CN102634659A - Process for recycling gallium from gallium and germanium contained concentrate - Google Patents
Process for recycling gallium from gallium and germanium contained concentrate Download PDFInfo
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- CN102634659A CN102634659A CN2012100742341A CN201210074234A CN102634659A CN 102634659 A CN102634659 A CN 102634659A CN 2012100742341 A CN2012100742341 A CN 2012100742341A CN 201210074234 A CN201210074234 A CN 201210074234A CN 102634659 A CN102634659 A CN 102634659A
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Abstract
A process for recycling gallium from gallium and germanium contained concentrate belongs to the field of metallurgy, and particularly relates to a wet process for recycling gallium from gallium and germanium contained concentrate. The process includes germanium concentrate breaking, germanium evaporation and separation, press-filtering, separating, filtrate acidity adjustment, gallium extraction, organic-phase rich gallium reverse extraction and refined gallium preparation. The process effective and feasible for gallium recycling is proposed for recycling gallium concentrate, has bright application prospect, and is a low-cost and effective process for recycling gallium from residue left in germanium extraction from germanium concentrate.
Description
Technical field
The invention belongs to field of metallurgy, especially a kind of wet method reclaims the technology of gallium from contain the gallium germanium concentrate.
Background technology
The GALLIUM metal pure purposes mainly is as semi-conductive base mateiral; Application in semicon industry and photovoltaic industry such as its compound gallium arsenide, gallium phosphide, gan, gallium aluminum arsenide very extensively; Gallium arsenide can be made high-power laser apparatus, light emitting diode, solar cell; Application is very widely arranged in fields such as powerful unicircuit, nuclear industry, alloy and opticinstrument, chemical catalyst, special thermopairs; Consumption every year of whole world high purity gallium, the speed with 20～25% increased, and annual requirement has reached more than 200 ton at present.Though the content of gallium in the earth's crust is abundant, because of its concentration is extremely low, distributes and relatively disperse, therefore can not exploit separately.Because it has certain enrichment in bauxite; The metal current gallium mainly is to use bauxite producing with Bayer process in the process of aluminum oxide as raw material; And extract in the zinc hydrometallurgy process of the zinc oxide fumes of zink sulphide, its output is subject to the output of aluminum oxide and the output of zinc.
In addition, in carrying the germanium concentrate that germanium uses, also often contain abundant gallium, this is because contain gallium in the leach liquor that zinc baking sand obtains after leaching with sulfuric acid in the lead-zinc smelting process; When precipitating the germanium in the leach liquor with tanpic acid or tannin extract; Except germanium, other valuable metal gallium, indium, zinc, lead etc. also have partly precipitated to enter into germanium concentrate, particularly GALLIUM metal pure; Deposition rate can reach about 80%; Therefore all be rich in gallium in many germanium concentrates, the gallium content in the part germanium concentrate can reach 0.1～1.0%, and indivedual rich gallium germanium concentrates can reach 3.0～4.0%.The annual germanium concentrate of handling of domestic germanium manufacturing enterprise is about 2500～3000 tons; The germanium concentrate that wherein is rich in gallium is about 1200～1500 tons; Be rich in gallium metal and can reach about 1.1～5.0 tons; Therefore, germanium concentrate is the raw material that a kind of fine extracts gallium, can remedy the deficiency of from aluminum oxide and electrolytic zinc, extracting gallium output.Yet the maturation process method that up to the present from germanium concentrate, reclaims gallium does not also have, and most of germanium manufacturer one does not know also to contain abundant gallium in the germanium concentrate, though two serve producer and know and contain gallium do not have ability that it is reclaimed.
Summary of the invention
The problem that from germanium concentrate, how to reclaim gallium exactly to be solved by this invention provides the process method that reclaims the high efficiency, low cost of gallium a kind of raffinate after germanium concentrate is carried germanium.
