CN101117662A - Method for producing metal gallium with coproduction of alumina - Google Patents
Method for producing metal gallium with coproduction of alumina Download PDFInfo
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- CN101117662A CN101117662A CNA2007101451323A CN200710145132A CN101117662A CN 101117662 A CN101117662 A CN 101117662A CN A2007101451323 A CNA2007101451323 A CN A2007101451323A CN 200710145132 A CN200710145132 A CN 200710145132A CN 101117662 A CN101117662 A CN 101117662A
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- gallium
- stripping
- grog
- filter cake
- coproduction
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000002184 metal Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 48
- 239000012065 filter cake Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 36
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 25
- 238000004131 Bayer process Methods 0.000 claims abstract description 16
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 239000003245 coal Substances 0.000 claims abstract description 13
- 239000010881 fly ash Substances 0.000 claims abstract description 13
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 110
- 239000000243 solution Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 34
- 238000001556 precipitation Methods 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- 230000029087 digestion Effects 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229940074391 gallic acid Drugs 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 5
- 238000005272 metallurgy Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
Images
Classifications
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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 discloses a method for producing gallium joint alumina, and comprises the following steps: firstly, grog refractory is prepared; secondly, grog refractory is dissolved out to get filtrate and filter cake; thirdly, dissolved-out grog refractory is circulated; fourthly, aluminium hydroxide filter cake containing gallium with high content is enriched into 70 to 700 ppm gallium oxide through a bayer process dissolved-out system; fifthly, gallium oxide is prepared; sixthly, aluminium hydroxide filter cake in the step (4) is used as metallurgical alumina after being washed and baked. The present invention has the advantages that the art is simple, alumina can be separated from fly ash, coal gangue, and kaoline, and also the gallium can be extracted, thereby making the non-bauxite ores such as the fly ash mine, the coal gangue mine, and the kaoline mine get the comprehensive utilization fully, and through adopting the method, the cost of producing gallium is low, the recovery percent of gallium is high, the method is simple and convenient, and the industrialization production is convenient.
Description
Technical field
The present invention relates to a kind of production method of gallium, especially relate to a kind of method of further producing 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 produce in the aluminium circulating mother liquor in oxidation with resin, and the absorption gallium carries out desorption, 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 aluminium loss of can effectively reducing, improve the concentration of gallium in the circulating mother liquor, a kind of method of from contain the non-bauxite of aluminium, producing metal gallium with coproduction of alumina that cost is effectively reduced.
Purpose of the present invention is implemented by following technical scheme: a kind of method of from contain the non-bauxite of aluminium, producing metal gallium with coproduction of alumina, include following steps,
(1). preparation grog: utilize flyash, or coal gangue, or the non-bauxite of any one or two kinds of above combinations of kaolin and Wingdale carry out sintering and prepare grog;
(2). the stripping grog, get filtrate and filter cake: utilize yellow soda ash alkali lye with the grog stripping in the step (1), make aluminum oxide in the stripping grog and gallium oxide with sodium aluminate and the stripping of gallic acid na form, get thick liquid and silico-calcium slag filter cake through solid-liquid separation, in described thick liquid through CO
2The thorough carbonating of gas is decomposed, through liquid-solid separation, and the aluminum hydroxide filter cake that gained filtrate and gallium content are high;
(3). circulation stripping grog: described step (2) gained filtrate turns back in the described stripping grog of step (2), circulation stripping grog;
(4). it is the 70-700ppm gallium oxide that the aluminum hydroxide filter cake that described gallium content is high is enriched to concentration by the Bayer process digestion series: the high aluminum hydroxide filter cake of gallium content described in the step (2) is entered the Bayer process digestion series, be that described Bayer process digestion series is that aluminum hydroxide filter cake that gallium content described in the step (2) is high carries out liquid-solid separation after by the sodium hydroxide solution stripping, gained refined liquid and red mud, described refined liquid adds aluminium hydroxide crystal seed and carries out the seed decomposition, wherein every liter of refined liquid adds the aluminium hydroxide crystal seed of 400g-800g, decomposition obtains aluminum hydroxide precipitation, is aluminum hydroxide filter cake; Gallium oxide is stayed in the described seed precipitation solution; Described seed precipitation solution warp concentrates, and mends sodium hydroxide, makes its sodium hydroxide lye concentration that reaches described stripping, and described seed precipitation solution continues stripping gallium aluminium composite salt, and through the circulation stripping, extremely gallium oxide concentration is rich long-pending to 70-700ppm in the described seed precipitation solution;
(5). the preparation of gallium: take in the seed precipitation solution of resin adsorption method from above-mentioned steps (4) gallium to be adsorbed, the gallium ion desorption that will be adsorbed in the resin with desorbing agent comes out to divide to parse again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer;
(6). aluminum hydroxide filter cake described in the step (4) through washing, after the roasting as the metallurgy aluminum oxide.
