CN105714113B - The method that tungsten is separated from tungsten sulfide molybdenum concntrate - Google Patents
The method that tungsten is separated from tungsten sulfide molybdenum concntrate Download PDFInfo
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- CN105714113B CN105714113B CN201610252191.XA CN201610252191A CN105714113B CN 105714113 B CN105714113 B CN 105714113B CN 201610252191 A CN201610252191 A CN 201610252191A CN 105714113 B CN105714113 B CN 105714113B
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
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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
Abstract
The present invention relates to a kind of method of separating tungsten in molybdenum concntrate from tungsten sulfide.By tungsten sulfide molybdenum concntrate ammonia solvent, extracted after adjustment pH with an organic extractant two-stage, ammoniacal liquor is stripped extract and obtains ammonium molybdate solution.Extracted after raffinate addition hydrogen peroxide and sulfuric acid with No. two organic extractant one-levels, raffinate ammoniacal liquor neutralizes and obtains ammonium molybdate solution.Ammonium molybdate solution evaporation twice is recrystallized to give ammonium molybdate crystal.This method technique advantages of simple, satisfies the requirements easily-controllable, technological process is short, equipment investment is few, the advantages of product yield is high, with huge practical value, and the mass percent of the W/Mo in obtained ammonium molybdate crystal is less than 0.05%, and molybdenum recovery is more than 90%.
Description
Technical field
The present invention relates to rare metal field, the method that tungsten is separated in more particularly to a kind of molybdenum concntrate from tungsten sulfide.
Background technology
China is the production and consumption big country of tungsten, and tungsten has a wide range of applications in industrial every field, and molybdenum is not only
For in the catalyst of oil, enamel pigment and medicine etc., be additionally operable to prepare hard alloy, superalloy, various stainless steels and
On the products such as heavy chemicals.With the popularization of molybdenum product purpose, to the purity requirement more and more higher of molybdenum product, the tungsten in molybdenum product
Need to carry out depth separation；At present, tungsten isolation technics tends to belong to extensive style at home, and the tungsten in molybdenum product is still difficult to
It is completely separated, the technical problem of tungsten separating factor how is improved, at home also in development；And external moral, Japan and the United States etc.
The enterprise development of country is more early, but to technical know-how.
The content of the invention
Based on this, it is necessary to provide a kind of simple and fast, cost is relatively low, divides in the high molybdenum concntrate from tungsten sulfide of product yield
From the method for tungsten.
A kind of method that tungsten is separated in molybdenum concntrate from tungsten sulfide, comprises the following steps：
Dissolving：Tungsten sulfide molybdenum concntrate is added in the first ammonia spirit and dissolved, tungsten acid ammonium solution is obtained；
Extract for the first time：Sulfuric acid solution adjustment pH value is added in tungsten acid ammonium solution, an organic extraction is then added to
Extracted in agent, obtain extract and raffinate containing molybdenum；
It is stripped for the first time：Ammonium molybdate solution is obtained with extract of the second ammonia spirit back extraction containing molybdenum；
Second of extraction：Hydrogen peroxide is added in raffinate, sulfuric acid solution adjustment acidity is then added, after being well mixed
To mixed liquor, add No. two organic extractants and extracted, obtain tungstenic extract and raffinate containing molybdenum, by the raffinate containing molybdenum
Liquid is neutralized with the second ammonia spirit and obtains ammonium molybdate solution；
Second of back extraction：Ammonium tungstate solution is obtained with the second ammonia spirit back extraction tungstenic extract；
Crystallization：Merge above-mentioned ammonium molybdate solution, evaporative crystallization obtains ammonium molybdate crystal.
In one of the embodiments, the solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15~25, first
The molar concentration of ammonia spirit is 1.20~1.30mol/L.
In one of the embodiments, in first time extraction step, by the pH value of tungsten acid ammonium solution adjust to pH2~
3。
In one of the embodiments, in first time extraction step, extracting operation is two grades of extractions, tungsten acid ammonium solution
Volume ratio with an organic extractant is 1:1~2.
In one of the embodiments, in second of extraction step, extracting operation is one-level extraction, raffinate and No. two
The volume ratio of organic extractant is 6~4:1.
