CN109182746A - A kind of tungsten slag decomposition extraction process - Google Patents

A kind of tungsten slag decomposition extraction process Download PDF

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Publication number
CN109182746A
CN109182746A CN201811217349.5A CN201811217349A CN109182746A CN 109182746 A CN109182746 A CN 109182746A CN 201811217349 A CN201811217349 A CN 201811217349A CN 109182746 A CN109182746 A CN 109182746A
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China
Prior art keywords
tungsten
hydrochloric acid
extraction process
organic phase
time
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CN201811217349.5A
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Chinese (zh)
Inventor
王水龙
王启桂
刘鹏
潘明然
黄星
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Ganzhou Seabird Tungsten Industry Co Ltd
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Ganzhou Seabird Tungsten Industry Co Ltd
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Priority to CN201811217349.5A priority Critical patent/CN109182746A/en
Publication of CN109182746A publication Critical patent/CN109182746A/en
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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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • C22B3/28—Amines
    • 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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of tungsten slags to decompose extraction process, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, the pH of the organic phase is 2-3, mixed economy is at low cost, provides convenience for subsequent extract, the ratio of the organic phase and water phase is 0.5:1-1.5:1, the leaching rate of tungsten can be improved, the time of the oscillation is 4-8min, and the time of the stratification is 5-15min, can further increase the leaching rate of tungsten, the tungsten slag, which decomposes extraction process, has the advantages that mixed economy is at low cost, the rate of recovery is high, has a vast market foreground.