Flyash in the described step (1), or coal gangue, or the non-bauxite and the Wingdale of any one or two kinds of above combinations of kaolin, by weight, described non-bauxite: Wingdale is 1: 1.5-4, sintering temperature is 1200 ℃-1450 ℃.
Grog in the described step (2) and described yellow soda ash alkali lye are pressed the solid-liquid weight part, and grog in the step (2) and described yellow soda ash alkali lye are 1: 3-6.
Described yellow soda ash alkali lye in the described step (2) is counted 30g/l-90g/l with Na2O.
Stripping temperature described in the described step (2) is 50 ℃-90 ℃; Dissolution time 0.5-1.5 hour.
The temperature that thorough carbonating is decomposed described in the described step (2) is at 50 ℃-90 ℃; Resolving time was at 0.5-4 hour.
The aluminum hydroxide filter cake that gallium content is high described in the described step (4) and the solid-liquid weight part of described sodium hydroxide solution are 1: 5-10, the concentration of wherein said sodium hydroxide solution is with Na
2O counts 180g/l-220g/l.
130 ℃-160 ℃ of stripping temperature in the described step (4) in described sodium hydroxide solution, dissolution time are 20 minutes-90 minutes.
It is 40 ℃-80 ℃ that the adding of refined liquid described in the described step (4) aluminium hydroxide crystal seed carries out the seed decomposition temperature; Resolving time 48-80 hour.
Resin adsorption method described in the described step (5) is to adopt resin from described seed precipitation solution gallium to be adsorbed in the into described resin, the gallium ion desorption that will be adsorbed in the described resin with desorbing agent comes out to divide to parse again again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer.
The invention has the advantages that: technology is simple, not only from flyash, coal gangue, kaolin aluminum oxide is separated, and also gallium is extracted simultaneously.Non-bauxite such as flyash, coal gangue, kaolin are fully utilized fully.It is low to adopt this method to produce the gallium cost simultaneously, gallium rate of recovery height, and method is easy, and easily row is convenient to suitability for industrialized production.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
Embodiment 1: a kind of method of from contain the non-bauxite of aluminium, producing metal gallium with coproduction of alumina, include following steps,
(1). preparation grog: get 1 ton in flyash, carry out sintering with 1.5 tons of Wingdales at 1200 ℃ and be prepared into 1.6 tons of grogs;
(2). the stripping grog gets filtrate and filter cake: get yellow soda ash alkali lye 4.8m
3With 1.6 tons of grog strippings, wherein yellow soda ash alkali lye is with Na
2O counts 90g/l.The stripping temperature is 50 ℃; Dissolution time 0.5 hour.Make aluminum oxide in the stripping grog and gallium oxide with sodium aluminate and the stripping of gallic acid na form, get thick liquid 3.7m through solid-liquid separation
3With 2.7 tons of silico-calcium slag filter cakes, at 3.7m
3In the thick liquid through CO
2The thorough carbonating of gas is decomposed, and thoroughly the temperature of carbonating decomposition is at 50 ℃; Resolving time was at 0.5 hour.Through liquid-solid separation, gained filtrate 2.6m
3With 303 kilograms of the high aluminum hydroxide filter cakes of gallium content;
(3). circulation stripping grog: step (2) gained filtrate turns back in the stripping grog of step (2) again, circulation stripping grog;
(4) the high aluminum hydroxide filter cake of .303 kilogram gallium content, be enriched to the gallium oxide that concentration is 70ppm by the Bayer process digestion series: the high aluminum hydroxide filter cake of gallium content in the step (2) is entered the Bayer process digestion series for 303 kilograms, and promptly the Bayer process digestion series is that the aluminum hydroxide filter cake that gallium content in the step (2) is high is with Na by concentration for 303 kilograms
2O counts 1515 kilograms of strippings of 180g/l sodium hydroxide solution, 130 ℃ of the stripping temperature in the sodium hydroxide solution, and dissolution time is 20 minutes.Carry out liquid-solid separation after the stripping, gained refined liquid 1.16m
3And red mud, 1.16m
3The aluminium hydroxide crystal seed that the refined liquid adding is 460 kilograms carries out seed and decomposes, and decomposition temperature is 40 ℃-60 ℃; 48 hours resolving times.Decomposition obtains aluminum hydroxide precipitation, promptly gets 152 kilograms of aluminum hydroxide filter cakes; Gallium oxide is stayed in the seed precipitation solution; Seed precipitation solution concentrates through tube-type down-flow evaporator, mends sodium hydroxide, and making its sodium hydroxide lye concentration that reaches stripping is 180g/l, continues stripping gallium aluminium composite salt, and through the circulation stripping, gallium oxide concentration is 70ppm to the seed precipitation solution, the 101g gallium oxide;
(5). the preparation of gallium: taking resin adsorption method is to adopt resin from seed precipitation solution gallium to be adsorbed in the resin, the gallium ion desorption that will be adsorbed in the resin with desorbing agent comes out to divide to parse again again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer.
