CN102634659B - 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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- CN102634659B CN102634659B CN2012100742341A CN201210074234A CN102634659B CN 102634659 B CN102634659 B CN 102634659B CN 2012100742341 A CN2012100742341 A CN 2012100742341A CN 201210074234 A CN201210074234 A CN 201210074234A CN 102634659 B CN102634659 B CN 102634659B
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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 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 are very extensive, 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 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 be that raw material is being produced with Bayer process in the process of aluminum oxide with bauxite, 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 the germanium that precipitates with tannic acid or tannin extract in the leach liquor, except germanium, other valuable metal gallium, indium, zinc, lead etc. also have partly precipitated to enter into germanium concentrate, gallium particularly, deposition rate can reach about 80%, therefore all be rich in gallium in many germanium concentrates, 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 a kind of raw material of extraction gallium of high-quality, can remedy the deficiency of extracting gallium output from aluminum oxide and electrolytic zinc.Yet the maturation process method that up to the present reclaims gallium from germanium concentrate 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 how to reclaim gallium exactly from germanium concentrate to be solved by this invention provides the processing method that reclaims the high efficiency, low cost of gallium a kind of raffinate after germanium concentrate is carried germanium.
A kind of processing method that reclaims gallium from contain the gallium germanium concentrate 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: the technical hydrochloric acid that in the germanium concentrate through 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: distillation residue and vinasse pressure filter press filtration with the second step gained, and distillation residue are separated with vinasse, wash distillation residue again with water, make the gallium in the distillation residue enter into vinasse, thus do not contained gallium in and slag and be rich in the filtered liquid of gallium;
The 4th step, filtered liquid acidity adjustment: be 49% industrial sulphuric acid adjusting acidity to 7.85～8.25mol/L with the filtered liquid massfraction of the 3rd step gained;
In the 5th step, the extraction of gallium: adopting massfraction is 260 of 15～20% TBP
#Solvent oil extracts gallium in the filtered liquid as extraction agent, organic phase: filtered liquid=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 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 containing gallium germanium concentrate granularity generally at 40～200 orders, for ease of the leaching of germanium and gallium and separate, need be broken to more than 200 orders with raymond grinding powder.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 and in the slag, part is with discharge of wastewater, and fail to reclaim gallium, caused the waste of gallium resource.This processing method is by after the hydrochloric acid fractionation by distillation germanium, separate residue and raffinate with the pressure filter press filtration again, behind the washing residue, the acidity of regulating raffinate is come gallium in the extracting and separating raffinate with tributyl phosphate then, 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 processing 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 by following processing 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 reactor 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 control is at 95～110 ℃, obtain 12.12 kilograms germanium tetrachloride and distillation residue and the vinasse of 780L after the distillation, to prepare 5.94 kilograms of high-purity germanium dioxides after the multiple steaming of germanium tetrachloride process, rectifying, the hydrolysis again, the germanium rate of recovery reaches 89.76%.
The 3rd step: the distillation residue of the 780L that obtains are separated with the pressure filter press filtration with vinasse, wash residue with water, make the gallium in the residue enter into vinasse, obtain filtered liquid 830L, gallium content is 0.47g/L in this filtered liquid, and the leaching yield of gallium is 97.53%.
The 4th step: be that 49% industrial sulphuric acid 8.6L regulates its acidity to 7.90mol/L again with the filtered liquid massfraction.
The 5th step: filtered liquid is transferred in the extraction tank 260 of the TBP with 20%
#Solvent oil solution 166L comes the gallium in the filtered liquid 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% the strip liquor of sodium hydroxide solution 8L again and alkalize, 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 by following processing 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 reactor 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 control is at 95～110 ℃, distillation obtains 17.19 kilograms germanium tetrachloride and distillation residue and the vinasse of 775L, will prepare 7.87 kilograms of high-purity germanium dioxides after the multiple steaming of germanium tetrachloride process, rectifying, the hydrolysis again, and the germanium rate of recovery reaches 95.82%.
The 3rd step: the distillation residue with the 775L that obtains separate with the pressure filter press filtration with vinasse then, wash residue with water, make the gallium in the residue enter into vinasse, obtain filtered liquid 840L, gallium content is 0.88g/L in the filtered liquid, and the leaching yield of gallium is 94.77%.
The 4th step: be that to regulate its acidity be 8.20mol/L for 49% industrial sulphuric acid 9.3L again with the filtered liquid massfraction.
The 5th step: then filtered liquid is transferred in the extraction tank, the 260# solvent oil solution 210L of TBP with 15% comes the gallium in the filtered liquid 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 liquid behind the extraction gallium is 0.017mg/L, and 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. processing method that reclaims gallium from contain the gallium germanium concentrate 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: the technical hydrochloric acid that in the germanium concentrate through 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: distillation residue and vinasse pressure filter press filtration with the second step gained, and distillation residue are separated with vinasse, wash distillation residue again with water, make the gallium in the distillation residue enter into vinasse, thus do not contained gallium in and slag and be rich in the filtered liquid of gallium;
The 4th step, filtered liquid acidity adjustment: be 49% industrial sulphuric acid adjusting acidity to 7.85～8.25mol/L with the filtered liquid massfraction of the 3rd step gained;
In the 5th step, the extraction of gallium: adopting massfraction is 260 of 15～20% TBP
#Solvent oil extracts gallium in the filtered liquid as extraction agent, extraction agent: filtered liquid=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 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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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN106498168B (en) * | 2016-11-16 | 2018-01-23 | 广东先导稀材股份有限公司 | The method that gallium is reclaimed 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 |
| 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 |
| 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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| 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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| 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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