In one of the embodiments, an organic extractant is that volume ratio is 10~30:70~90 di(2-ethylhexyl)phosphate is different pungent
The mixed solution of ester and kerosene.
In one of the embodiments, No. two organic extractants are that volume ratio is 15~30:3~6:64~82 three octanes
The mixed solution of base tertiary amine, tributyl phosphate and kerosene.
In one of the embodiments, the extract containing molybdenum also comprise the following steps before back extraction operation for the first time：
The sulfuric acid solution that pH is 2~3 is added in the extract containing molybdenum and carries out washing impurity-removing.
In one of the embodiments, the molar concentration of the second ammonia spirit is 5~7mol/L.
In one of the embodiments, in second of extraction step, concentration of the hydrogen peroxide in mixed liquor be 0.5~
1mol/L, adjustment acidity to H2SO4Concentration in mixed liquor is 0.5~1mol/L.
The principle and advantage of the present invention is as follows：
The separation method of the present invention is dissolved tungsten sulfide molybdenum concntrate by ammoniacal liquor, is obtained after tungsten acid ammonium solution, adjustment pH
Progress two-stage extraction in an organic extractant is added to, most molybdenum is extracted in organic phase, then be stripped with ammoniacal liquor
A number extract, obtains ammonium molybdate solution；And a small amount of molybdenum and most tungsten have been stayed in raffinate, due to tungsten separation not
Thoroughly, added in raffinate after appropriate hydrogen peroxide and sulfuric acid, add in No. two extractants and carry out one-level extraction again, make whole
Tungsten and micro molybdenum be extracted in organic phase, containing only molybdenum in raffinate, raffinate ammoniacal liquor neutralize obtain ammonium molybdate product
Solution.Ammonium molybdate product solution twice is evaporated, recrystallized, that is, has obtained ammonium molybdate crystal.
Tungsten sulfide molybdenum concntrate is mainly made up of tungsten sulfide and molybdenum sulfide, in the case where not heating, and ammonia spirit just can be with
The dissolving of tungsten sulfide molybdenum concntrate is complete；When the concentration control of ammonia spirit is 1.20~1.30mol/L, it can not only ensure vulcanization
The concentration of ammoniacal liquor, also helps the environment of optimization Workplace needed for the dissolving of tungsten concentrate.
When the solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and ammonia spirit is less than 1:When 15, tungsten sulfide molybdenum concntrate will dissolve incomplete,
So as to reduce the yield of product.When the solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and ammonia spirit is more than 1:When 25, tungsten sulfide molybdenum concntrate
Although dissolving is complete, in order to adjust the acidity of feed liquid, it is necessary to neutralize excess of ammonia water with substantial amounts of sulfuric acid, so as to add
Production cost.
In first time extraction step, the pH value of tungsten acid ammonium solution is adjusted to pH2~3, is to improve product
Yield；When the pH value of tungsten acid ammonium solution is less than 2, there is the precipitation of molybdic acid and wolframic acid in solution meeting, so as to reduce product
Yield, meanwhile, first time extractant can also extract a small amount of tungsten, so as to influence product quality；When the pH value of tungsten acid ammonium solution
During more than 3, an organic extractant will decline to the extraction efficiency of molybdenum, also just not reach the effect of initial gross separation tungsten.
In second of extraction step, concentration of the hydrogen peroxide in mixed liquor is 0.5~1mol/L, H2SO4In mixed liquor
Concentration be 0.5~1mol/L.When concentration of the hydrogen peroxide in mixed liquor is less than 0.5mol/L, tungsten just occurs in mixed liquor
The precipitation of acid and molybdic acid, so as to influence the yield of product；When concentration of the hydrogen peroxide in mixed liquor is more than 1mol/L, excessive
Hydrogen peroxide generates complex compound with tungsten, so as to cause tungsten not extracted by No. two organic extractants, is also just not reaching to separation tungsten
Purpose.Work as H2SO4When concentration in mixed liquor is less than 0.5mol/L, No. two organic extractants are serious to the extraction efficiency of tungsten
Decline, tungsten is trapped in raffinate simultaneously, so that tungsten is not efficiently separated；Work as H2SO4Concentration in mixed liquor
During more than 1mol/L, wolframic acid and precipitate molybdic acid just occur in mixed liquor, in addition, under this acidity, No. two organic extractions
Agent extracts tungsten simultaneously, so as to both have impact on the yield of product, the effect of separation tungsten is not reached again.