(6). in the step (4) aluminum hydroxide filter cake after washing, roasting as the metallurgy aluminum oxide.
Embodiment 2: a kind of method of from contain the non-bauxite of aluminium, producing metal gallium with coproduction of alumina, include following steps,
(1). preparation grog: get 1 ton of flyash and coal gangue, carry out sintering with 4 tons of Wingdales at 1450 ℃ and be prepared into 3.1 tons of grogs;
(2). the stripping grog gets filtrate and filter cake: get yellow soda ash alkali lye 18.6m
3With 3.1 tons of grog strippings, wherein yellow soda ash alkali lye is with Na
2O counts 30g/l.The stripping temperature is 90 ℃; Dissolution time 1.5 hours.Make aluminum oxide in the stripping grog and gallium oxide with sodium aluminate and the stripping of gallic acid na form, get thick liquid 16.5m through solid-liquid separation
3With 5.2 tons of silico-calcium slag filter cakes, at 16.5m
3In the thick liquid through CO
2The thorough carbonating of gas is decomposed, and thoroughly the temperature of carbonating decomposition is at 90 ℃; 4 hours resolving times.Through liquid-solid separation, gained filtrate 16.3m
3With 390 kilograms of the high aluminum hydroxide filter cakes of gallium content;
(3). circulation stripping grog: step (2) gained filtrate turns back in the stripping grog of step (2) again, circulation stripping grog;
(4) to be enriched to concentration by the Bayer process digestion series be the 700ppm gallium oxide to the aluminum hydroxide filter cake that .390 kilogram gallium content is high: the high aluminum hydroxide filter cake of gallium content in the step (2) is entered the Bayer process digestion series for 390 kilograms, and promptly the Bayer process digestion series is 390 kilograms of aluminum hydroxide filter cakes that gallium content in the step (2) is high by concentration for Na
2O counts 3900 kilograms of strippings of 220g/l sodium hydroxide solution, 160 ℃ of the stripping temperature in the sodium hydroxide solution, and dissolution time is 90 minutes.Carry out liquid-solid separation after the stripping, gained refined liquid 3.44m
3And red mud, 3.44m
3The aluminium hydroxide crystal seed that the refined liquid adding is 2752 kilograms carries out seed and decomposes, and decomposition temperature is 60 ℃-80 ℃; 80 hours resolving times.Decomposition obtains aluminum hydroxide precipitation, promptly gets 195 kilograms of aluminum hydroxide filter cakes; Gallium oxide is stayed in the seed precipitation solution; Seed precipitation solution concentrates through tube-type down-flow evaporator, mends sodium hydroxide, and making its sodium hydroxide lye concentration that reaches stripping is 220g/1, continues stripping gallium aluminium composite salt, and through the circulation stripping, gallium oxide concentration is 700ppm to the seed precipitation solution, the 3010g gallium oxide;
(5). the preparation of gallium: taking resin adsorption method is to adopt resin from seed precipitation solution gallium to be adsorbed in the resin, the gallium ion desorption that will be adsorbed in the resin with desorbing agent comes out to divide to parse again again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer.
(6). in the step (4) aluminum hydroxide filter cake after washing, roasting as the metallurgy aluminum oxide.