A kind of process method that from contain the gallium germanium concentrate, reclaims gallium of the present invention is characterized in that this method may further comprise the steps:
The first step, the fragmentation of germanium concentrate: will contain the gallium germanium concentrate and be crushed at least 200 orders;
Second step; The fractionation by distillation of germanium: at the technical hydrochloric acid that in the germanium concentrate of pulverizing, adds 7.5～8.5mol/L; The technical hydrochloric acid that adds and the mass ratio of germanium concentrate are 5～8:1; Be heated to 65～70 ℃ then, be warming up to 90～110 ℃ behind agitation leach 0.5～1.0 h and carry out fractionation by distillation, isolate germanium tetrachloride and distillation residue, vinasse;
The 3rd step; Press filtration separates: the distillation residue and the vinasse of the second step gained are used the pressure filter press filtration, distillation residue are separated with vinasse, use the water washing distillation residue again; Make the gallium in the distillation residue enter into vinasse, thus do not contained gallium in slag be rich in the filtered liq of gallium;
In the 4th step, the filtered liq acidity adjustment: it is that 49% industrial sulphuric acid is regulated acidity to 7.85～8.25mol/L that the filtered liq of the 3rd step gained is used massfraction;
In the 5th step, the extraction of gallium: adopting massfraction is 260 of 15～20% TBP
#Solvent oil extracts the gallium in the filtered liq as extraction agent, organic phase: filtered liq=1:3～5, and extraction times 3～5 times obtains rich gallium organic phase and collection back liquid;
In the 6th step, the reextraction of rich gallium organic phase: it is that 1～5% sodium hydroxide solution is stripped rich gallium organic phase that rich gallium organic phase is adopted massfraction: sodium hydroxide solution=6～8:1, and the back extraction number of times is 2～3 times, obtains rich gallium strip liquor;
In the 7th step, smart gallium preparation: the adding massfraction is 30%～50% sodium hydroxide solution alkalization in the strip liquor of the 6th step gained, and the consumption of alkali is 10%～30% of a strip liquor volume, carries out electrolysis then and obtains thick gallium, and thick gallium can obtain smart gallium again after purifying.In technology of the present invention, because of containing gallium germanium concentrate granularity, for ease of the leaching of germanium and gallium and separate, need be broken to more than 200 orders with raymond grinding powder generally at 40～200 orders.In germanium concentrate, mainly be present in the germanium concentrate with the form of Gallium trioxide because of gallium; After germanium concentrate is carried germanium; The Gallium trioxide major part all forms to enter into behind the gallium trichloride with hydrochloric acid reaction carries the germanium raffinate, again in the alkali neutralization remains in the rear section with slag in, part is with discharge of wastewater; And fail to reclaim gallium, caused the waste of gallium resource.This process method is through after the hydrochloric acid fractionation by distillation germanium, separates residue and raffinate with the pressure filter press filtration again, behind the washing residue; Regulate the acidity of raffinate, come the gallium in the extracting and separating raffinate with tributyl phosphate then, the rich gallium extraction liquid behind the separating gallium is stripped with sodium hydroxide solution again; Obtain the strip liquor of rich gallium, after strip liquor hydro-oxidation sodium is adjusted to alkalescence, carries out electrolysis and obtain smart gallium; Smart gallium after further purifying, can obtain high purity gallium again.
The principal reaction equation that relates in the technology of the present invention is:
GeO
2+4HCl?=?GeCl
4 +2H
2O;
Ga
2O
3+6HCl=2GaCl
3+3H
2O;
GaCl
3+HCl=?HGaCl
4;
HGaCl
4+TBP=HGaCl
4·TBP+H
2O;
HGaCl
4·TBP+4NaOH=Ga(OH)
3? +TBP+4NaCl+H
20;
The gallium that the present invention is directed in the germanium concentrate reclaims, and has proposed to reclaim the effective and feasible method of gallium, has great application prospect, and is the process method that reclaims the low-cost high-efficiency of gallium the raffinate after germanium concentrate is carried germanium.
Embodiment
Embodiment 1: get and contain gallium germanium concentrate double centner, ge content is 4.5% in this germanium concentrate, and gallium content is 0.40%, extracts gallium through following process method.
The first step: the double centner germanium concentrate is crushed to 200 orders.
Second step: the germanium concentrate after will pulverizing is put into the reaction kettle of 1000L, adds the hydrochloric acid that 800kg concentration is 7.95mol/L then, heats to leach to 65 ℃ and reacts 1h.Heat up then and distill; Distillation temperature is controlled at 95～110 ℃; Obtain 12.12 kilograms germanium tetrachloride and distillation residue and the vinasse of 780L after the distillation; With preparing 5.94 kilograms of high-purity germanium dioxides after the multiple steaming of germanium tetrachloride process, rectifying, the hydrolysis, the germanium recovery reaches 89.76% again.
The 3rd step: the distillation residue of the 780L that obtains are separated with the pressure filter press filtration with vinasse; Use the water washing residue, make the gallium in the residue enter into vinasse, obtain filtered liq 830L; Gallium content is 0.47g/L in this filtered liq, and the leaching yield of gallium is 97.53%.
The 4th step: again filtered liq being used massfraction is that 49% industrial sulphuric acid 8.6L regulates its acidity to 7.90mol/L.
The 5th step: filtered liq is transferred in the extraction tank 260 of the TBP with 20%
#Solvent oil solution 166L comes the gallium in the filtered liq is extracted as extraction agent, and extraction times 3 times obtains rich gallium organic phase 498L and collection back liquid 790L, and containing gallium in the liquid after the collection behind the extraction gallium is 0.012mg/L, and the percentage extraction of gallium is 97.63%.