The method that tungsten is separated in this molybdenum concntrate from tungsten sulfide, technique advantages of simple, technological process easily-controllable with condition
Short, equipment investment is few, the advantages of product yield is high, with huge practical value, and the W/Mo in obtained ammonium molybdate crystal
Mass percent be less than 0.05%, molybdenum recovery be more than 90%.
Brief description of the drawings
Fig. 1 is the flow chart of the method that tungsten is separated from tungsten sulfide molybdenum concntrate of an embodiment；
Fig. 2 is the schematic diagram of the method that tungsten is separated from tungsten sulfide molybdenum concntrate of an embodiment.
Embodiment
To enable objects, features and advantages of the present invention more obvious understandable, below in conjunction with the accompanying drawings to the tool of the present invention
Body embodiment is described in detail.Elaborate many details in the following description to facilitate a thorough understanding of the present invention,
But the present invention can be implemented with being much different from other modes described here, those skilled in the art can without prejudice to
Similar improvement is done in the case of intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
The method that tungsten is separated from tungsten sulfide molybdenum concntrate of an embodiment as depicted in figs. 1 and 2, including following step
Suddenly：
S10, dissolving：Tungsten sulfide molybdenum concntrate is added in the first ammonia spirit and dissolved, tungsten acid ammonium solution is obtained.
Preferably, dissolving step is carried out at normal temperatures, specially 10~40 DEG C.
Preferably, the solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15~25.
Preferably, the molar concentration of the first ammonia spirit is 1.20~1.30mol/L.
S20, for the first time extraction：In tungsten acid ammonium solution add sulfuric acid solution adjustment pH value, be then added to No. one it is organic
Extracted in extractant, obtain extract and raffinate containing molybdenum.
Preferably, in first time extraction step, the pH value of tungsten acid ammonium solution is adjusted to pH2~3.
Preferably, in first time extraction step, extracting operation is two grades of extractions, tungsten acid ammonium solution and an organic extraction
The volume ratio for taking agent is 1:1~2.
Preferably, an organic extractant is the mixed solution of di (isooctyl) phosphate and kerosene, di (isooctyl) phosphate and coal
The volume ratio of oil is 10~30:70~90.
S30, for the first time back extraction：Ammonium molybdate solution is obtained with extract of the second ammonia spirit back extraction containing molybdenum.
Preferably, the molar concentration of the second ammonia spirit is 5~7mol/L.
Preferably, the extract containing molybdenum also comprise the following steps before back extraction operation for the first time：It is 2~3 by pH
Sulfuric acid solution be added in the extract containing molybdenum carry out washing impurity-removing.
Preferably, the volume ratio of the second ammonia spirit and the extract containing molybdenum is 1:1.
Preferably, reused after an organic extractant after back extraction is balanced with sulfuric acid solution.
S40, second of extraction：Hydrogen peroxide is added in raffinate, sulfuric acid solution adjustment acidity is then added, is well mixed
After obtain mixed liquor, be then added in No. two organic extractants and extracted, obtain tungstenic extract and raffinate containing molybdenum, will contain
The raffinate of molybdenum is neutralized with the second ammonia spirit and obtains ammonium molybdate solution.
Preferably, in second of extraction step, concentration of the hydrogen peroxide in mixed liquor is 0.5~1mol/L, adjustment acid
Spend to H2SO4Concentration in mixed liquor is 0.5~1mol/L.
Preferably, in second of extraction step, extracting operation is one-level extraction, raffinate and No. two organic extractants
Volume ratio is 6~4:1.
Preferably, No. two organic extractants are the mixed solution of three octyl tertiary amines, tributyl phosphate and kerosene, three octanes
The volume ratio of base tertiary amine, tributyl phosphate and kerosene is 15~30:3~6:64~82.
Preferably, reused after No. two organic extractants after back extraction are balanced with sulfuric acid solution.
