CN102181649A - Method for recovering germanium from germanium extraction residues - Google Patents
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Abstract
A method for recovering germanium from germanium extraction residues relates to the technical field of wet process metallurgy, in particular to a method for extracting germanium for a second time from distillation residues after germanium extraction by wet process treatment. The method is implemented by the following technical steps: washing of germanium extraction residues for deacidification, heating pretreatment of sodium hydroxide, solution treatment by concentrated alkali, sodium chlorate oxidation and hydrochloric acid distillation to separate germanium, and preparation of germanium dioxide and the like. The method is used for recovering germanium from germanium extraction residues and germanium tetrachloride at the rate up to over 75%. The successful research of the germanium extraction technology has actually positive significance in high-efficiency recovery of germanium in the residues, full utilization of rare germanium resource, reduction of residue pileup, environmental protection and other aspects.
Description
Technical field
The present invention relates to technical field of wet metallurgy, specifically is that a kind of distillation residue of carrying behind the germanium are carried out wet processing, carries out the method for second extraction germanium.
Background technology
Germanic brown coal adopt the pyrogenic process enrichment to carry in the germanium process, and when being higher than 710 ℃ of germanous oxide volatilization temperatures, germanium mainly enters into dust collecting system with the form volatilization of GeO, and at the lower stove tail of temperature, most GeO generates GeO again by dioxygen oxidation
2, temperature reduces postadhesion on coal smoke dirt particulate surface, and a spot of not oxidized GeO reduces along with temperature, also attached to the soot dust granule surface, also has part germanium then to be present in the germanium oxide dust with the oxide morphology volatilization.Therefore, in coal smoke dirt, germanium is except with GeO
2Form exist outside, also have a spot of with GeO, GeS, GeS
2, Ge
2S
3And GeO
2.SiO
2Deng form have and GeO wherein
2There are amorphous, six square crystal, three kinds of forms of cubic N-type waferN to exist again.
At present, the method for extracting germanium from contain germanium oxide dust generally is to adopt the Manganse Dioxide oxidation, and the method for concentrated hydrochloric acid fractionation by distillation is carried out then.In the method, the arsenic trichloride boiling point that forms because of arsenic (III) and hydrochloric acid is low, when distillation, enter into germanium tetrachloride easily, therefore needing with Manganse Dioxide arsenic oxide arsenoxide (III) is arsenic (V), so that arsenic together is not distilled out with germanium when distillation, the post-heating fractionation by distillation is finished in oxidation can obtain germanium tetrachloride.When chlorinated distillation, the GeO of unformed, six squares
2Very easily form GeCl with the hydrochloric acid effect
4, GeCl
4Separate with other impurity through distillation and after steaming rectification and purification again and obtain pure GeCl
4And the GeO of cubic type
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Etc. the germanium of form but be difficult to with hydrochloric acid reaction, therefore remained in and carried in the germanium residue.If in containing germanium oxide dust, if the shared ratio of the germanium of this part form is big more, then cause the distillation rate of recovery of germanium tetrachloride to reduce, the germanium that remains in the chlorinated distillation residue is just many more.So want to contain germanium oxide dust the higher rate of recovery is arranged when chlorinated distillation, should control the volatilization condition when then coal combustion volatilizees as far as possible, make germanium generate the cubic type GeO of hydrochloric acid indissoluble less
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Deng compound.
But, because the restriction of brown coal composition, the smelting furnace type of furnace, process control condition and the operational condition of the company that has, to generate this compounds unavoidably, therefore the chlorination of hydrochloric acid distillation rate of recovery that has caused germanium is less than 70%, and the ge content of staying in the residue after chlorination of hydrochloric acid is carried germanium has reached more than 30%.
Summary of the invention
The present invention is directed to cubic type GeO
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Be insoluble in hydrochloric acid Deng compound, so still be present in the problem in the residue behind the hydrochloric acid extracting germanium by distillation, a kind of method that reclaims germanium efficiently, cheaply in the distillation residue after carrying germanium is provided.
