CN101249983B - Preparation method of high-purity gallium oxide - Google Patents
Preparation method of high-purity gallium oxide Download PDFInfo
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- CN101249983B CN101249983B CN200810014780XA CN200810014780A CN101249983B CN 101249983 B CN101249983 B CN 101249983B CN 200810014780X A CN200810014780X A CN 200810014780XA CN 200810014780 A CN200810014780 A CN 200810014780A CN 101249983 B CN101249983 B CN 101249983B
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- Prior art keywords
- gallium
- sulfate
- purity
- ammonium
- gallium oxide
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229910000373 gallium sulfate Inorganic materials 0.000 claims abstract description 61
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims abstract description 61
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims abstract 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 47
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001953 recrystallisation Methods 0.000 claims description 13
- 235000011149 sulphuric acid Nutrition 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 10
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910052745 lead Inorganic materials 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HLNYIAPJLJSOQM-GTKRZRNESA-N (5s)-1-[(2s)-1-[(2s)-2-[[(6s)-6-benzyl-2,3-dioxopiperazin-1-yl]methyl]pyrrolidin-1-yl]-3-phenylpropan-2-yl]-5-[(4-hydroxyphenyl)methyl]-4-(2-phenylethyl)piperazine-2,3-dione Chemical compound C1=CC(O)=CC=C1C[C@@H]1N(CCC=2C=CC=CC=2)C(=O)C(=O)N([C@H](CN2[C@@H](CCC2)CN2C(C(=O)NC[C@@H]2CC=2C=CC=CC=2)=O)CC=2C=CC=CC=2)C1 HLNYIAPJLJSOQM-GTKRZRNESA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention relates to a preparing process for high purity gallium oxide, which is used to prepare the high-purity gallium oxide, wherein the process comprises steps of utilizing gallium metal to react with sulfuric acid to form gallium sulfate, polymerizing the gallium sulfate and ammonia sulfate in water solution, separating crystal of gallium ammonia sulfate from the crystallization and then drying and sintering, finally obtaining high purity gallium oxide. Because of bringing the process of purifying, crude gallium can be used as the essential material absolutely, thereby the limit of raw material purity of others processes is overcame and the production cost is reduced greatly, further as employing the gallium ammonia sulfate process to prepare the gallium oxide, the process is easy to be carried out, the product is not only high in purity which can reach 5N, wherein contents of impurities of Cu, Zn, Ni, Pb, Al, C are all less than 1 ppm, and contents of Na, Fe are less than 3 ppm, but also reliable in quality and easy in controlling.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity gallium oxide, be used to prepare high-purity gallium oxide.
Background technology
High-purity gallium oxide is mainly used in synthetic gadolinium gallium garnet, and gadolinium gallium garnet is main magnetic memory materials, and along with the develop rapidly of information industry, its consumption heightens.Gallium oxide also can be used as catalyzer, LED fluorescent material of organic reaction etc., and in recent years along with the development and use of novel material, the purposes of gallium oxide more and more widely.
The preparation method of high-purity gallium oxide mainly contains two kinds: neutralisation and hydrothermal synthesis method, two kinds of methods are basic raw material with the 6N high purity gallium all.During neutralisation adopts and sodium solution gallate, obtain the gallium hydroxide precipitation, washing, oven dry, roasting make gallium oxide, and its shortcoming is that purity is influenced by mother liquor composition, the foreign matter content height.Hydrothermal synthesis method need adopt high-temperature high-voltage reaction, yield poorly, and product purity influences by body material the foreign matter content instability.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-purity gallium oxide, easy to implement, cost is low, and the product purity height of acquisition, and constant product quality are easy to control.
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Wherein:
Gallium uses the 4N gallium;
Sulfuric acid uses the analytical pure sulfuric acid of 50-98%;
The pure ammonium sulfate of ammonium sulfate operational analysis;
The aqueous solution uses deionized water.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and the 50-98% vitriol oil reacted 0.5-5 hour under temperature 50-80 ℃, can obtain the gallium sulfate solution of gallium content 50-100 grams per liter.
(2) crystallisation by cooling: gallium sulfate and chemistry at-10 ℃ of following crystallisation by cooling 12-48 hours, become ammonium gallium sulfate double salt than excessive 2-5 ammonium sulfate mixing in the aqueous solution doubly.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 2-6 time again, can make high-purity sulphuric acid gallium ammonium.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 5-10 hour under 80-200 ℃ of temperature, through 800-1200 ℃ high-temperature roasting 2-5 hour, made high-purity β-Yang Hua gallium.
