CN1693492A - Method of recovering gallium and arsenic from gallium arsenate industry waste material - Google Patents
Method of recovering gallium and arsenic from gallium arsenate industry waste material Download PDFInfo
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- CN1693492A CN1693492A CNA2005100315318A CN200510031531A CN1693492A CN 1693492 A CN1693492 A CN 1693492A CN A2005100315318 A CNA2005100315318 A CN A2005100315318A CN 200510031531 A CN200510031531 A CN 200510031531A CN 1693492 A CN1693492 A CN 1693492A
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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
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Abstract
A process for recovering Ga and As from the industrial gallium arsenide dregs includes such steps as grinding, extracting in nitric acid, using sulfide to selectively deposit As, using hydroxide to deposit Ga, dissolving gallium hydroxide in alkali solution, electrolyzing for recovering Ga, and purifying Ga and As.
Description
Technical field
The present invention relates to a kind of method that from the gallium arsenide industrial waste, reclaims gallium and arsenic.
Technical background
Gallium does not form the independent gallium mineral deposit with extraction value at occurring in nature, but with the association of isomorphism attitude in mineral deposits such as copper-sulphide ores, aluminium, zinc, germanium, germanic coal, produce gallium at present and be from the byproduct that extracts metals such as aluminium, zinc, germanium and comprehensively reclaim; Another source that produces gallium is exactly to reclaim from the waste material that contains gallium, mainly is the waste material of gallium arsenide, accounts for about 80%.This is because in monocrystalline and wafer process process, can produce a large amount of gallium arsenide waste materials.So the gallium arsenide waste material just becomes the important raw and processed materials of producing gallium.CN200410040272.0 discloses and has adopted the method for vacuum metallurgy to reclaim gallium and arsenic, and its ultimate principle is under the vacuum high-temperature condition that the ratio of gallium steam and arsenic steam is very little, after gallium arsenide decomposes, the non-volatile formation liquid of gallium, and the arsenic volatilization forms gas, thus gallium is separated with arsenic.This method is very high to equipment requirements, requires harsh to the waste material composition of handling simultaneously.UN4094753 adopts wet chemistry method to reclaim gallium, this method mainly be molten by acid, add calcium dearsenification, precipitation of hydroxide, molten, the last electrolysis system gallium of alkali.It is not thorough that this method shortcoming is to add the calcium dearsenification, and the calcium arsenate that obtains reclaims difficulty, causes secondary pollution easily, and pH changes greatly in operation simultaneously, operational difficulty.
Summary of the invention
The objective of the invention is to improve sour molten technology, provide a kind of can dearsenification thorough, gallium and arsenic rate of recovery height, operation with low cost, easy can not cause the method that reclaims gallium and arsenic from the gallium arsenide industrial waste of secondary pollution.
Technical scheme of the present invention is by sulfide selective precipitation arsenic, isolate and contain Gallium solution, contain Gallium solution by adding alkali control pH, generate gallium hydroxide, adopt molten, the electrolytic method of alkali to reclaim gallium then, it is that the gallium of 4N can further be purified to the high purity metal gallium that purity is 6N that electrolysis obtains purity, arsenic sulfide can be handled by the further deep processing of current technology as raw material and obtain high purity arsenic, high purity gallium that obtains like this and arsenic can be used as gallium arsenide semiconductor synthetic raw material, thereby realize the recycling of gallium arsenide industrial waste.
The present invention includes following steps:
1, with the gallium arsenide industrial waste fragmentation of gallium content more than 10%, powder to the 100-200 order;
2, powder adds 1.0-5.0mol/L nitric acid, is 40-70 ℃ in temperature, and stirring velocity is autocatalysis dissolving 1-3h under 100-300 rev/min the condition;
3. filtration residue obtains containing the solution of arsenic and gallium;
4. sulfide selective precipitation arsenic: in the solution that contains arsenic and gallium, feed H
2The Na of arsenic mol ratio 1: 1.0-1.5 in S or adding and the solution
2S or FeS are 30-70 ℃ in temperature, and stirring velocity is under the 100-300 rev/min of condition, reaction 1-3h, and obtaining main component is As
2S
3Contain arsenic precipitation and contain Gallium solution;
5, contain Gallium solution and produce gallium hydroxide: contain Gallium solution and add alkali, make pH value of solution=5-7, especially at pH=6-7, stirring velocity 100-300 rev/min, reaction 1-3h obtains gallium hydroxide and filters back liquid after the filtration;
6, electrolytic recovery gallium: with traditional method the wet hydrogen gallium oxide is dissolved in the NaOH solution, control pH=10-12, the best is pH=11, electrolysis obtains gallium.