A kind of method that reclaims germanium from carry the germanium residue of the present invention is characterized in that this method is to realize by following step:
The first step, washing is carried the germanium residue and is carried out depickling:
In carrying the germanium residue, add the water of weight for 2 ~ 3 times of its weight, be heated to 80～90 ℃, agitator treating 30～45min under this temperature, filter then, filtrate is stand-by, be that the boiling water of the filter residue weight 1/10 ~ 3/20 after filtering washs with weight again, clean back filter solid carbon dioxide branch, the filter residue that obtains cleaning;
Second step, the sodium hydroxide heat pre-treatment:
Filter residue is put into container, and to add weight be to carry the water of 2～2.5 times of the sodium hydroxide of germanium residue weight 3/20～1/5 and germanium residue weight, be heated to 80～85 ℃, stir process 1～1.5h forms the solution after the alkaline purification;
In the 3rd step, concentrate alkaline purification solution:
With the solution heat temperature raising after the alkaline purification to boiling, and evaporate 1～3h to its volume be after the former alkaline purification liquor capacity 2/5～9/20, its cooling is stand-by;
The 4th step, sodium chlorate oxidation-hydrochloric acid fractionation by distillation germanium:
Filtrate stand-by in the above-mentioned the first step joined in the 3rd solid-liquid mixed solution that obtain of step neutralize, wait to neutralize and finish, wash with water or pH value that acid solution is regulated this liquid to less than after 4, add weight again and be 1/100～1/50 the sodium chlorate of putting forward the germanium residue weight, carry 1～2 times the magnesium chloride and the technical hydrochloric acid of putting forward 4～7 times of germanium residue weight of germanium residue weight, making the preceding solution acidity of distillation is 5～6mol/L, stir and be heated to 60～70 ℃, oxidation is germanium at a low price, oxidization time is 45～60 minutes, heat up then and distill, distillation distilled liquid volume is per minute 10～15mL, time is 20～30min, the distillation finish after, from distilled liquid with isolating germanium tetrachloride;
The 5th step, the germanium dioxide preparation:
Germanium tetrachloride is made high-purity germanium dioxide by multiple steaming, rectifying, hydrolysis and oven dry.
Described germanium dioxide obtains distinguishing molten germanium after reduction, the residue of chlorinated distillation is then in lime and the press filtration reduction processing of back.
In the described the first step with in second step, the speed setting of stirring is that per minute 115～120 changes.
Adopt the germanium residue main chemical compositions of carrying of art breading of the present invention to list in the table 1:
Table 1 unit: massfraction, %
| Numbering | 600 ℃ of loss on ignitions | SiO 2 | Fe 2O 3 | Al 2O 3 | MgO | CaO | Cl — | H 2O |
| Z～01 | 34.73 | 24.38 | 3.53 | 7.34 | 1.56 | 4.03 | 29.88 | 56.89 |
| Z～02 | 31.10 | 28.62 | 4.85 | 6.64 | 1.78 | 3.58 | 25.11 | 53.13 |
The principle of technology of the present invention is behind a large amount of hydrochloric acid residual when carrying the germanium residue with the distillation of hot water flush away, to leach the GeO of cubic type with the sodium hydroxide solution heating again
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2All easy and sodium hydroxide reaction finally forms germanic acid root (GeO Deng compound
3 2～) and inclined to one side germanic acid root (GeO
2 2～) entering into solution, after the alkali-soluble material on surface and the silicon dissolving, the germanium of parcel is also further come out, and is heated to boiling then, removes redundant moisture in the leach liquor with evaporation concentration, to reach the purpose of enriched germanium and minimizing hydrochloric acid consumption.With in the washing lotion of washing behind the residue and concentrated solution, to reclaim the germanium in the residual acid, after making concentrated solution become acidity, add magnesium chloride again, to increase the chlorine ion concentration in the solution, reduce the consumption of technical hydrochloric acid, germanium ion and hydrochloric acid reaction when adding hydrochloric acid in the leach liquor, the inclined to one side germanic acid root (GeO of lower valency
2 2～) wait in acidic solution and be oxidized to germanic acid root (GeO by sodium chlorate
3 2～) back and hydrochloric acid reaction generation germanium tetrachloride (GeCl
4), adding and to regulate acidity behind the technical hydrochloric acid to the 6.0mol/L, chlorinated distillation is carried out in heating, and germanium tetrachloride is overflowed with gaseous form, thereby realizes germanium tetrachloride and other separate impurities, germanium tetrachloride (GeCl
4) after hydrolysis, make high-purity germanium dioxide (GeO
2).
The main chemical reactions formula that relates to during we are bright has:
GeO
2(tetrahedron)+2NaOH=Na
2GeO
3+ H
2O
GeO
2.SiO
2+4NaOH=Na
2GeO
3+Na
2SiO
3+2H
2O
GeS+?4NaOH=Na
2GeO
2+Na
2S+2H
2O
GeS
2+6NaOH=Na
2GeO
3+2Na
2S+3H
2O
Ge
2S
3+10NaOH=Na
2GeO
2+Na
2GeO
3+3Na
2S+5H
2O
Na
2GeO
3+6HCl=GeCl
4+2NaCl+3H
2O
3Na
2GeO
2+18HCl+NaClO
3=3GeCl
4+7NaCl+9H
2O
GeCl
4+2H
2O=GeO
2+4HCl
According to above principle; reclaim germanium with processing method of the present invention; can reach more than 75% from carrying the germanium residue to the rate of recovery of germanium tetrachloride; the research of this germanium-extracting technology success is for the high efficiente callback that solves germanium in this type of residue, make full use of rare germanium resource, at the aspect such as environment of storing up, protect that reduces residue very positive meaning arranged.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1:
The first step: 500g is carried the germanium residue, and the moisture massfraction is 52.40%, and the wet germanium massfraction of residue is 0.26%, amount of metal is 1.30g, places the Erlenmeyer flask of 5000mL, adds the 1000mL tap water, after starting agitator and stirring, place to be heated to 80～85 ℃ on the electric furnace, stirring velocity per minute 115 changes agitator treating 30min, vacuum filtration, filtrate 950mL, contain a large amount of hydrochloric acid and germanium because of filtrate, can be used as alkaline purification, to concentrate post neutralization stand-by.Divide the filter residue behind the washing and filtering three times with 50mL boiling water, clean back filter solid carbon dioxide branch, then the filter residue of cleaning is transferred in the former triangular flask.