Embodiment 3: a kind of method of from contain the non-bauxite of aluminium, producing metal gallium with coproduction of alumina, include following steps,
(1). preparation grog: get 1 ton of flyash, coal gangue and kaolin, carry out sintering with 2 tons of Wingdales at 1350 ℃ and be prepared into 1.9 tons of grogs;
(2). the stripping grog gets filtrate and filter cake: get yellow soda ash alkali lye 7.6m
3With 1.9 tons of grog strippings, wherein yellow soda ash alkali lye is with Na
2O counts 60g/l.The stripping temperature is 70 ℃; Dissolution time 1.0 hours.Make aluminum oxide in the stripping grog and gallium oxide with sodium aluminate and the stripping of gallic acid na form, get thick liquid 6.3m through solid-liquid separation
3With 3.2 tons of silico-calcium slag filter cakes, at 6.3m
3In the thick liquid through CO
2The thorough carbonating of gas is decomposed, and thoroughly the temperature of carbonating decomposition is at 70 ℃; 2.5 hours resolving times.Through liquid-solid separation, gained filtrate 6.2m
3With 290 kilograms of the high aluminum hydroxide filter cakes of gallium content;
(3). circulation stripping grog: step (2) gained filtrate turns back in the stripping grog of step (2) again, circulation stripping grog;
(4) to be enriched to concentration by the Bayer process digestion series be the 400ppm gallium oxide to the aluminum hydroxide filter cake that .290 kilogram gallium content is high: the high aluminum hydroxide filter cake of gallium content in the step (2) is entered the Bayer process digestion series for 290 kilograms, and promptly the Bayer process digestion series is 290 kilograms of aluminum hydroxide filter cakes that gallium content in the step (2) is high by concentration for Na
2O counts 1740 kilograms of strippings of 200g/l sodium hydroxide solution, 150 ℃ of the stripping temperature in the sodium hydroxide solution, and dissolution time is 60 minutes.Carry out liquid-solid separation after the stripping, gained refined liquid 2.09m
3And red mud, 2.09m
3The aluminium hydroxide crystal seed that the refined liquid adding is 1254 kilograms carries out seed and decomposes, and decomposition temperature is 50 ℃; 60 hours resolving times.Decomposition obtains aluminum hydroxide precipitation, is 145 kilograms of aluminum hydroxide filter cakes; Gallium oxide is stayed in the seed precipitation solution; Seed precipitation solution concentrates through tube-type down-flow evaporator, mends sodium hydroxide, and making its sodium hydroxide lye concentration that reaches stripping is 200g/l, continues stripping gallium aluminium composite salt, and through the circulation stripping, gallium oxide concentration is 400ppm to the seed precipitation solution, the 1045g gallium oxide;
(5). the preparation of gallium: taking resin adsorption method is to adopt resin from seed precipitation solution gallium to be adsorbed in the resin, the gallium ion desorption that will be adsorbed in the resin with desorbing agent comes out to divide to parse again again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer.
(6). in the step (4) aluminum hydroxide filter cake after washing, roasting as the metallurgy aluminum oxide.
Non-bauxite among the embodiment 1,2,3 also can adopt coal gangue or kaolinic any, or coal gangue and kaolin can be as carrying out the raw material that sintering prepares grog with Wingdale, or flyash and kaolin also can be as carrying out the raw material that sintering prepares grog with Wingdale.
Claims (10)
1. a method of producing metal gallium with coproduction of alumina is characterized in that it includes following steps,
(1). preparation grog: utilize flyash, or coal gangue, or the non-bauxite of any one or two kinds of above combinations of kaolin and Wingdale carry out sintering and prepare grog;
(2). the stripping grog, get filtrate and filter cake: utilize yellow soda ash alkali lye with the grog stripping in the step (1), make aluminum oxide in the stripping grog and gallium oxide with sodium aluminate and the stripping of gallic acid na form, get thick liquid and silico-calcium slag filter cake through solid-liquid separation, in described thick liquid through CO
2The thorough carbonating of gas is decomposed, through liquid-solid separation, and the aluminum hydroxide filter cake that gained filtrate and gallium content are high;
(3). circulation stripping grog: described step (2) gained filtrate turns back in the described stripping grog of step (2), circulation stripping grog;
(4). it is the 70-700ppm gallium oxide that the aluminum hydroxide filter cake that described gallium content is high is enriched to concentration by the Bayer process digestion series: the high aluminum hydroxide filter cake of gallium content described in the step (2) is entered the Bayer process digestion series, be that described Bayer process digestion series is that aluminum hydroxide filter cake that gallium content described in the step (2) is high carries out liquid-solid separation after by the sodium hydroxide solution stripping, gained refined liquid and red mud, described refined liquid adds aluminium hydroxide crystal seed and carries out the seed decomposition, wherein every liter of refined liquid adds the aluminium hydroxide crystal seed of 400g-800g, decomposition obtains aluminum hydroxide precipitation, is aluminum hydroxide filter cake; Gallium oxide is stayed in the described seed precipitation solution; Described seed precipitation solution is mended sodium hydroxide through concentrating, and makes its sodium hydroxide lye concentration that reaches described stripping, and described seed precipitation solution continues stripping gallium aluminium composite salt, and through the circulation stripping, the gallium oxide concentration enrichment is to 70-700ppm to the described seed precipitation solution;
(5). the preparation of gallium: take in the seed precipitation solution of resin adsorption method from above-mentioned steps (4) gallium to be adsorbed, the gallium ion desorption that will be adsorbed in the resin with desorbing agent comes out to divide to parse again, dissolving, removal of impurities, prepare qualified electrolytic solution, electrolysis obtains gallium in electrolyzer;
(6). aluminum hydroxide filter cake described in the step (4) through washing, after the roasting as the metallurgy aluminum oxide.