Embodiment
Embodiment 1
50 grams are contained Ga48.6%, contain As51.2%, all the other are that the fragmentation of gallium arsenide industrial waste, powder of small amount of impurities elements such as Si, P, Al, In is to the 100-200 order; Join the HNO of 2L 2mol/L
3Solution, the control stirring velocity is at 300 rev/mins, and temperature is 60 ℃, reaction 2h; After reaction finished, filtering solution did not have filter residue to occur substantially, adopts the HNO of 200mL 2mol/L
3Solution acid filter wash slag, washings mixes with filtrate, detect in the solution gallium content be 10.93g/L, arsenic content is 11.53g/L.
Sulfide selective precipitation arsenic: the salpeter solution that above-mentioned 2.2L is contained gallium, arsenic feeds H in closed reactor
2S gas, 40 ℃ of control reaction temperature, 300 rev/mins of stirring velocitys, reaction times 1.5h.After reaction finished, filtering solution was washed filter residue with 300mL, washed back liquid and mixed with filtering solution.Detect in the solution gallium content be 9.6g/L, arsenic content is 1.0mg/L.The As that surveys after the filter residue and drying
2S
3Grade reaches more than 95%.The rate of recovery to arsenic after the above-mentioned technology reaches 99%.
With 1L gallium content 9.6g/L, arsenic content is the HNO of 1.0mg/L
3Solution adds NH
3H
2O, control pH=7,200 rev/mins of stirring velocitys, reaction times 2h.After reaction finished, filtering solution was washed filter residue with 500mL, washed back liquid and mixed with filtering solution.Detect gallium content 0.6g/L in the solution, arsenic content is 0.7mg/L.Filter residue detects and is gallium hydroxide.
The wet hydrogen gallium oxide is dissolved into 100mL and contains in the NaOH solution of 100g/L, adjusts the pH=12 of solution, at electric current 0.05A/cm
2, electrolysis 6h under the voltage 4.5V, obtain the 7.5g gallium, purity is at 4N.
Liquid and filtering solution mixed solution store after above-mentioned the washing, and add a certain amount of pyrite or As
2S
3The sulphur slag that deep processing produces, to arsenic content less than 0.5mg/L, discharging.
Embodiment 2
The 100g granularity is at 100-200 purpose gallium arsenide waste material powder, and its composition is that gallium is 20%, and arsenic is 20%, and SiO2 is 50%, and Al is 4%, and Ca is 3%, and Fe is 1%, small amount of impurities elements such as P, In.Join in the HNO3 solution of 2L 2mol/L, the control stirring velocity is at 300 rev/mins, and temperature is 70 ℃, and the reaction times is 2h.After reaction finishes, filtering solution, the filter residue main component is SiO2, adopts the HNO3 solution acid filter wash slag of 200mL 2mol/L, washings mixes with filtrate, detect in the solution gallium content be 9.0g/L, arsenic content is 9.1g/L.
The salpeter solution that 2.2L is contained gallium, arsenic feeds H in closed reactor
2S gas, 40 ℃ of control reaction temperature, 300 rev/mins of stirring velocitys, after reaction times 1.5h. reaction finished, filtering solution was washed filter residue with 300mL, washed back liquid and mixed with filtering solution.Detect gallium content 7.6g/L in the solution, arsenic content is 0.9mg/L.Record As after the filter residue and drying
2S
3Grade reaches more than 80%, and all the other are SiO
2, impurity such as FeS.The rate of recovery to arsenic after the above-mentioned technology reaches 99%.
Add NaOH, control pH=6.5,300 rev/mins of stirring velocitys, reaction times 3h.After reaction finishes, filtering solution, 1000mL washes filter residue, washes back liquid and mixes with filtering solution.Detect in the solution gallium content be 0.6g/L, arsenic content is 0.6mg/L, filter residue detects and is gallium hydroxide.
The wet hydrogen gallium oxide is dissolved into 200mL and contains in the 100g/LNaOH solution, adjusts the pH=12 of solution, at electric current 0.05A/cm
2, electrolysis 10h under the voltage 4.5V, obtain the 11.0g gallium, purity is 4N.
Liquid and filtering solution mixed solution store after above-mentioned the washing, and add a certain amount of pyrite or As
2S
3The sulphur slag that deep processing produces, to arsenic content less than 0.5mg/L, discharging.
Embodiment 3
The 50g granularity is at 100-200 purpose gallium arsenide waste material powder, and composition is that Ga is 48.6%, and As is 51.2%, and all the other are small amount of impurities elements such as Si, P, Al, In.Join the HNO of 2L 3mol/L
3In the solution, the control stirring velocity is at 200 rev/mins, and temperature is 50 ℃, and the reaction times is 1.5h.After reaction finished, filtering solution did not have filter residue to occur substantially, adopts the HNO of 100mL 3mol/L
3Solution acid filter wash slag, washings mixes with filtrate, detect in the solution gallium content be 11.4g/L, arsenic content is 12.0g/L.
