CN109988923A - A kind of tungsten separation method - Google Patents
A kind of tungsten separation method Download PDFInfo
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- CN109988923A CN109988923A CN201910246806.1A CN201910246806A CN109988923A CN 109988923 A CN109988923 A CN 109988923A CN 201910246806 A CN201910246806 A CN 201910246806A CN 109988923 A CN109988923 A CN 109988923A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B34/34—Obtaining molybdenum
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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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- 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 kind of tungsten separation methods.It is the following steps are included: acid adding, adjusting pH are 6-9 into high concentration tungsten solution；Again plus ammonium salt stirs；After the completion of dissolution, it is stored at room temperature；Ammonium paratungstate sodium double salt precipitation is obtained by filtration, acid adding, which filters, is made wolframic acid；The mother liquor of the ammonium paratungstate sodium double salt precipitation is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.Method of the invention is easy to operate, and generated ammonium sodium double salt precipitation processing is easy, can be converted into wolframic acid product using room temperature tune acid.Tungsten good separating effect, resulting ammonium sodium double salt precipitation tungsten mass ratio are (200~500): 1, direct yield is up to 80~95%.
Description
Technical field
The present invention relates to metallurgy of rare metal field, in particular to a kind of tungsten separation method.
Background technique
Due to lanthanide contract, tungsten and molybdenum atomic structure having the same and show very similar chemical property.Therefore,
Tungsten is in the frequent symbiosis of nature.With the continuous exploitation of tungsten resource, high-quality tungsten concentrate is gradually decreased, the higher tungsten ore containing molybdenum
The primary raw material of tungsten metallurgy will be become, therefore tungsten separates the importance of this project and urgency increasingly shows.
The extremely similar chemical property of tungsten causes tungsten to efficiently separate the technical problem for becoming puzzlement tungsten metallurgy.At present
It has made a breakthrough in some fields, has developed some tungsten separation methods.Utilize thiomolybdate ion and tungstate ion
Matter difference is separated using the precipitation method, extraction or ion-exchange.Such method other than there is sulphur pollution,
There is also removing, molybdenum depth is inadequate, or the inadaptable high molybdenum solution of processing, inefficient problem.
Currently it is directed to magnanimity tungsten separating technology, the selective precipitation method, as CN101565778B utilizes tungsten certain
Property is different within the scope of PH, and the bivalent compound of manganese is added and tungsten is preferentially produced precipitating, obtains molybdate solution and rich tungsten slag, rich
Tungsten slag carries out high temperature and pressure decomposition referring to wolframite decomposition method, obtains sodium tungstate solution, to realize that tungsten separates.This method
Gained richness tungsten slag subsequent decomposition has certain slag tungstenic, and there are tungsten damages, and tungsten separation degree is not high, in production practices, gained
Ammonium molybdate solution molybdenum tungsten mass ratio be about 5-40:1, and sodium tungstate solution tungsten than be about 10-20:1.This part feed liquid carries out
Successive depths separation costs are higher.
Therefore, based on the above analysis, it is very necessary to develop new magnanimity tungsten isolation technics.
Summary of the invention
The purpose of the present invention is to provide a kind of efficient tungsten separation methods, are particularly suitable for processing high concentration tungsten mixing
Solution.This method considers the production technology of tungsten product, and the tungsten separated or molybdenum is made to be directly used in the preparation of its product, point
Good from effect, operating process is simple and easy to control, is easy to industrial application.
To achieve the above object, the present invention provides a kind of tungsten separation method, which comprises the following steps:
PH: the acid adding into high concentration tungsten solution is adjusted, adjusting pH is 6-9；The tungsten concentration of the high concentration tungsten solution
For 150-400g/l, molybdenum concentration 5-50g/l；
Add ammonium salt: in Xiang Shangshu acquired solution plus ammonium salt stirs；After the completion of dissolution, it is stored at room temperature；
It obtains wolframic acid: refiltering to obtain ammonium paratungstate sodium double salt precipitation, acid adding, which filters, is made wolframic acid；
Obtain ammonium tetramolybdate: the mother liquor of the ammonium paratungstate sodium double salt precipitation is ammonium molybdate solution, through heavy obtained four molybdenums of acid
Sour ammonium.