Description

A kind of tungsten slag decomposition extraction process
Technical field
The present invention relates to tungsten ore field of smelting, in particular to a kind of tungsten slag decomposes extraction process.
Background technique
China is state of tungsten sparetime university, and the reserves of tungsten ore are extremely abundant.But with the fast development that tungsten produces, Chinese tungsten Resource reserve is day by day cut down, wherein the most obvious with black tungsten resource, the black tungsten resource in China is closely exhausted.Research finds tertiary amine to low The tungsten of concentration extraction yield with higher, so urgently needing the processing tungsten of a kind of clean and environmental protection, low cost and high extraction yield The technique of slag.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of tungsten slags to decompose extraction process, to solve to lead in the prior art The above-mentioned defects of cause.
To achieve the above object, the present invention provides technical solution below: a kind of tungsten slag decomposition extraction process, including as follows Step:
(1) acid solution is prepared
Hydrochloric acid is mixedly configured into the hydrochloric acid solution of various concentration with water first, the proportion of the hydrochloric acid and water is respectively 7: 3,1:1,3:7；
(2) it is acidified
Tungsten slag is stirred acidification by hydrochloric acid solution, in the process, successively adding hydrochloric acid, concentration that concentration is 70% is The hydrochloric acid that 50% hydrochloric acid and concentration is 30% obtains acidifying solution, and souring temperature is controlled at 50-65 DEG C, the time of the stirring For 3-4h；
(3) it filters
Then acidifying solution is filtered, obtains filtrate and filter residue；
(4) preparation of organic phase
By N235, sec-octyl alcohol and sulfonated kerosene mixed by stirred tank, obtain organic phase, the mixed time is 30-50min；
(5) preparation of water phase
Acidifying solution is subjected to pH adjusting by NaOH respectively, the pH of acid solution is adjusted to 14 and obtains water phase, the NaOH Concentration be 5-15%；
(6) it extracts
Organic phase and water phase are mixed into oscillation, then stratification, obtains tungsten extract liquor；
(7) it recycles
The tungsten in tungsten extract liquor is passed through into ion exchange by ion-exchange, obtains APT.
Preferably, N in the step (4)235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8.
Preferably, the pH of organic phase is 2-3 in the step (4).
Preferably, the ratio of organic phase and water phase is 0.5:1-1.5:1 in the step (6).
Preferably, the time vibrated in the step (6) is 4-8min, and the time of the stratification is 5-15min.
Preferably, the rate of recovery is 91-95% after ion exchange in the step (7).
Be using the beneficial effect of above technical scheme: the present invention provides a kind of tungsten slags to decompose extraction process, the extraction Technique, step is simple, entire technical process, clean and environmental protection.By adding the hydrochloric acid of various concentration in batches, the anti-of tungsten slag is improved Answer efficiency, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, the pH of the organic phase is 2-3, mixed economy cost It is low, convenience is provided for subsequent extract, the ratio of the organic phase and water phase is 0.5:1-1.5:1, the leaching rate of tungsten can be improved, The time of the oscillation is 4-8min, and the time of the stratification is 5-15min, can further increase the leaching rate of tungsten, The tungsten slag, which decomposes extraction process, has the advantages that mixed economy is at low cost, the rate of recovery is high, has a vast market foreground.
Specific embodiment
The following detailed description of the preferred embodiment of the present invention.
Embodiment 1:
A kind of tungsten slag decomposition extraction process, includes the following steps:
(1) acid solution is prepared
Hydrochloric acid is mixedly configured into the hydrochloric acid solution of various concentration with water first, the proportion of the hydrochloric acid and water is respectively 7: 3,1:1,3:7；
(2) it is acidified
Tungsten slag is stirred acidification by hydrochloric acid solution, in the process, successively adding hydrochloric acid, concentration that concentration is 70% is The hydrochloric acid that 50% hydrochloric acid and concentration is 30%, obtains acidifying solution, and souring temperature control is in 65 DEG C, the time of the stirring 3h；
(3) it filters
Then acidifying solution is filtered, obtains filtrate and filter residue；
(4) preparation of organic phase
By N235, sec-octyl alcohol and sulfonated kerosene mixed by stirred tank, obtain organic phase, the mixed time is 30min, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, the pH of the organic phase is 2；
(5) preparation of water phase
Acidifying solution is subjected to pH adjusting by NaOH respectively, the pH of acid solution is adjusted to 14 and obtains water phase, the NaOH Concentration be 5%；
(6) it extracts
Organic phase and water phase are mixed into oscillation, then stratification, obtains tungsten extract liquor, the ratio of the organic phase and water phase Example is 0.5:1, and the time of the oscillation is 4min, and the time of the stratification is 5min；
(7) it recycles
The tungsten in tungsten extract liquor is passed through into ion exchange by ion-exchange, obtains APT, it is described after ion exchange The rate of recovery is 91%.
Embodiment 2:
A kind of tungsten slag decomposition extraction process, includes the following steps:
(1) acid solution is prepared
Hydrochloric acid is mixedly configured into the hydrochloric acid solution of various concentration with water first, the proportion of the hydrochloric acid and water is respectively 7: 3,1:1,3:7；
(2) it is acidified
Tungsten slag acidification be will be stirred by hydrochloric acid solution, and in the process, hydrochloric acid, the concentration that concentration is 70% successively added The hydrochloric acid that hydrochloric acid and concentration for 50% are 30% obtains acidifying solution, and souring temperature is controlled at 58 DEG C, the time of the stirring For 3.5h；
(3) it filters
Then acidifying solution is filtered, obtains filtrate and filter residue；
(4) preparation of organic phase
By N235, sec-octyl alcohol and sulfonated kerosene mixed by stirred tank, obtain organic phase, the mixed time is 40min, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, the pH of the organic phase is 2.5；
(5) preparation of water phase
Acidifying solution is subjected to pH adjusting by NaOH respectively, the pH of acid solution is adjusted to 14 and obtains water phase, the NaOH Concentration be 10%；
(6) it extracts
Organic phase and water phase are mixed into oscillation, then stratification, obtains tungsten extract liquor, the ratio of the organic phase and water phase Example is 1:1, and the time of the oscillation is 6min, and the time of the stratification is 10min；
(7) it recycles
The tungsten in tungsten extract liquor is passed through into ion exchange by ion-exchange, obtains APT, it is described after ion exchange The rate of recovery is 95%.
Embodiment 3:
A kind of tungsten slag decomposition extraction process, includes the following steps:
(1) acid solution is prepared
Hydrochloric acid is mixedly configured into the hydrochloric acid solution of various concentration with water first, the proportion of the hydrochloric acid and water is respectively 7: 3,1:1,3:7；
(2) it is acidified
Tungsten slag is stirred acidification by hydrochloric acid solution, in the process, successively adding hydrochloric acid, concentration that concentration is 70% is The hydrochloric acid that 50% hydrochloric acid and concentration is 30%, obtains acidifying solution, and souring temperature is controlled at 65 DEG C, the time of the stirring is 4h；
(3) it filters
Then acidifying solution is filtered, obtains filtrate and filter residue；
(4) preparation of organic phase
By N235, sec-octyl alcohol and sulfonated kerosene mixed by stirred tank, obtain organic phase, the mixed time is 50min, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, the pH of the organic phase is 3；
(5) preparation of water phase
Acidifying solution is subjected to pH adjusting by NaOH respectively, the pH of acid solution is adjusted to 14 and obtains water phase, the NaOH Concentration be 15%；
(6) it extracts
Organic phase and water phase are mixed into oscillation, then stratification, obtains tungsten extract liquor, the ratio of the organic phase and water phase Example is 1.5:1, and the time of the oscillation is 8min, and the time of the stratification is 15min；
(7) it recycles
The tungsten in tungsten extract liquor is passed through into ion exchange by ion-exchange, obtains APT, it is described after ion exchange The rate of recovery is 93%.
After above method, sample is taken out respectively, and measurement result is as follows:
Detection project Embodiment 1 Embodiment 2 Embodiment 3 Existing index
The rate of recovery (%) 91 95 93 89
Mixed economy cost It is low It is low It is low It is lower
Impurity element It is few It is few It is few It is less
According to above table data it can be concluded that, when the parameter of embodiment 2, tungsten after the recovery than the prior art recycle after The rate of recovery of tungsten increase, mixed economy is at low cost, and impurity element is few, is more advantageous to the recycling of tungsten at this time.
The present invention provides a kind of tungsten slag decomposition extraction process, the N235, sec-octyl alcohol and sulfonated kerosene ratio be 1:1:8, The pH of the organic phase is 2-3, and mixed economy is at low cost, provides convenience, the ratio of the organic phase and water phase for subsequent extraction For 0.5:1-1.5:1, the leaching rate of tungsten can be improved, the time of the oscillation is 4-8min, and the time of the stratification is 5-15min can further increase the leaching rate of tungsten, tungsten slag decomposition extraction process at low cost, rate of recovery with mixed economy High advantage, has a vast market foreground.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention Protection scope.