With solution behind the above-mentioned autocatalysis nitric acid dissolve of 1L, in reactor, add 20gFeS, 60 ℃ of control reaction temperature, 300 rev/mins of stirring velocitys, after reaction times 1.5h. reaction finished, filtering solution was washed filter residue with 100mL, washed back liquid and mixed with filtering solution.Detect gallium content 10.2g/L in the solution, arsenic content is 1.5mg/L.
With solution behind the above-mentioned selective precipitation arsenic of 1L, add NH
3H
2O, control pH=7,300 rev/mins of stirring velocitys, reaction times 2h.After reaction finished, filtering solution was washed filter residue with 500mL, washed back liquid and mixed with filtering solution.Detect gallium content 1.0g/L in the solution, arsenic content is 1.0mg/L.Filter residue detects and is gallium hydroxide.
The wet hydrogen gallium oxide is dissolved into 150mL and contains in the 100g/LNaOH solution, adjusts the pH=12 of solution, at electric current 0.05A/cm
2, electrolysis 8h under the voltage 4.5V, obtain the 11.5g gallium, purity is at 4N.Liquid and filtering solution mixed solution store after above-mentioned the washing, and add a certain amount of pyrite or As
2S
3The sulphur slag that deep processing produces, to arsenic content less than 0.5mg/L, discharging.
Embodiment 4
The 50g granularity is at 100-200 purpose gallium arsenide waste material powder, and composition is that Ga is 48.6%, and As is 51.2%, and all the other are small amount of impurities elements such as Si, P, Al, In.Join the HNO of 2L 3mol/L
3In the solution, the control stirring velocity is at 200 rev/mins, and temperature is 40 ℃, and the reaction times is 2.0h.After reaction finished, filtering solution did not have filter residue to occur substantially, adopts the HNO3 solution acid filter wash slag of 200mL 3mol/L, and washings mixes with filtrate, detect in the solution gallium content be 10.90g/L, arsenic content is 11.55g/L.
With solution behind the 1L autocatalysis nitric acid dissolve, in reactor, add 16gNa
2S, 40 ℃ of control reaction temperature, 100 rev/mins of stirring velocitys, reaction times 1.5h.After reaction finished, filtering solution was washed filter residue with 100mL, washed back liquid and mixed with filtering solution.Detect in the solution gallium content be 9.7g/L, arsenic content is 1.0mg/L.
With solution behind the above-mentioned selective precipitation arsenic of 1L, add NH
3H
2O, control pH=7,200 rev/mins of stirring velocitys, reaction times 2h.After reaction finished, filtering solution was washed filter residue with 500mL, washed back liquid and mixed with filtering solution.Detect gallium content 0.6g/L in the solution, arsenic content is 0.7mg/L.Filter residue detects and is gallium hydroxide.
The wet hydrogen gallium oxide is dissolved into 100mL and contains in the 100g/LNaOH solution, adjusts the pH=12 of solution, at electric current 0.05A/cm
2, electrolysis 6h under the voltage 4.5V, obtain the 7.5g gallium, purity is 4N.
Liquid and filtering solution mixed solution store after above-mentioned the washing, and add a certain amount of pyrite or As
2S
3The sulphur slag that deep processing produces, to arsenic content less than 0.5mg/L, discharging.
Claims (2)
1, from the gallium arsenide industrial waste, reclaim the method for gallium and arsenic, it is characterized in that may further comprise the steps:
(1) the gallium arsenide industrial waste of gallium content more than 10% is crushed to the 100-200 order;
(2) powder adds 1.0-5.0mol/L nitric acid, is 40-70 ℃ in temperature, and stirring velocity is autocatalysis dissolving 1-3h under 100-300 rev/min the condition;
(3) filter the solution that obtains containing arsenic and gallium;
(4) sulfide selective precipitation arsenic: in the solution that contains arsenic and gallium, feed H
2Arsenic mol ratio 1: 1.0-1.5Na in S or adding and the solution
2S or FeS are 30-70 ℃ in temperature, and stirring velocity is under the 100-300 rev/min of condition, reaction 1-3h, and obtaining main component is As
2S
3Contain arsenic precipitation and contain Gallium solution;
(5) contain Gallium solution and produce gallium hydroxide: contain Gallium solution and add alkali, make pH value of solution=5-7,100-300 rev/min of control stirring velocity, reaction 1-3h obtains gallium hydroxide and filters back liquid after the filtration;
(6) electrolytic recovery gallium: with traditional method the wet hydrogen gallium oxide is dissolved in the NaOH solution, control pH=10-12, the best is pH=11, electrolysis obtains gallium.