Further, in the adjusting pH step, the high concentration tungsten solution is concentrated by evaporation to obtain by the dense material of low tungsten.
Further, in the adjusting pH step, the acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
Further, in described plus ammonium salt step, the ammonium salt is one of ammonium chloride, ammonium sulfate and ammonium carbonate or several
Kind.
Further, in described plus ammonium salt step, the molar ratio of tungsten is (2~5) in the additional amount and solution of the ammonium salt: 1.
The ratio can guarantee tungsten sufficient crystallising precipitating while not waste ammonium salt, is higher than and is lower than this ratio, cannot make tungsten sufficient crystallising heavy
It forms sediment.
Further, in described plus ammonium salt step, described be stored at room temperature refers to and stands 6-30h at room temperature.
Further, described to obtain in wolframic acid step, the additional amount of the acid is rubbed with tungsten in ammonium paratungstate sodium double salt precipitation
You are than being (3~5): 1.To guarantee that wolframic acid is insoluble, the minimum 3:1 of molar ratio can be excessive in right amount, from avoiding wasting, saves
The about angle of cost, therefore select (3~5): 1.
Further, described to obtain in wolframic acid step, the acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
Tungsten good separating effect of the present invention, raw material tungsten mass ratio is about 10:1, resulting ammonium sodium double salt precipitation tungsten matter
Amount is than being (200~500): 1, direct yield is up to 80~95%.The resulting ammonium sodium double salt precipitation tungsten mass ratio of embodiment 1-5 is
(286~500): 1, direct yield is up to 86~95.2%.
Method of the invention is easy to operate, and generated ammonium sodium double salt precipitation processing is easy, can be turned using room temperature tune acid
Turn to wolframic acid product.
The cost consideration of the present invention production technology of tungsten product, makes the tungsten separated or molybdenum be directly used in its product
Preparation, it is successive good, it is at low cost, it is easy to industrial application.
Specific embodiment
The embodiment of the present invention is described below in detail, the examples of the embodiments are intended to be used to explain the present invention, and cannot
It is interpreted as limitation of the present invention.In the examples where no specific technique or condition is specified, described according to the literature in the art
Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to
Cross the conventional products of commercially available acquisition.
A kind of embodiment 1: tungsten separation method
Be concentrated by evaporation: the low dense material 500ml of tungsten obtained by low tungsten ore caustic digestion, tungsten concentration are 126.3g/l, tungsten mass ratio
For 11.5:1, it is concentrated by evaporation the solution 250ml, molybdenum concentration 21.9g/l that are 252.4g/l to tungsten concentration；
It adjusts pH: sulfuric acid being added into solution, is stirred to react, makes pH 7；
Add ammonium salt: 45g ammonium chloride stirring and dissolving is added；After the completion of dissolution, 26 DEG C of room temperature are stood for 24 hours.
Obtain wolframic acid: after the reaction was completed through the ammonium paratungstate sodium double salt precipitation that tungsten mass ratio is 286:1 is obtained by filtration, to
The dilute sulfuric acid 200ml of 500g/l is added in precipitating, stirs evenly, obtains wolframic acid through filtration washing after the reaction was completed, wolframic acid contains WO3
Amount is 55.4g, and the direct yield for calculating tungsten is 87.8%, and the mass ratio of tungsten is 286:1 in wolframic acid.
Obtain ammonium tetramolybdate: ammonium paratungstate sodium double salt precipitation mother liquor is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
A kind of embodiment 2: tungsten separation method
Be concentrated by evaporation: the low dense material 500ml of tungsten obtained by low tungsten ore caustic digestion, tungsten concentration are 103.2g/l, tungsten mass ratio
For 10:1, it is concentrated by evaporation the solution 170ml, molybdenum concentration 30.2g/l that are 302.5g/l to tungsten concentration；
It adjusts pH: hydrochloric acid being added into solution, is stirred to react, makes pH 7.5；
Add ammonium salt: 80g ammonium sulfate stirring and dissolving is added；After the completion of dissolution, 26 DEG C of room temperature are stood for 24 hours.