The 6th step: the sodium hydroxide solution 65L with 2% strips 2 times to rich gallium organic phase, obtains rich gallium strip liquor 40L.
The 7th step: rich gallium strip liquor being transferred in the electrolyzer, adding 30% sodium hydroxide solution 8L again strip liquor is alkalized, carry out electrolysis then, obtain thick gallium 326g, is 81.50% from containing the gallium germanium concentrate to the comprehensive recovery of thick gallium.
Embodiment 2: get and contain gallium germanium concentrate double centner, this germanium concentrate ge content is 5.7%, and gallium content is 0.78%.Extract gallium through following process method.
The first step: the double centner germanium concentrate is crushed to 200 orders.
Second step: the germanium concentrate through pulverizing all is put in the reaction kettle of 1000L, and adding 800kg concentration is the hydrochloric acid of 8.40mol/L, heats to 70 ℃ and leaches reaction 1.5h.Heat up then and distill; Distillation temperature is controlled at 95～110 ℃; Distillation obtains 17.19 kilograms germanium tetrachloride and distillation residue and the vinasse of 775L, and with preparing 7.87 kilograms of high-purity germanium dioxides after the multiple steaming of germanium tetrachloride process, rectifying, the hydrolysis, the germanium recovery reaches 95.82% again.
The 3rd step: the distillation residue with the 775L that obtains separate with the pressure filter press filtration with vinasse then; Use the water washing residue, make the gallium in the residue enter into vinasse, obtain filtered liq 840L; Gallium content is 0.88g/L in the filtered liq, and the leaching yield of gallium is 94.77%.
The 4th step: again filtered liq being used massfraction is that 49% industrial sulphuric acid 9.3L regulates its acidity and is 8.20mol/L.
The 5th step: then filtered liq is transferred in the extraction tank; The 260# solvent oil solution 210L of TBP with 15% comes the gallium in the filtered liq is extracted as extraction agent; Extraction times gets rich gallium organic phase 840L 4 times; Collection back liquid 849.3L, containing gallium in the filtered liq behind the extraction gallium is 0.017mg/L, the percentage extraction of gallium is 98.15%.
The 6th step: the sodium hydroxide solution 105L with 5% strips 3 times to rich gallium organic phase, obtains rich gallium strip liquor 90L.
The 7th step: rich gallium strip liquor being transferred in the electrolyzer, adding 50% sodium hydroxide solution 9L richer gallium strip liquor is alkalized, carry out electrolysis then, obtain thick gallium 697g, is 89.36% from containing the gallium germanium concentrate to the comprehensive recovery of thick gallium.
Claims (1)
1. process method that from contain the gallium germanium concentrate, reclaims gallium is characterized in that this method may further comprise the steps:
The first step, the fragmentation of germanium concentrate: will contain the gallium germanium concentrate and be crushed at least 200 orders;
Second step; The fractionation by distillation of germanium: at the technical hydrochloric acid that in the germanium concentrate of pulverizing, adds 7.5～8.5mol/L; The technical hydrochloric acid that adds and the mass ratio of germanium concentrate are 5～8:1; Be heated to 65～70 ℃ then, be warming up to 90～110 ℃ behind agitation leach 0.5～1.0 h and carry out fractionation by distillation, isolate germanium tetrachloride and distillation residue, vinasse;
The 3rd step; Press filtration separates: the distillation residue and the vinasse of the second step gained are used the pressure filter press filtration, distillation residue are separated with vinasse, use the water washing distillation residue again; Make the gallium in the distillation residue enter into vinasse, thus do not contained gallium in slag be rich in the filtered liq of gallium;
In the 4th step, the filtered liq acidity adjustment: it is that 49% industrial sulphuric acid is regulated acidity to 7.85～8.25mol/L that the filtered liq of the 3rd step gained is used massfraction;
In the 5th step, the extraction of gallium: adopting massfraction is 260 of 15～20% TBP
#Solvent oil extracts the gallium in the filtered liq as extraction agent, organic phase: filtered liq=1:3～5, and extraction times 3～5 times obtains rich gallium organic phase and collection back liquid;
In the 6th step, the reextraction of rich gallium organic phase: it is that 1～5% sodium hydroxide solution is stripped rich gallium organic phase that rich gallium organic phase is adopted massfraction: sodium hydroxide solution=6～8:1, and the back extraction number of times is 2～3 times, obtains rich gallium strip liquor;