Claims (6)

1. a kind of tungsten slag decomposes extraction process, which comprises the steps of:
(1) acid solution is prepared
Hydrochloric acid is mixedly configured into the hydrochloric acid solution of various concentration with water first, the proportion of the hydrochloric acid and water is respectively 7:3,1: 1,3:7；
(2) it is acidified
Tungsten slag is stirred acidification by hydrochloric acid solution, in the process, successively adds the hydrochloric acid that concentration is 70%, concentration 50% Hydrochloric acid and concentration be 30% hydrochloric acid, obtain acidifying solution, souring temperature is controlled at 50-65 DEG C, and the time of the stirring is 3- 4h；
(3) it filters
Then acidifying solution is filtered, obtains filtrate and filter residue；
(4) preparation of organic phase
By N235, sec-octyl alcohol and sulfonated kerosene mixed by stirred tank, obtain organic phase, the mixed time is 30- 50min；
(5) preparation of water phase
Acidifying solution is subjected to pH adjusting by NaOH respectively, the pH of acid solution is adjusted to 14 and obtains water phase, the NaOH's is dense Degree is 5-15%；
(6) it extracts
Organic phase and water phase are mixed into oscillation, then stratification, obtains tungsten extract liquor；
(7) it recycles
The tungsten in tungsten extract liquor is passed through into ion exchange by ion-exchange, obtains APT.
2. a kind of tungsten slag according to claim 1 decomposes extraction process, which is characterized in that N in the step (4)235, it is secondary The ratio of octanol and sulfonated kerosene is 1:1:8.
3. a kind of tungsten slag according to claim 1 decomposes extraction process, which is characterized in that organic phase in the step (4) PH be 2-3.
4. a kind of tungsten slag according to claim 1 decomposes extraction process, which is characterized in that organic phase in the step (6) Ratio with water phase is 0.5:1-1.5:1.
5. a kind of tungsten slag according to claim 1 decomposes extraction process, which is characterized in that vibrated in the step (6) Time is 4-8min, and the time of the stratification is 5-15min.
6. a kind of tungsten slag according to claim 1 decomposes extraction process, which is characterized in that in the step (7) by from The tungsten of son exchange is recovered as 91-95%.
CN201811217349.5A 2018-10-18 2018-10-18 A kind of tungsten slag decomposition extraction process Pending CN109182746A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110093511A (en) * 2019-05-29 2019-08-06 湖南长宏新能源材料有限责任公司 A kind of totally-enclosed technique for handling hazardous waste-tungsten slag and recycling valuable metal
CN113058289A (en) * 2021-02-19 2021-07-02 江钨世泰科钨品有限公司 Extraction system of sodium tungstate solution transformation

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Publication number Priority date Publication date Assignee Title
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CN103290224A (en) * 2013-05-31 2013-09-11 刘甲祥 Recovery process for valuable metals in tungsten residues
CN103614545A (en) * 2013-11-22 2014-03-05 中南大学 Method for treating low-grade tungsten concentrate and tungsten slag
CN103805793A (en) * 2013-09-13 2014-05-21 江西理工大学 Method for decomposing scheelite
CN105154683A (en) * 2015-08-20 2015-12-16 湖南世纪垠天新材料有限责任公司 Method for separating and recycling valuable metal in tungsten slag

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212697A (en) * 2011-05-18 2011-10-12 湖南稀土金属材料研究院 Tungsten slag treatment method
CN103290224A (en) * 2013-05-31 2013-09-11 刘甲祥 Recovery process for valuable metals in tungsten residues
CN103805793A (en) * 2013-09-13 2014-05-21 江西理工大学 Method for decomposing scheelite
CN103614545A (en) * 2013-11-22 2014-03-05 中南大学 Method for treating low-grade tungsten concentrate and tungsten slag
CN105154683A (en) * 2015-08-20 2015-12-16 湖南世纪垠天新材料有限责任公司 Method for separating and recycling valuable metal in tungsten slag

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110093511A (en) * 2019-05-29 2019-08-06 湖南长宏新能源材料有限责任公司 A kind of totally-enclosed technique for handling hazardous waste-tungsten slag and recycling valuable metal
CN113058289A (en) * 2021-02-19 2021-07-02 江钨世泰科钨品有限公司 Extraction system of sodium tungstate solution transformation

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Application publication date: 20190111