CN101130835A - Production method for extracting gallium - Google Patents

Production method for extracting gallium Download PDF

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Publication number
CN101130835A
CN101130835A CNA200710141488XA CN200710141488A CN101130835A CN 101130835 A CN101130835 A CN 101130835A CN A200710141488X A CNA200710141488X A CN A200710141488XA CN 200710141488 A CN200710141488 A CN 200710141488A CN 101130835 A CN101130835 A CN 101130835A
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gallium
mother liquid
liquid filtrate
carbon mother
filtrate
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CN100494428C (en
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魏一林
周立平
杜鸿逵
赵雄慧
沈军
李淑振
张凤英
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Inner Mongolia Mengxi Ordos Aluminum Co ltd
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Mengxi High Tech Group Co Ltd Inner Mongolia
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention discloses a production method for extracting metal gallium by utilizing carbonous mother liquor filtrate-intermediate product obtained in production process of aluminium oxide from non-bauxite. Said production method includes the following steps: adding sodium hydrogen carbonate into the carbonous mother liquor, stirring them, making carbonization decomposition reaction to obtain gallium concentrate, using sodium hydroxide to dissolve said gallium concentrate, filtering and separating to obtain electrolytic solution, electrolyzing to obtain the invented metal gallium. Said invention can utilize fly-ash, coal gangue and kaoline to produce aluminium oxide, at the same time can produce metal gallium.