Preferably, extraction time is 30min.
S50, second of back extraction：Ammonium tungstate solution is obtained with the second ammoniacal liquor back extraction tungstenic extract.
S60, crystallization：Merge above-mentioned ammonium molybdate solution, evaporative crystallization obtains ammonium molybdate crystal.
The application is further elaborated by the following examples.
Embodiment 1
The method that tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide of the present embodiment, comprises the following steps：
Dissolving：Weigh 50 grams of tungsten sulfide molybdenum concntrate raw materials to be placed in glass, wherein MoS282.5%, WS217.5%；Press
The solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15 add the first ammonia spirit, and 5min is stirred at room temperature, molten
Solution to limpid, wherein, the molar concentration of the first ammonia spirit is 1.25mol/L.
Extract for the first time：It is 2 to adjust feed liquid to pH with 3mol/L sulfuric acid solutions, is by volume 1：1 addition one is organic
Two grades of extractions are carried out in extractant, extraction time is 30min, obtains extract and raffinate containing molybdenum.An organic extraction used
It is di (isooctyl) phosphate and the mixture of kerosene to take agent, is measured according to percent by volume, wherein, di (isooctyl) phosphate volume accounts for mixed
The 30% of compound and the volume of kerosene account for the 70% of mixture.
It is stripped for the first time：It is that 2 sulfuric acid solutions are added in the extract containing molybdenum with pH, washing impurity-removing obtains containing after removal of impurities
Molybdenum extract.
It is 1 by volume：1, be stripped extract containing molybdenum with the second ammonia spirit, wherein, the second ammonia spirit it is mole dense
Spend for 5mol/L, obtain ammonium molybdate solution.
Second of extraction：Appropriate hydrogen peroxide is added in raffinate and sulfuric acid obtains mixed liquor, wherein, hydrogen peroxide is in mixed liquor
In concentration be 0.5mol/L, H2SO4Concentration is 0.5mol/L in mixed liquor.
The mixed liquor is added and extracted in No. two organic extractants, volume ratio is 6：1, extraction time is 30min, its
In, No. two organic extractants are the mixed liquor of three octyl tertiary amines, tributyl phosphate and kerosene, three octyl tertiary amines, tricresyl phosphate
The volume ratio of butyl ester and kerosene is 15:3:82.
Its raffinate neutralizes to obtain ammonium molybdate solution with the second ammonia spirit, wherein, the molar concentration of the second ammonia spirit is
5mol/L。
Second of back extraction：Ammonium tungstate solution is obtained with the second ammonia spirit back extraction tungstenic extract.
Crystallization：The ammonium molybdate solution of gained twice is evaporated, recrystallized, ammonium molybdate crystal product analysis result is obtained
As shown in table 1.
Table 1
| Composition | Mo | W | W/Mo | Yield % |
| Content (%) | 52.12 | 0.023 | 0.044 | 90.17 |
Embodiment 2
The method that tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide of the present embodiment, comprises the following steps：
Dissolving：Weigh 40 grams of tungsten sulfide molybdenum concntrate raw materials to be placed in glass, wherein MoS279.4%, WS220.2%；Press
The solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:25 add the first ammonia spirit, and 5min is stirred at room temperature, molten
Solution to limpid, wherein, the molar concentration of the first ammonia spirit is 1.25mol/L.
Extract for the first time：It is 3 to adjust feed liquid to pH with 3mol/L sulfuric acid solutions, is by volume 1：2 additions one are organic
Two grades of extractions are carried out in extractant, extraction time is 30min, obtains extract and raffinate containing molybdenum.An organic extraction used
It is di (isooctyl) phosphate and the mixture of kerosene to take agent, is measured according to percent by volume, wherein, di (isooctyl) phosphate volume accounts for mixed
The 10% of compound and the volume of kerosene account for the 90% of mixture.
It is stripped for the first time：It is that 3 sulfuric acid solutions are added in the extract containing molybdenum with pH, washing impurity-removing obtains containing after removal of impurities
Molybdenum extract.
It is 1 by volume：1, be stripped extract containing molybdenum with the second ammonia spirit, wherein, the second ammonia spirit it is mole dense
Spend for 7mol/L, obtain ammonium molybdate solution.
