 8%) be raw material, its processing parameter is:
The NaOH:372g, the 85%H that in former slip, add 1.5 times of theoretical consumptions
3PO
4: 257g, Al
2O
3: 75g, pulp density 1.59, basicity 110g/l, the 3000ml slip, all the other and disaggregating treatment etc. all with
Embodiment 1 together;
Filtering separation gets 1850mlNa
2WO
4Solution contains WO in the slag liquid
3: 370g/l, P content 0.47g/l, SiO
2Content: 0.08g/l, the filter residue dry weight 1109g after the washing, WO in the slag
3Be 0.15%, rate of decomposition is 99.75%.
Embodiment 4
Present embodiment is a raw material with the high seyrigite powder of 1500g, wherein: WO
3: SiO 71.0%,
2: 0.8%, Mo:0.3%.Its processing parameter is:
In former slip, add WO
3NaOH:553g, 85%H that theoretical expense is 1.5 times
3PO
4: 361g, Al
2O
3: 15g, NaNO
3: 15g is mixed with pulp density 1.58, basicity 92g/l, the slip of volume 3000ml; All the other parameters and processing step are all same with embodiment 1.
Filter 2260mlNa
2WO
4Solution, WO in the solution
3Content 405g/l, free alkali content 34g/l, P content 0.15g/l, SiO
2: 0.14g/l, washing back filter residue dry measure 689g, insoluble WO in the slag
3: 0.2%, rate of decomposition is 99.87%.
Claims (4)
1, a kind of to contain the method that the scheelite powder is the raw material production sodium tungstate solution; It is characterized in that this method comprises:
A, batching: behind calcareous raw material tungsten ore grinding fine tuning slurry, under whipped state, press WO in the raw material breeze
31.4～1.6 of theoretical consumption is extraordinarily gone into NaOH, presses CaWO
41.02～1.10 of the theoretical consumption of middle calcium contents is extraordinarily gone into H
3PO
4, and add Al respectively by 1～6% and 0.5～1.2% amount of raw material breeze weight
2O
3And NaNO
3And with the density of slip be adjusted into 1.55～1.60, basicity adjusts to 90～110g/l;
B, disaggregating treatment: in above-mentioned deployed slip input reactor, stir process is 2～3 hours under 0.4～0.9MPa pressure and 140～180 ℃ of conditions;
C, filtering separation: will import filter through the slip that disaggregating treatment finishes, and get sodium tungstate solution after filtration; Filter residue is then through no Ca
2+Water washing, filtration, its washings are incorporated slip filtrate into and are the object of the invention thing.
2, press the method for the described production sodium tungstate solution of claim 1; It is characterized in that described calcareous raw material tungsten ore powder comprises white tungsten fine ore powder, middle grade sheelite powder, Scheelite-Wolframite Mixed Mine powder and high seyrigite powder; The granularity of various powders≤45 μ m.
3, press the method for the described production sodium tungstate solution of claim 1; It is characterized in that in batching, directly adopting Na
3PO
4Replace H
3PO
4Add in the slip, the amount of its adding still is CaWO
4In 1.02～1.10 times of calcareous theoretical consumption; As Na with capacity
3PO
4Replace H
3PO
4Add fashionablely, the NaOH consumption that is added in the batching should be adjusted into by WO in the raw material breeze
30.3～0.6 times of theoretical consumption.
4, press the method for the described production sodium tungstate solution of claim 1; It is characterized in that the slip that finishes through disaggregating treatment, band is pressed output, heat filtering or is cooled to normal temperature and filters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031178685A CN1219896C (en) | 2003-05-16 | 2003-05-16 | Method of producing sodium tungstate solution using scheelite powder as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031178685A CN1219896C (en) | 2003-05-16 | 2003-05-16 | Method of producing sodium tungstate solution using scheelite powder as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1455008A CN1455008A (en) | 2003-11-12 |
| CN1219896C true CN1219896C (en) | 2005-09-21 |
Family
ID=29260197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031178685A Expired - Fee Related CN1219896C (en) | 2003-05-16 | 2003-05-16 | Method of producing sodium tungstate solution using scheelite powder as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1219896C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328540B (en) * | 2008-08-01 | 2012-05-23 | 自贡硬质合金有限责任公司 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
| CN104843791B (en) * | 2015-05-06 | 2017-06-13 | 江西稀有金属钨业控股集团有限公司 | A kind of method for processing tungsten contained material |
| CN106745631B (en) * | 2017-01-04 | 2020-02-14 | 江西理工大学 | Method for removing fluorine and arsenic in tungsten smelting wastewater |
| CN108823434A (en) * | 2018-06-11 | 2018-11-16 | 成都虹波钼业有限责任公司 | A kind of molybdenite removes tungsten method |
| CN113684380B (en) * | 2021-08-30 | 2023-04-07 | 中南大学 | Tungsten extraction process and application thereof |
-
2003
- 2003-05-16 CN CNB031178685A patent/CN1219896C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1455008A (en) | 2003-11-12 |
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Granted publication date: 20050921 Termination date: 20140516 |