Description

A kind of production method of extracting gallium
Technical field:
The present invention relates to a kind of production method of extracting gallium, especially relate to a kind of method of extracting gallium in the alumina process of from non-bauxite such as flyash, coal gangue, kaolin, producing.
Background technology:
Gallium is the important source material of electronic industry.Along with the fast development of electronic industry, increasing to the demand of gallium, and also the source of gallium is also very rare.The source of gallium mainly is to rely on to reclaim in the bauxite into alumina process to obtain at present.Its production method is milk of lime carbonation method and resin adsorption method etc. mostly; Wherein the milk of lime carbonation method is a logical carbon dioxide gas in alumina carbon mother liquid, carries out thorough carbonating and decomposes, and adds lime milk dealuminium again, reaches the enrichment of gallium, and this method forms calcium aluminate, and a large amount of aluminium losses are arranged; Resin adsorption method is directly to use resin in the alumina producing circulating mother liquor, and the absorption gallium carries out desorption again, reaches the enrichment of gallium, if the concentration of gallium is low in the circulating mother liquor, its cost is higher relatively.
Summary of the invention:
The object of the present invention is to provide a kind of production technique simple, the processing condition of from non-bauxite such as flyash, coal gangue, kaolin, producing aluminum oxide have been made full use of, mend in the alkali process at the carbon operation break-down, need not increase any operation, just can reach a kind of method of extracting gallium of the enrichment of gallium.
Purpose of the present invention is implemented by following technical scheme: a kind of method of extracting gallium, include following steps: utilize flyash, or coal gangue, or in the process of the non-bauxite into alumina of any one or two kinds of above combinations of kaolin, production obtains intermediate product carbon mother liquid filtrate, alumina content is 0.64~2.0g/l in the wherein said carbon mother liquid filtrate, and gallium enrichment concentration is 0.05~0.064g/l; Get the carbon mother liquid filtrate of the volume percent 10%-40% of described intermediate product carbon mother liquid filtrate, in the described carbon mother liquid filtrate of being got, add sodium bicarbonate, stir, the concentration range of wherein said sodium bicarbonate is 30~90g/l, temperature is 60~90 ℃, churning time is 1~8 hour, obtain degree of depth carbon mother liquid filtrate and gallium concentrate filter cake, to obtain the gallium concentrate and partly remain degree of depth carbon mother liquid filtrate after the thorough carbonating decomposition of the gallium in the degree of depth carbon mother liquid filtrate, use dissolution of sodium hydroxide gallium concentrate again, obtain electrolytic solution after the filtering separation, obtain gallium through electrolysis.
Described gallium concentrate gallium aluminium ratio is 10~40.
Described residue intermediate product carbon mother liquid filtrate and part turn back in the stripping alkali lye in the aluminum oxide production process after remaining the mixing of degree of depth carbon mother liquid filtrate.
The invention has the advantages that: production technique is simple, with low cost, made full use of the processing condition of from non-bauxite such as flyash, coal gangue, kaolin, producing aluminum oxide, mend in the alkali process at the carbon operation break-down, need not increase any operation, just can reach the enrichment of gallium.
Description of drawings:
Fig. 1 is technological process of production figure of the present invention.
Embodiment:
Embodiment 1: the present invention utilizes 1 ton in flyash, 4 tons of preparations of Wingdale raw material, under 1200 ℃, sinter 3.1 tons in grog into, stripping is after 0.5 hour under 70 ℃ of temperature for the yellow soda ash alkali lye of grog usefulness 60g/l, and liquid-solid separation obtains silico-calcium slag filter cake and the sour sodium of aluminium (gallium) (NaAl (Ga) O 2) filtrate 16.5m 3The sour sodium of aluminium (gallium) (NaAl (Ga) O wherein 2) the concentration of aluminum oxide in the filtrate is 30g/l, the concentration of gallium oxide is 0.067g/l.The sour sodium filtrate of aluminium (gallium) is adopted CO 2The continuous carbonation decomposition obtains aluminum hydroxide filter cake and intermediate product carbon mother liquid filtrate 16.3m 3Alumina concentration is 0.64g/l in the mensuration intermediate product carbon mother liquid filtrate, when the concentration of gallium oxide is 0.064g/l, gets the carbon mother liquid filtrate 1.63m of the volume percent 10% of intermediate product carbon mother liquid filtrate 3In the carbon mother liquid filtrate of being got, add sodium bicarbonate 30g/l, stir, temperature is 60 ℃, churning time is 1 hour, obtains degree of depth carbon mother liquid filtrate, obtains the gallium concentrate and partly remains degree of depth carbon mother liquid filtrate after the thorough carbonating of the gallium in the degree of depth carbon mother liquid filtrate is decomposed, with obtaining electrolytic solution after dissolution of sodium hydroxide gallium concentrate, the filtering separation, obtain gallium again through electrolysis.Gallium concentrate gallium aluminium ratio is 10.Residue intermediate product carbon mother liquid filtrate 14.67m 3And part remains degree of depth carbon mother liquid filtrate 1.60m 3After the mixing, turn back in the stripping alkali lye of producing in the alumina process, continue the stripping grog.
Embodiment 2: the present invention utilizes 0.7 ton in flyash, 0.3 ton of coal gangue, 1.5 tons of preparations of Wingdale raw material, under 1450 ℃, sinter 1.6 tons in grog into, stripping is after 1 hour under 70 ℃ of temperature for the yellow soda ash alkali lye of grog usefulness 60g/l, and liquid-solid separation obtains silico-calcium slag filter cake and the sour sodium of aluminium (gallium) (NaAl (Ga) O 2) filtrate 3.7m 3The sour sodium of aluminium (gallium) (NaAl (Ga) O wherein 2) the concentration of aluminum oxide in the filtrate is 40g/l, the concentration of gallium oxide is 0.06g/l.The sour sodium filtrate of aluminium (gallium) is adopted CO 2The continuous carbonation decomposition obtains aluminum hydroxide filter cake and intermediate product carbon mother liquid filtrate 2.6m 3Measure alumina concentration 1.42g/l in the intermediate product carbon mother liquid filtrate, when the concentration of gallium oxide is 0.057g/l, get the carbon mother liquid filtrate 0.65m of the volume percent 25% of intermediate product carbon mother liquid filtrate 3In the carbon mother liquid filtrate of being got, add sodium bicarbonate 60g/l, stir, temperature is 70 ℃, churning time is 4 hours, obtains degree of depth carbon mother liquid filtrate, obtains the gallium concentrate and partly remains degree of depth carbon mother liquid filtrate after the thorough carbonating of the gallium in the degree of depth carbon mother liquid filtrate is decomposed, with obtaining electrolytic solution after dissolution of sodium hydroxide gallium concentrate, the filtering separation, obtain gallium again through electrolysis.Gallium concentrate gallium aluminium ratio is 25.Residue intermediate product carbon mother liquid filtrate 1.95m 3 And part remains degree of depth carbon mother liquid filtrate 0.62m 3After the mixing, turn back in the stripping alkali lye of producing in the alumina process, continue the stripping grog.
Embodiment 3: the present invention utilizes 0.6 ton in flyash, 0.2 ton of coal gangue, 0.2 ton of kaolin and 2 tons of preparations of Wingdale raw material, under 1350 ℃, sinter 1.9 tons in grog into, stripping is after 1 hour under 70 ℃ of temperature for the yellow soda ash alkali lye of grog usefulness 60g/l, and liquid-solid separation obtains silico-calcium slag filter cake and the sour sodium of aluminium (gallium) (NaAl (Ga) O 2) filtrate 6.3m 3The sour sodium of aluminium (gallium) (NaAl (Ga) O wherein 2) the concentration of aluminum oxide in the filtrate is 26g/l, the concentration of gallium oxide is 0.05g/l.The sour sodium filtrate of aluminium (gallium) is adopted CO 2The continuous carbonation decomposition obtains aluminum hydroxide filter cake and intermediate product carbon mother liquid filtrate 6.2m 3Alumina concentration is 2.0g/l in the mensuration intermediate product carbon mother liquid filtrate, when the concentration of gallium oxide is 0.05g/l, gets the carbon mother liquid filtrate 2.48m of the volume percent 40% of intermediate product carbon mother liquid filtrate 3In the carbon mother liquid filtrate of being got, add sodium bicarbonate 90g/l, stir, temperature is 90 ℃, churning time is 8 hours, obtains degree of depth carbon mother liquid filtrate, obtains the gallium concentrate and partly remains degree of depth carbon mother liquid filtrate after the thorough carbonating of the gallium in the degree of depth carbon mother liquid filtrate is decomposed, with obtaining electrolytic solution after dissolution of sodium hydroxide gallium concentrate, the filtering separation, obtain gallium again through electrolysis.Gallium concentrate gallium aluminium ratio is 30.Residue intermediate product carbon mother liquid filtrate 3.72m 3And part remains degree of depth carbon mother liquid filtrate 2.45m 3After the mixing, turn back in the stripping alkali lye of producing in the alumina process, continue the stripping grog.