Second of extraction：Appropriate hydrogen peroxide is added in raffinate and sulfuric acid obtains mixed liquor, wherein, hydrogen peroxide is in mixed liquor
In concentration be 1mol/L, H2SO4Concentration is 1mol/L in mixed liquor..
The mixed liquor is added and extracted in No. two organic extractants, volume ratio is 4：1, extraction time is 30min, its
In, No. two organic extractants are the mixed liquor of three octyl tertiary amines, tributyl phosphate and kerosene, three octyl tertiary amines, tricresyl phosphate
The volume ratio of butyl ester and kerosene is 30:6:64.
Its raffinate neutralizes to obtain ammonium molybdate solution with the second ammonia spirit, wherein, the molar concentration of the second ammonia spirit is
7mol/L。
Second of back extraction：The tungstenic extract is stripped with the second ammonia spirit and obtains ammonium tungstate solution, ammonium tungstate solution is returned
Receipts processing.
Crystallization：The ammonium molybdate solution of gained twice is evaporated, recrystallized, ammonium molybdate crystal product analysis result is obtained
As shown in table 2.
Table 2
| Composition | Mo | W | W/Mo | Yield % |
| Content (%) | 53.17 | 0.021 | 0.039 | 90.42 |
Embodiment 3
The method that tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide of the present embodiment, comprises the following steps：
Dissolving：Weigh 50 grams of tungsten sulfide molybdenum concntrate raw materials to be placed in glass, wherein MoS282.5%, WS217.5%；Press
The solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15 add the first ammonia spirit, and 5min is stirred at room temperature, molten
Solution to limpid, wherein, the molar concentration of the first ammonia spirit is 1.25mol/L.
Extract for the first time：It is 3 to adjust feed liquid to pH with 3mol/L sulfuric acid solutions, is by volume 1：1 addition one is organic
Two grades of extractions are carried out in extractant, extraction time is 30min, obtains extract and raffinate containing molybdenum.An organic extraction used
It is di (isooctyl) phosphate and the mixture of kerosene to take agent, is measured according to percent by volume, wherein, di (isooctyl) phosphate volume accounts for mixed
The 30% of compound and the volume of kerosene account for the 70% of mixture.
It is stripped for the first time：It is that 2 sulfuric acid solutions are added in the extract containing molybdenum with pH, washing impurity-removing obtains containing after removal of impurities
Molybdenum extract.
It is 1 by volume：1, be stripped extract containing molybdenum with the second ammonia spirit, wherein, the second ammonia spirit it is mole dense
Spend for 5mol/L, obtain ammonium molybdate solution.
Second of extraction：Appropriate hydrogen peroxide is added in raffinate and sulfuric acid obtains mixed liquor, wherein, hydrogen peroxide is in mixed liquor
In concentration be 0.5mol/L, H2SO4Concentration is 0.5mol/L in mixed liquor.
The mixed liquor is added and extracted in No. two organic extractants, volume ratio is 6：1, extraction time is 30min, its
In, No. two organic extractants are the mixed liquor of three octyl tertiary amines, tributyl phosphate and kerosene, three octyl tertiary amines, tricresyl phosphate
The volume ratio of butyl ester and kerosene is 15:3:82.
Its raffinate neutralizes to obtain ammonium molybdate solution with the second ammonia spirit, wherein, the molar concentration of the second ammonia spirit is
5mol/L。
Second of back extraction：The tungstenic extract is stripped with the second ammonia spirit and obtains ammonium tungstate solution, ammonium tungstate solution is returned
Receipts processing.
Crystallization：The ammonium molybdate solution of gained twice is evaporated, recrystallized, ammonium molybdate crystal product analysis result is obtained
As shown in table 3.
Table 3
| Composition | Mo | W | W/Mo | Yield % |
| Content (%) | 54.07 | 0.026 | 0.048 | 91.65 |
Embodiment 4
The method that tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide of the present embodiment, comprises the following steps：
Dissolving：Weigh 50 grams of tungsten sulfide molybdenum concntrate raw materials to be placed in glass, wherein MoS282.5%, WS217.5%；Press
The solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15 add the first ammonia spirit, and 5min is stirred at room temperature, molten
Solution to limpid, wherein, the molar concentration of the first ammonia spirit is 1.25mol/L.