2, method according to claim 1 is characterized in that the described best pH=6-7 that Gallium solution is produced gallium hydroxide that contains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2005100315318A CN1693492A (en) | 2005-05-13 | 2005-05-13 | Method of recovering gallium and arsenic from gallium arsenate industry waste material |
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| CNA2005100315318A CN1693492A (en) | 2005-05-13 | 2005-05-13 | Method of recovering gallium and arsenic from gallium arsenate industry waste material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413064B (en) * | 2008-10-29 | 2010-06-23 | 南京金美镓业有限公司 | Vacuum decomposing apparatus for separating gallium arsenide as metal gallium and metal arsenic |
| CN102951618A (en) * | 2011-08-31 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Method for recycling germanium, gallium, indium and selenium in waste diode |
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
| CN104445375A (en) * | 2014-12-17 | 2015-03-25 | 苏方宁 | Preparation method of gallium hydroxide |
| CN106399696A (en) * | 2016-10-11 | 2017-02-15 | 华东师范大学 | Method for preparing sulfide of arsenic from gallium arsenide chip production waste |
| CN108570684A (en) * | 2017-03-13 | 2018-09-25 | 中国科学院过程工程研究所 | A kind of electrochemical process for treating containing arsenic smoke dust |
| CN108707927A (en) * | 2018-06-14 | 2018-10-26 | 汉能新材料科技有限公司 | A method of recycling arsenic and gallium from the waste material containing GaAs |
| CN108728641A (en) * | 2018-06-22 | 2018-11-02 | 汉能新材料科技有限公司 | A kind of recovery method of GaAs waste material |
| CN113512652A (en) * | 2021-06-29 | 2021-10-19 | 四川顺应动力电池材料有限公司 | Method for extracting gallium metal from coal-series solid waste |
| CN113666410A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | Method for directly preparing gallium oxide by using gallium nitride waste |
| CN114655979A (en) * | 2022-04-08 | 2022-06-24 | 云南锡业集团（控股）有限责任公司研发中心 | Method for preparing gallium hydroxide by utilizing gallium arsenide waste |
-
2005
- 2005-05-13 CN CNA2005100315318A patent/CN1693492A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413064B (en) * | 2008-10-29 | 2010-06-23 | 南京金美镓业有限公司 | Vacuum decomposing apparatus for separating gallium arsenide as metal gallium and metal arsenic |
| CN102951618A (en) * | 2011-08-31 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Method for recycling germanium, gallium, indium and selenium in waste diode |
| CN102951618B (en) * | 2011-08-31 | 2014-07-30 | 深圳市格林美高新技术股份有限公司 | Method for recycling germanium, gallium, indium and selenium in waste diode |
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
| CN103388159B (en) * | 2012-05-11 | 2016-08-03 | 格林美股份有限公司 | A kind of method reclaiming gallium from nitrogen gallium garbage |
| CN104445375A (en) * | 2014-12-17 | 2015-03-25 | 苏方宁 | Preparation method of gallium hydroxide |
| CN104445375B (en) * | 2014-12-17 | 2015-11-04 | 苏方宁 | The preparation method of gallium hydroxide |
| CN106399696A (en) * | 2016-10-11 | 2017-02-15 | 华东师范大学 | Method for preparing sulfide of arsenic from gallium arsenide chip production waste |
| CN108570684A (en) * | 2017-03-13 | 2018-09-25 | 中国科学院过程工程研究所 | A kind of electrochemical process for treating containing arsenic smoke dust |
| CN108570684B (en) * | 2017-03-13 | 2020-06-16 | 中国科学院过程工程研究所 | Electrochemical treatment method of arsenic-containing soot |
| CN108707927A (en) * | 2018-06-14 | 2018-10-26 | 汉能新材料科技有限公司 | A method of recycling arsenic and gallium from the waste material containing GaAs |
| CN108728641A (en) * | 2018-06-22 | 2018-11-02 | 汉能新材料科技有限公司 | A kind of recovery method of GaAs waste material |
| CN113512652A (en) * | 2021-06-29 | 2021-10-19 | 四川顺应动力电池材料有限公司 | Method for extracting gallium metal from coal-series solid waste |
| CN113666410A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | Method for directly preparing gallium oxide by using gallium nitride waste |
| CN114655979A (en) * | 2022-04-08 | 2022-06-24 | 云南锡业集团（控股）有限责任公司研发中心 | Method for preparing gallium hydroxide by utilizing gallium arsenide waste |
| 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 |
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