2. a kind of method of producing metal gallium with coproduction of alumina according to claim 1, it is characterized in that, flyash in the described step (1), or coal gangue, or the non-bauxite and the Wingdale of any one or two kinds of above combinations of kaolin, by weight, described non-bauxite: Wingdale is 1: 1.5-4, sintering temperature is 1200 ℃-1450 ℃.
3. a kind of method of producing metal gallium with coproduction of alumina according to claim 1 is characterized in that, grog in the described step (2) and described yellow soda ash alkali lye are pressed the solid-liquid weight part, and grog in the step (2) and described yellow soda ash alkali lye are 1: 3-6.
4. according to claim 1 or 3 described a kind of methods of producing metal gallium with coproduction of alumina, it is characterized in that the described yellow soda ash alkali lye in the described step (2) is with Na
2O counts 30g/l-90g/l.
5. a kind of method of producing metal gallium with coproduction of alumina according to claim 1 is characterized in that, stripping temperature described in the described step (2) is 50 ℃-90 ℃; Dissolution time 0.5-1.5 hour.
6. a kind of method of producing metal gallium with coproduction of alumina according to claim 1 is characterized in that, the temperature that thorough carbonating is decomposed described in the described step (2) is at 50 ℃-90 ℃; Resolving time was at 0.5-4 hour.
7. a kind of method of producing metal gallium with coproduction of alumina according to claim 1, it is characterized in that, the aluminum hydroxide filter cake that gallium content is high described in the described step (4) and the solid-liquid weight part of described sodium hydroxide solution are 1: 5-10, the concentration of wherein said sodium hydroxide solution is with Na
2O counts 180g/l-220g/l.
8. a kind of method of producing metal gallium with coproduction of alumina according to claim 1 is characterized in that, 130 ℃-160 ℃ of the stripping temperature in the described step (4) in described sodium hydroxide solution, and dissolution time is 20 minutes-90 minutes.
9. a kind of method of producing metal gallium with coproduction of alumina according to claim 1 is characterized in that, it is 40 ℃-80 ℃ that the adding of refined liquid described in the described step (4) aluminium hydroxide crystal seed carries out the seed decomposition temperature; Resolving time 48-80 hour.