Extract for the first time：It is 2 to adjust feed liquid to pH with 3mol/L sulfuric acid solutions, is by volume 1：1 addition one is organic
Two grades of extractions are carried out in extractant, extraction time is 30min, obtains extract and raffinate containing molybdenum.An organic extraction used
It is di (isooctyl) phosphate and the mixture of kerosene to take agent, is measured according to percent by volume, wherein, di (isooctyl) phosphate volume accounts for mixed
The 30% of compound and the volume of kerosene account for the 70% of mixture.
It is stripped for the first time：It is that 2 sulfuric acid solutions are added in the extract containing molybdenum with pH, washing impurity-removing obtains containing after removal of impurities
Molybdenum extract.
It is 1 by volume：1, be stripped extract containing molybdenum with the second ammonia spirit, wherein, the second ammonia spirit it is mole dense
Spend for 5mol/L, obtain ammonium molybdate solution.
Second of extraction：Appropriate hydrogen peroxide is added in raffinate and sulfuric acid obtains mixed liquor, wherein, hydrogen peroxide is in mixed liquor
In concentration be 1mol/L, H2SO4Concentration is 1mol/L in mixed liquor.
The mixed liquor is added and extracted in No. two organic extractants, volume ratio is 6：1, extraction time is 30min, its
In, No. two organic extractants are the mixed liquor of three octyl tertiary amines, tributyl phosphate and kerosene, three octyl tertiary amines, tricresyl phosphate
The volume ratio of butyl ester and kerosene is 15:3:82.
Its raffinate neutralizes to obtain ammonium molybdate solution with the second ammonia spirit, wherein, the molar concentration of the second ammonia spirit is
5mol/L。
Second of back extraction：Obtained with the second ammonia spirit back extraction tungstenic extract at ammonium tungstate solution, ammonium tungstate solution recovery
Reason.
Crystallization：The ammonium molybdate solution of gained twice is evaporated, recrystallized, ammonium molybdate crystal product analysis result is obtained
As shown in table 4.
Table 4
| Composition | Mo | W | W/Mo | Yield % |
| Content (%) | 52.31 | 0.025 | 0.048 | 91.02 |
Embodiment 5
The method that tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide of the present embodiment, comprises the following steps：
Dissolving：Weigh 50 grams of tungsten sulfide molybdenum concntrate raw materials to be placed in glass, wherein MoS282.5%, WS217.5%；Press
The solid-to-liquid ratio of tungsten sulfide molybdenum concntrate and the first ammonia spirit is 1:15 add the first ammonia spirit, and 5min is stirred at room temperature, molten
Solution to limpid, wherein, the molar concentration of the first ammonia spirit is 1.25mol/L.
Extract for the first time：It is 2 to adjust feed liquid to pH with 3mol/L sulfuric acid solutions, is by volume 1：1 addition one is organic
Two grades of extractions are carried out in extractant, extraction time is 30min, obtains extract and raffinate containing molybdenum.An organic extraction used
It is di (isooctyl) phosphate and the mixture of kerosene to take agent, is measured according to percent by volume, wherein, di (isooctyl) phosphate volume accounts for mixed
The 30% of compound and the volume of kerosene account for the 70% of mixture.
It is stripped for the first time：It is that 2 sulfuric acid solutions are added in the extract containing molybdenum with pH, washing impurity-removing obtains containing after removal of impurities
Molybdenum extract.
It is 1 by volume：1, be stripped extract containing molybdenum with the second ammonia spirit, wherein, the second ammonia spirit it is mole dense
Spend for 5mol/L, obtain ammonium molybdate solution.
Second of extraction：Appropriate hydrogen peroxide is added in raffinate and sulfuric acid obtains mixed liquor, wherein, hydrogen peroxide is in mixed liquor
In concentration be 0.5mol/L, H2SO4Concentration is 0.5mol/L in mixed liquor.