In the 7th step, smart gallium preparation: the adding massfraction is 30%～50% sodium hydroxide solution alkalization in the strip liquor of the 6th step gained, and the consumption of alkali is 10%～30% of a strip liquor volume, carries out electrolysis then and obtains thick gallium, and thick gallium can obtain smart gallium again after purifying.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276407A (en) * | 2013-05-13 | 2013-09-04 | 攀枝花学院 | Method for recovering gallium and iron from low-grade raw materials containing gallium and iron |
| CN103468977A (en) * | 2013-10-10 | 2013-12-25 | 郴州市金贵银业股份有限公司 | Method for selectively leaching germanium and gallium from complex smelting slag with germanium and gallium or ore with germanium and gallium |
| CN103695657A (en) * | 2013-12-24 | 2014-04-02 | 广西博士海意信息科技有限公司 | Method for enriching and recovering gallium and germanium from zinc hydrometallurgy waste residues |
| CN106498168A (en) * | 2016-11-16 | 2017-03-15 | 广东先导稀材股份有限公司 | The method for reclaiming gallium from oil-containing GaAs mud |
| CN106995885A (en) * | 2017-03-29 | 2017-08-01 | 广东先导稀材股份有限公司 | The method for mixing gallium and germanium in Ore Leaching waste residue |
| CN110184483A (en) * | 2019-06-25 | 2019-08-30 | 广西大学 | A method of enrichment and gallium-purifying from alkaline solution |
| CN110964924A (en) * | 2019-11-27 | 2020-04-07 | 昆明理工大学 | Pretreatment method for recycling nickel-based high-temperature alloy |
| CN112760497A (en) * | 2021-01-26 | 2021-05-07 | 云南东昌金属加工有限公司 | Recovery method for absorbing germanium in alkali liquor by purifying germanium-extracting tail gas |
| CN113528862A (en) * | 2021-06-30 | 2021-10-22 | 昆明理工大学 | Method for recovering gallium from gallium-containing waste |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705378A (en) * | 2009-12-01 | 2010-05-12 | 南京中锗科技股份有限公司 | Method for comprehensively recovering valuable metals from complex alloys containing stibium, tellurium, indium, germanium and silver |
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2012
- 2012-03-20 CN CN2012100742341A patent/CN102634659B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705378A (en) * | 2009-12-01 | 2010-05-12 | 南京中锗科技股份有限公司 | Method for comprehensively recovering valuable metals from complex alloys containing stibium, tellurium, indium, germanium and silver |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276407A (en) * | 2013-05-13 | 2013-09-04 | 攀枝花学院 | Method for recovering gallium and iron from low-grade raw materials containing gallium and iron |
| CN103276407B (en) * | 2013-05-13 | 2016-12-28 | 攀枝花学院 | A kind of from low-grade containing gallium, ferrum raw material reclaim gallium and the method for ferrum |
| CN103468977A (en) * | 2013-10-10 | 2013-12-25 | 郴州市金贵银业股份有限公司 | Method for selectively leaching germanium and gallium from complex smelting slag with germanium and gallium or ore with germanium and gallium |
| CN103468977B (en) * | 2013-10-10 | 2015-08-19 | 郴州市金贵银业股份有限公司 | The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium |
| CN103695657A (en) * | 2013-12-24 | 2014-04-02 | 广西博士海意信息科技有限公司 | Method for enriching and recovering gallium and germanium from zinc hydrometallurgy waste residues |
| CN106498168A (en) * | 2016-11-16 | 2017-03-15 | 广东先导稀材股份有限公司 | The method for reclaiming gallium from oil-containing GaAs mud |
| CN106995885A (en) * | 2017-03-29 | 2017-08-01 | 广东先导稀材股份有限公司 | The method for mixing gallium and germanium in Ore Leaching waste residue |
| CN110184483A (en) * | 2019-06-25 | 2019-08-30 | 广西大学 | A method of enrichment and gallium-purifying from alkaline solution |
| CN110964924A (en) * | 2019-11-27 | 2020-04-07 | 昆明理工大学 | Pretreatment method for recycling nickel-based high-temperature alloy |
| CN112760497A (en) * | 2021-01-26 | 2021-05-07 | 云南东昌金属加工有限公司 | Recovery method for absorbing germanium in alkali liquor by purifying germanium-extracting tail gas |
| CN112760497B (en) * | 2021-01-26 | 2022-09-09 | 云南东昌金属加工有限公司 | Recovery method for absorbing germanium in alkali liquor by purifying germanium-extracting tail gas |
| CN113528862A (en) * | 2021-06-30 | 2021-10-22 | 昆明理工大学 | Method for recovering gallium from gallium-containing waste |
| CN113528862B (en) * | 2021-06-30 | 2022-09-02 | 昆明理工大学 | Method for recovering gallium from gallium-containing waste |
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