The present invention adopts the ammonium gallium sulfate legal system to be equipped with gallium oxide, owing to introduce intermediate purification technology, fully can be with thick gallium as basic raw material, overcome the limitation of other method to material purity, greatly reduce production cost, and adopt sour gallium ammonium legal system to be equipped with gallium oxide, technology is easy to implement, the product purity height that obtains, can reach 5N (5N represents that purity is 99.999%), impurity Cu, Zn wherein, Ni, Pb, Al, Ca equal size are all less than 1ppm, and Na, Fe equal size are less than 3ppm, and constant product quality is easy to control.
Embodiment
The invention will be further described below in conjunction with embodiment.
Raw materials used:
Gallium uses the 4N gallium;
Sulfuric acid uses the analytical pure sulfuric acid of 50-98%;
The pure ammonium sulfate of ammonium sulfate operational analysis;
The aqueous solution uses deionized water.
Embodiment 1
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and 98% the vitriol oil reacted 3 hours under 50 ℃ of temperature, can obtain the gallium sulfate solution of gallium content 70 grams per liters.
(2) crystallisation by cooling: gallium sulfate and chemistry are than excessive 3 times ammonium sulfate mixing in the aqueous solution, and crystallisation by cooling is 24 hours under-10 ℃ of temperature, becomes ammonium gallium sulfate double salt.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 4 times again, can make high-purity sulphuric acid gallium ammonium.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 7 hours under 180 ℃ of temperature, through 1000 ℃ high-temperature roastings 3 hours, made high-purity β-Yang Hua gallium.
Impurity Cu, Zn in the product, Ni, Pb, Al, Ca content are all less than 1ppm, and Na, Fe content are less than 3ppm.
Embodiment 2
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and 75% vitriol oil reacted 2 hours under 60 ℃ of temperature, can obtain the gallium sulfate solution of gallium content 60 grams per liters.
(2) crystallisation by cooling: gallium sulfate and chemistry-10 ℃ of following crystallisation by cooling 48 hours, become ammonium gallium sulfate double salt than excessive 4 times ammonium sulfate mixing in the aqueous solution.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 5 times again, can make high-purity sulphuric acid gallium ammonium crystal.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 10 hours under 150 ℃ of temperature, through 900 ℃ high-temperature roastings 3 hours, made high-purity β-Yang Hua gallium.
Impurity Cu, Zn in the product, Ni, Pb, Al, Ca content are all less than 1ppm, and Na, Fe content are less than 3ppm.
Embodiment 3
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and 75% vitriol oil reacted 4 hours under 70 ℃ of temperature, can obtain the gallium sulfate solution of gallium content 90 grams per liters.
(2) crystallisation by cooling: gallium sulfate and chemistry-10 ℃ of following crystallisation by cooling 30 hours, become ammonium gallium sulfate double salt than excessive 4 times ammonium sulfate mixing in the aqueous solution.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 3 times again, can make high-purity sulphuric acid gallium ammonium.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 7 hours under 120 ℃ of temperature, through 1100 ℃ high-temperature roastings 3.5 hours, made high-purity β-Yang Hua gallium.
Impurity Cu, Zn in the product, Ni, Pb, Al, Ca content are all less than 1ppm, and Na, Fe content are less than 3ppm.
Embodiment 4
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and 98% vitriol oil reacted 3 hours under 75 ℃ of temperature, can obtain the gallium sulfate solution of gallium content 750 grams per liters.
(2) crystallisation by cooling: gallium sulfate and chemistry-10 ℃ of following crystallisation by cooling 28 hours, become ammonium gallium sulfate double salt than excessive 5 times ammonium sulfate mixing in the aqueous solution.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 4 times again, can make high-purity sulphuric acid gallium ammonium.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 6 hours under 150 ℃ of temperature, through 950 ℃ high-temperature roastings 3 hours, made high-purity β-Yang Hua gallium.
Impurity Cu, Zn in the product, Ni, Pb, Al, Ca content are all less than 1ppm, and Na, Fe content are less than 3ppm.
Embodiment 5
The preparation method of high-purity gallium oxide of the present invention, utilize gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
Concrete reaction control is as follows:
(1) dissolving: the 4N gallium and 75% vitriol oil reacted 3.5 hours under 65 ℃ of temperature, can obtain the gallium sulfate solution of gallium content 75 grams per liters.