The mixed liquor is added and extracted in No. two organic extractants, volume ratio is 4：1, extraction time is 30min, its
In, No. two organic extractants are the mixed liquor of three octyl tertiary amines, tributyl phosphate and kerosene, three octyl tertiary amines, tricresyl phosphate
The volume ratio of butyl ester and kerosene is 15:3:82.
Its raffinate neutralizes to obtain ammonium molybdate solution with the second ammonia spirit, wherein, the molar concentration of the second ammonia spirit is
5mol/L。
Second of back extraction：Obtained with the second ammonia spirit back extraction tungstenic extract at ammonium tungstate solution, ammonium tungstate solution recovery
Reason.
Crystallization：The ammonium molybdate solution of gained twice is evaporated, recrystallized, ammonium molybdate crystal product analysis result is obtained
As shown in table 5.
Table 5
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. the method for tungsten is separated in a kind of molybdenum concntrate from tungsten sulfide, it is characterised in that comprise the following steps：
Dissolving：Tungsten sulfide molybdenum concntrate is added in the first ammonia spirit and dissolved, tungsten acid ammonium solution is obtained；
Extract for the first time：Sulfuric acid solution adjustment pH value is added in the tungsten acid ammonium solution, by the tungsten acid ammonium solution
PH value is adjusted to pH2~3, is then added in an organic extractant and is extracted, and obtains extract and raffinate containing molybdenum；
It is stripped for the first time：Ammonium molybdate solution is obtained with the second ammonia spirit back extraction extract containing molybdenum；
Second of extraction：Hydrogen peroxide is added in the raffinate, sulfuric acid solution adjustment acidity is then added, after being well mixed
To mixed liquor, add No. two organic extractants and extracted, obtain tungstenic extract and raffinate containing molybdenum, by the raffinate containing molybdenum
Liquid is neutralized with the second ammonia spirit and obtains ammonium molybdate solution, wherein concentration of the hydrogen peroxide in mixed liquor is 0.5~1mol/
L, adjustment acidity to H2SO4Concentration in mixed liquor is 0.5~1mol/L；
Second of back extraction：The tungstenic extract, which is stripped, with the second ammonia spirit obtains ammonium tungstate solution；
Crystallization：Merge above-mentioned ammonium molybdate solution, evaporative crystallization obtains ammonium molybdate crystal.
2. the method for tungsten is separated in the molybdenum concntrate according to claim 1 from tungsten sulfide, it is characterised in that the tungsten sulfide
The solid-to-liquid ratio of molybdenum concntrate and first ammonia spirit is 1:15~25, the molar concentration of first ammonia spirit for 1.20~
1.30mol/L。
3. the method for tungsten is separated in the molybdenum concntrate according to claim 1 from tungsten sulfide, it is characterised in that extract in first time
Take in step, extracting operation is two grades and extracted, the volume ratio of the tungsten acid ammonium solution and an organic extractant is 1:1
~2.
4. the method for tungsten is separated in the molybdenum concntrate according to claim 1 from tungsten sulfide, it is characterised in that extract at second
Take in step, extracting operation extracts for one-level, the volume ratio of the raffinate and No. two organic extractants is 6~4:1.
5. the method that tungsten is separated from tungsten sulfide molybdenum concntrate according to claim any one of 1-4, it is characterised in that institute
It is that volume ratio is 10~30 to state an organic extractant:70~90 di (isooctyl) phosphate and the mixed solution of kerosene.
6. the method that tungsten is separated from tungsten sulfide molybdenum concntrate according to claim any one of 1-4, it is characterised in that institute
It is that volume ratio is 15~30 to state No. two organic extractants:3~6:64~82 three octyl tertiary amines, tributyl phosphate and kerosene
Mixed solution.
7. the method that tungsten is separated from tungsten sulfide molybdenum concntrate according to claim any one of 1-4, it is characterised in that institute
The extract containing molybdenum is stated before back extraction operation for the first time also comprise the following steps：PH is added to for 2~3 sulfuric acid solution
Washing impurity-removing is carried out in the extract containing molybdenum.
8. the method that tungsten is separated from tungsten sulfide molybdenum concntrate according to claim any one of 1-4, it is characterised in that institute
The molar concentration for stating the second ammonia spirit is 5~7mol/L.
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