Obtain wolframic acid: after the reaction was completed through the ammonium paratungstate sodium double salt precipitation that tungsten mass ratio is 500:1 is obtained by filtration, to
The dilute sulfuric acid 200ml of 500g/l is added in precipitating, stirs evenly, obtains wolframic acid through filtration washing after the reaction was completed, wolframic acid contains WO3
Amount is 46.5g, and the direct yield for calculating tungsten is 90.4%, and the mass ratio of tungsten is 500:1 in wolframic acid.
Obtain ammonium tetramolybdate: ammonium paratungstate sodium double salt precipitation mother liquor is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
A kind of embodiment 3: tungsten separation method
Be concentrated by evaporation: the low dense material 500ml of tungsten obtained by low tungsten ore caustic digestion, tungsten concentration are 115.1g/l, tungsten mass ratio
For 8.7:1, it is concentrated by evaporation the solution 164ml for being 350.2g/l to tungsten concentration, molybdenum concentration 40.3 is g/l；
It adjusts pH: nitric acid being added into solution, is stirred to react, makes pH 8；
Add ammonium salt: 60g ammonium carbonate stirring and dissolving is added；After the completion of dissolution, it is cooled to 10 DEG C of reaction 6h.
Obtain wolframic acid: after the reaction was completed through the ammonium paratungstate sodium double salt precipitation that tungsten mass ratio is 388:1 is obtained by filtration, to
The dust technology 300ml of 200g/l is added in precipitating, stirs evenly, obtains wolframic acid through filtration washing after the reaction was completed, wolframic acid contains WO3
Amount is 54.7g, and the direct yield for calculating tungsten is 95.2%, and tungsten mass ratio is 388:1 in wolframic acid.
Obtain ammonium tetramolybdate: ammonium paratungstate sodium double salt precipitation mother liquor is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
A kind of embodiment 4: tungsten separation method
Be concentrated by evaporation: the low dense material 500ml of tungsten obtained by low tungsten ore caustic digestion, tungsten concentration are 98.6g/l, and tungsten mass ratio is
8:1 is concentrated by evaporation the solution 124.5ml, molybdenum concentration 49.5g/l that are 396.1g/l to tungsten concentration；
It adjusts pH: sulfuric acid being added into solution, is stirred to react, makes pH 9；
Add ammonium salt: 50g ammonium chloride stirring and dissolving is added；After the completion of dissolution, it is cooled to 10 DEG C of reaction 6h.
Obtain wolframic acid: after the reaction was completed through the ammonium paratungstate sodium double salt precipitation that tungsten mass ratio is 320:1 is obtained by filtration, to
The dust technology 400ml of 200g/l is added in precipitating, stirs evenly, obtains wolframic acid through filtration washing after the reaction was completed, wolframic acid contains WO3
Amount is 42.4g, and the direct yield for calculating tungsten is 86%, and the tungsten mass ratio in wolframic acid is 320:1.
Obtain ammonium tetramolybdate: ammonium paratungstate sodium double salt precipitation mother liquor is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
A kind of embodiment 5: tungsten separation method
Be concentrated by evaporation: the low dense material 500ml of tungsten obtained by low tungsten ore caustic digestion, tungsten concentration are 86.5g/l, and tungsten mass ratio is
20:1 is concentrated by evaporation the solution 282ml, molybdenum concentration 7.7g/l that are 153.4g/l to tungsten concentration；
It adjusts pH: sulfuric acid being added into solution, is stirred to react, makes pH 6；
Add ammonium salt: 50g ammonium chloride stirring and dissolving is added；After the completion of dissolution, it is cooled to 10 DEG C of reaction 6h.