10. a kind of method of producing metal gallium with coproduction of alumina according to claim 1, it is characterized in that, resin adsorption method described in the described step (5) is to adopt resin from described seed precipitation solution gallium to be adsorbed in the into described resin, the gallium ion desorption that will be adsorbed in the described resin with desorbing agent comes out to divide to parse again again, dissolving, qualified electrolytic solution is prepared in removal of impurities, and electrolysis obtains gallium in electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101451323A CN100443601C (en) | 2007-08-23 | 2007-08-23 | Method for producing metal gallium with coproduction of alumina |
Applications Claiming Priority (1)
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| CN100443601C CN100443601C (en) | 2008-12-17 |
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| CN102011019A (en) * | 2010-12-14 | 2011-04-13 | 中国铝业股份有限公司 | Method for removing heavy-metal impurities in process of producing gallium by resin adsorption method |
| CN102080162A (en) * | 2010-12-09 | 2011-06-01 | 中国铝业股份有限公司 | Gallium mud separation method of extracting gallium from pregnant solution using resin adsorption |
| CN102154565A (en) * | 2010-04-27 | 2011-08-17 | 中国神华能源股份有限公司 | Method for extracting gallium from pulverized fuel ash |
| CN102517461A (en) * | 2011-12-16 | 2012-06-27 | 紫金矿业集团股份有限公司 | Method for recycling gallium in alunite concentrate |
| DE112011101461T5 (en) | 2010-04-27 | 2013-02-28 | China Shenhua Energy Company Limited | Method for extracting gallium from fly ash |
| CN102976394A (en) * | 2012-12-14 | 2013-03-20 | 中国铝业股份有限公司 | Method for extracting gallium hydroxide from vanadium slag |
| CN103071595A (en) * | 2012-12-31 | 2013-05-01 | 西部矿业集团有限公司 | Flotation method for gallium in fly ash |
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| CN105540627A (en) * | 2016-01-19 | 2016-05-04 | 中国铝业股份有限公司 | Preparation method for clinker of alumina produced by sintering process |
| CN108609661A (en) * | 2018-06-11 | 2018-10-02 | 中国神华能源股份有限公司 | A method of preparing iron oxide red, aluminium oxide, gallium using except sago cycas fat eluent |
| CN109179467A (en) * | 2018-09-30 | 2019-01-11 | 中铝山东有限公司 | A method of gallium is removed to the low pregnant Bayer process liquor of concentration containing gallium |
| CN111519024A (en) * | 2020-04-24 | 2020-08-11 | 朔州西廊煤炭科技有限公司 | Method for extracting gallium metal by using coal solid waste or bauxite solid waste through sintering method |
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| CN102080162A (en) * | 2010-12-09 | 2011-06-01 | 中国铝业股份有限公司 | Gallium mud separation method of extracting gallium from pregnant solution using resin adsorption |
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| CN102517461A (en) * | 2011-12-16 | 2012-06-27 | 紫金矿业集团股份有限公司 | Method for recycling gallium in alunite concentrate |
| CN102976394A (en) * | 2012-12-14 | 2013-03-20 | 中国铝业股份有限公司 | Method for extracting gallium hydroxide from vanadium slag |
| CN103071595B (en) * | 2012-12-31 | 2016-08-03 | 西部矿业股份有限公司 | A kind of method of flotation gallium in flyash |
| CN103071595A (en) * | 2012-12-31 | 2013-05-01 | 西部矿业集团有限公司 | Flotation method for gallium in fly ash |
| CN104018012A (en) * | 2014-06-16 | 2014-09-03 | 中国神华能源股份有限公司 | Method of extracting gallium from aluminum chloride solution |
| CN105540627A (en) * | 2016-01-19 | 2016-05-04 | 中国铝业股份有限公司 | Preparation method for clinker of alumina produced by sintering process |
| CN108609661A (en) * | 2018-06-11 | 2018-10-02 | 中国神华能源股份有限公司 | A method of preparing iron oxide red, aluminium oxide, gallium using except sago cycas fat eluent |
| CN108609661B (en) * | 2018-06-11 | 2020-07-10 | 中国神华能源股份有限公司 | Method for preparing iron oxide red, aluminum oxide and gallium by using iron-removing resin eluent |
| CN109179467A (en) * | 2018-09-30 | 2019-01-11 | 中铝山东有限公司 | A method of gallium is removed to the low pregnant Bayer process liquor of concentration containing gallium |
| CN111519024A (en) * | 2020-04-24 | 2020-08-11 | 朔州西廊煤炭科技有限公司 | Method for extracting gallium metal by using coal solid waste or bauxite solid waste through sintering method |
| CN111519024B (en) * | 2020-04-24 | 2022-05-24 | 朔州西廊煤炭科技有限公司 | Method for extracting gallium metal by using coal solid waste or bauxite solid waste through sintering method |
| CN111961867A (en) * | 2020-09-15 | 2020-11-20 | 神华准格尔能源有限责任公司 | Method for extracting gallium from iron-removing waste liquid generated in process of preparing alumina from fly ash |
| CN112939046A (en) * | 2021-02-26 | 2021-06-11 | 四川顺应动力电池材料有限公司 | Comprehensive recycling method of coal-based solid waste |
| CN113430377A (en) * | 2021-05-13 | 2021-09-24 | 北京科技大学 | Method for comprehensively extracting valuable components from coal gangue |
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