Claims (3)

1. method of extracting gallium, it is characterized in that, include following steps: utilize flyash, or coal gangue, or in the process of the non-bauxite into alumina of any one or two kinds of above combinations of kaolin, production obtains intermediate product carbon mother liquid filtrate, alumina content is 0.64~2.0g/l in the wherein said carbon mother liquid filtrate, gallium enrichment concentration is the carbon mother liquid filtrate that 0.05-0.064g/l gets the volume percent 10%-40% of described intermediate product carbon mother liquid filtrate, in the described carbon mother liquid filtrate of being got, add sodium bicarbonate, stir, the concentration range of wherein said sodium bicarbonate is 30~90g/l, temperature is 60~90 ℃, churning time is 1~8 hour, obtains degree of depth carbon mother liquid filtrate and gallium concentrate filter cake, obtains the gallium concentrate and partly remains degree of depth carbon mother liquid filtrate after the thorough carbonating of the gallium in the degree of depth carbon mother liquid filtrate is decomposed, use dissolution of sodium hydroxide gallium concentrate again, obtain electrolytic solution after the filtering separation, obtain gallium through electrolysis.
2. a kind of method of extracting gallium according to claim 1 is characterized in that, described gallium concentrate gallium aluminium ratio is 10~40.
3. a kind of method of extracting gallium according to claim 1 is characterized in that, described residue intermediate product carbon mother liquid filtrate and part turn back in the stripping alkali lye of producing in the alumina process after remaining the mixing of degree of depth carbon mother liquid filtrate.
CNB200710141488XA 2007-08-23 2007-08-23 Production method for extracting gallium Active CN100494428C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864525A (en) * 2010-04-27 2010-10-20 中国神华能源股份有限公司 Method for extracting gallium from fly ash
DE112011101460T5 (en) 2010-04-27 2013-02-28 China Shenhua Energy Company Limited Method for extracting gallium from fly ash
RU2507280C1 (en) * 2012-07-23 2014-02-20 Открытое Акционерное Общество "Челябинский цинковый завод" Processing method of zinc-containing metallurgical waste
CN111778413A (en) * 2020-07-03 2020-10-16 神华准能资源综合开发有限公司 Method for extracting gallium from fly ash based on resin method
CN112430737A (en) * 2020-10-29 2021-03-02 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Method for recovering gallium from extraction gallium precipitation slag

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864525A (en) * 2010-04-27 2010-10-20 中国神华能源股份有限公司 Method for extracting gallium from fly ash
CN102191384A (en) * 2010-04-27 2011-09-21 中国神华能源股份有限公司 Method for extracting gallium from fly ash
CN102191384B (en) * 2010-04-27 2012-10-17 中国神华能源股份有限公司 Method for extracting gallium from fly ash
DE112011101460T5 (en) 2010-04-27 2013-02-28 China Shenhua Energy Company Limited Method for extracting gallium from fly ash
DE112011101461T5 (en) 2010-04-27 2013-02-28 China Shenhua Energy Company Limited Method for extracting gallium from fly ash
RU2506332C1 (en) * 2010-04-27 2014-02-10 Чайна Шэньхуа Энерджи Компани Лимитед Method for extraction of gallium from fly ash
RU2507282C1 (en) * 2010-04-27 2014-02-20 Чайна Шэньхуа Энерджи Компани Лимитед Method for extraction of gallium from fly ash
US8728296B2 (en) 2010-04-27 2014-05-20 China Shenhua Energy Company Limited Method for extracting gallium from fly ash
RU2507280C1 (en) * 2012-07-23 2014-02-20 Открытое Акционерное Общество "Челябинский цинковый завод" Processing method of zinc-containing metallurgical waste
CN111778413A (en) * 2020-07-03 2020-10-16 神华准能资源综合开发有限公司 Method for extracting gallium from fly ash based on resin method
CN112430737A (en) * 2020-10-29 2021-03-02 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Method for recovering gallium from extraction gallium precipitation slag

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