Obtain wolframic acid: after the reaction was completed through the ammonium paratungstate sodium double salt precipitation that tungsten mass ratio is 320:1 is obtained by filtration, to
The dilute hydrochloric acid 500ml of 200g/l is added in precipitating, stirs evenly, obtains wolframic acid through filtration washing after the reaction was completed, wolframic acid contains WO3
Amount is 38.5g, and the direct yield for calculating tungsten is 89%, and the tungsten mass ratio in wolframic acid is 420:1.
Obtain ammonium tetramolybdate: ammonium paratungstate sodium double salt precipitation mother liquor is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (8)
1. a kind of tungsten separation method, which comprises the following steps:
PH: the acid adding into high concentration tungsten solution is adjusted, adjusting pH is 6-9；The tungsten concentration of the high concentration tungsten solution is
150-400g/l, molybdenum concentration 5-50g/l；
Add ammonium salt: in Xiang Shangshu acquired solution plus ammonium salt stirs；After the completion of dissolution, it is stored at room temperature；
It obtains wolframic acid: refiltering to obtain ammonium paratungstate sodium double salt precipitation, acid adding, which filters, is made wolframic acid；
Obtain ammonium tetramolybdate: the mother liquor of the ammonium paratungstate sodium double salt precipitation is ammonium molybdate solution, through the heavy obtained ammonium tetramolybdate of acid.
2. the method according to claim 1, wherein in the adjusting pH step, the high concentration tungsten solution
It is concentrated by evaporation to obtain by the dense material of low tungsten.
3. the method according to claim 1, wherein in the adjusting pH step, the acid be sulfuric acid, hydrochloric acid and
One or more of nitric acid.
4. the method according to claim 1, wherein the ammonium salt is ammonium chloride, sulphur in described plus ammonium salt step
One or more of sour ammonium and ammonium carbonate.
5. the method according to claim 1, wherein in described plus ammonium salt step, the additional amount of the ammonium salt with
The molar ratio of tungsten is (2~5) in solution: 1.
6. the method according to claim 1, wherein described be stored at room temperature refers to room in described plus ammonium salt step
Temperature is lower to stand 6-30h.
7. the method according to claim 1, wherein described obtain in wolframic acid step, the additional amount of the acid with
The molar ratio of tungsten is (3~5) in ammonium paratungstate sodium double salt precipitation: 1.
8. the acid is sulfuric acid, hydrochloric acid the method according to claim 1, wherein described obtain in wolframic acid step
At least one of with nitric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470537A (en) * | 2020-05-07 | 2020-07-31 | 厦门钨业股份有限公司 | Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate |
| CN113025818A (en) * | 2021-03-19 | 2021-06-25 | 中南大学 | Method for recovering tungsten from molybdate solution through catalytic precipitation separation |
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|---|---|---|---|---|
| US4168296A (en) * | 1976-06-21 | 1979-09-18 | Lundquist Adolph Q | Extracting tungsten from ores and concentrates |
| CN1990387A (en) * | 2005-12-29 | 2007-07-04 | 中国石油化工股份有限公司 | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material |
| CN105200245A (en) * | 2015-10-22 | 2015-12-30 | 中南大学 | Method for efficiently separating tungsten and molybdenum |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
-
2019
- 2019-03-29 CN CN201910246806.1A patent/CN109988923A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168296A (en) * | 1976-06-21 | 1979-09-18 | Lundquist Adolph Q | Extracting tungsten from ores and concentrates |
| CN1990387A (en) * | 2005-12-29 | 2007-07-04 | 中国石油化工股份有限公司 | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material |
| CN105200245A (en) * | 2015-10-22 | 2015-12-30 | 中南大学 | Method for efficiently separating tungsten and molybdenum |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
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| Title |
|---|
| 李坚主编: "《轻稀贵金属冶金学》", 31 March 2018, 冶金工业出版社 * |
| 梁琥琪等: "关于冷反应制取仲钨酸铵钠复盐的研究", 《上海有色金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470537A (en) * | 2020-05-07 | 2020-07-31 | 厦门钨业股份有限公司 | Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate |
| CN113025818A (en) * | 2021-03-19 | 2021-06-25 | 中南大学 | Method for recovering tungsten from molybdate solution through catalytic precipitation separation |
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Application publication date: 20190709 |