(2) crystallisation by cooling: gallium sulfate and chemistry-10 ℃ of following crystallisation by cooling 42 hours, become ammonium gallium sulfate double salt than excessive 4 times ammonium sulfate mixing in the aqueous solution.
(3) recrystallization: after the ammonium gallium sulfate heating was water-soluble, crystallisation by cooling was 6 times again, can make high-purity sulphuric acid gallium ammonium.
(4) oven dry, roasting: the ammonium gallium sulfate crystal dewatered 8 hours under 100 ℃ of temperature, through 850 ℃ high-temperature roastings 5 hours, made high-purity β-Yang Hua gallium.
Impurity Cu, Zn in the product, Ni, Pb, Al, Ca content are all less than 1ppm, and Na, Fe content are less than 3ppm.
Claims (5)
1. the preparation method of a high-purity gallium oxide, it is characterized in that utilizing gallium and sulfuric acid reaction to generate gallium sulfate, make gallium sulfate and ammonium sulfate polymerizable crystallizable in the aqueous solution separate out the ammonium gallium sulfate crystal, the ammonium gallium sulfate crystal is handled through recrystallization repeatedly, make high-purity sulphuric acid gallium ammonium crystal, through oven dry, roasting, obtain high-purity gallium oxide at last.
2. the preparation method of high-purity gallium oxide according to claim 1 is characterized in that gallium is the 4N gallium.
3. the preparation method of high-purity gallium oxide according to claim 2 is characterized in that sulfuric acid is the analytical pure sulfuric acid of 50-98%.
4. the preparation method of high-purity gallium oxide according to claim 3 is characterized in that ammonium sulfate is the analytical pure sulfuric acid ammonium.
5. the preparation method of high-purity gallium oxide according to claim 4 is characterized in that the aqueous solution uses deionized water.
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| CN200810014780XA CN101249983B (en) | 2008-03-21 | 2008-03-21 | Preparation method of high-purity gallium oxide |
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| CN200810014780XA CN101249983B (en) | 2008-03-21 | 2008-03-21 | Preparation method of high-purity gallium oxide |
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| CN101249983B true CN101249983B (en) | 2011-07-06 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993110B (en) * | 2010-11-14 | 2012-06-27 | 青岛理工大学 | Method for preparing beta-gallium oxide by microwave hydrothermal method |
| CN102491406B (en) * | 2011-11-24 | 2013-08-14 | 中国铝业股份有限公司 | Method for preparing gallium sulfate |
| CN102978649B (en) * | 2012-12-14 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of high-purity gallium oxide |
| CN103708533B (en) * | 2014-01-06 | 2015-10-21 | 贵州万方铝化科技开发有限公司 | One prepares nanometer Ga 2o 3the method of powder |
| CN103787403B (en) * | 2014-02-26 | 2015-08-05 | 贵州万方铝化科技开发有限公司 | A kind of method containing fluorochemical recycle in gallium compound production |
| CN104229872B (en) * | 2014-09-18 | 2015-10-21 | 株洲科能新材料有限责任公司 | A kind of technique of continuous seepage micron order gallium oxide powder |
| CN107841785B (en) * | 2017-10-27 | 2020-06-02 | 浙江理工大学 | Gallium oxide phase-combination nano-column array and preparation method thereof |
| CN108821329A (en) * | 2018-07-10 | 2018-11-16 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity gallium oxide |
| CN110937622A (en) * | 2019-11-12 | 2020-03-31 | 中铝山东有限公司 | Method for preparing 4N gallium oxide from sponge gallium |
| CN110655104A (en) * | 2019-11-19 | 2020-01-07 | 武汉拓材科技有限公司 | Novel preparation process of high-purity gallium oxide |
| CN114655979B (en) * | 2022-04-08 | 2023-12-19 | 云南锡业集团（控股）有限责任公司研发中心 | Method for preparing gallium hydroxide by using gallium arsenide waste |
| CN114715932A (en) * | 2022-04-22 | 2022-07-08 | 珠海经济特区方源有限公司 | Method for preparing high-purity gallium sulfate from sponge gallium |
| CN114715931A (en) * | 2022-04-22 | 2022-07-08 | 珠海经济特区方源有限公司 | Method for preparing high-purity gallium nitrate from sponge gallium |
| WO2024053010A1 (en) * | 2022-09-07 | 2024-03-14 | 住友電気工業株式会社 | High-purity digallium trioxide, and method for producing same |
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2008
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