Second step: triangular flask is placed on the temperature control electric furnace, add the sodium hydroxide of 75g and the tap water of 1000mL, start mechanical stirrer, stirring velocity per minute 115 changes, and after stirring, is heated to 80～85 ℃, stir process 1h, the solution after the formation alkaline purification.
The 3rd step: the solution after the alkaline purification is placed on the temperature control electric furnace, and heat temperature raising evaporates 1h to boiling, and being concentrated into mixeding liquid volume is that the 450mL cooling is stand-by.
The 4th step: filtrate 950mL stand-by in the above-mentioned the first step joined among the 3rd solid-liquid mixed solution 450mL that obtain of step neutralize, after treating that neutralization is finished, after wash water regulator solution pH value to 3.8, add the 5g sodium chlorate, the technical hydrochloric acid of 500g magnesium chloride and 2000mL, it is 5.2mol/L that adjusting makes the preceding solution acidity of distillation, after stirring, be heated to 65 ℃, carried out oxidizing reaction 45 minutes, heat up then and distill, the volume of control distillate is per minute 10～12mL, distillation time is 60min, after distillation is finished, isolates germanium tetrachloride with separating funnel from distillate, obtaining germanium tetrachloride metal 0.977g, is 75.12% from carrying the germanium residue to the rate of recovery of germanium tetrachloride.
The 5th step: the germanium tetrachloride that obtains after traditional multiple steaming, rectifying, hydrolysis and oven dry, can be prepared high-purity germanium dioxide.
Embodiment 2:
The first step: 500g is carried the germanium residue, the moisture massfraction is 56.12%, the wet germanium massfraction of residue is 0.68%, amount of metal is 3.4g, place the Erlenmeyer flask of 5000mL, add residue weight 1250mL tap water, after starting agitator and stirring, place and be heated to 80～85 ℃ on the electric furnace, stirring velocity per minute 115 changes agitator treating 40min, vacuum filtration, obtain wash filtrate 980mL, because of wash filtrate contains a large amount of hydrochloric acid and germanium, it is stand-by to concentrate post neutralization as alkaline purification, divides the filter residue behind the washing and filtering three times with 60mL boiling water, clean back filter solid carbon dioxide branch, then the filter residue of cleaning is transferred in the former triangular flask.
Second step: triangular flask is placed on the temperature control electric furnace, add the sodium hydroxide of 87.5g and the tap water of 1100mL, start mechanical stirrer, stirring velocity per minute 115 changes, after stirring, be heated to 80～85 ℃, stir process 1.25h forms the solution after the alkaline purification.
The 3rd step: the solution after the alkaline purification is placed on the temperature control electric furnace, and heat temperature raising evaporates 1.1h to boiling, and being concentrated into mixeding liquid volume is that the 480mL cooling is stand-by.
The 4th step: filtrate 980mL stand-by in the above-mentioned the first step joined among the 3rd solid-liquid mixed solution 480mL that obtain of step neutralize, after treating that neutralization is finished, after wash water regulator solution pH value to 3.6, add the 7.5g sodium chlorate, the technical hydrochloric acid of 750g magnesium chloride and 2200mL, it is 5.56mol/L that adjusting makes the preceding solution acidity of distillation, after stirring, be heated to 70 ℃, carried out oxidizing reaction 50 minutes, heat up then and distill, the volume of control distillate is per minute 12～15mL, distillation time is 65min, after distillation is finished, isolates germanium tetrachloride with separating funnel from distillate, obtaining germanium tetrachloride metal 2.743g, is 80.76% from carrying the germanium residue to the rate of recovery of germanium tetrachloride.
The 5th step: the germanium tetrachloride that obtains after traditional multiple steaming, rectifying, hydrolysis and oven dry, can be prepared high-purity germanium dioxide.
Embodiment 3:
The first step: 500g is carried the germanium residue, the moisture massfraction is 54.10%, the wet germanium massfraction of residue is 1.21%, amount of metal is 6.050g, place the Erlenmeyer flask of 5000mL, add residue weight 1500mL tap water, after starting agitator and stirring, place and be heated to 85～90 ℃ on the electric furnace, stirring velocity per minute 120 changes agitator treating 45min, vacuum filtration, obtain wash filtrate 990mL, because of wash filtrate contains a large amount of hydrochloric acid and germanium, it is stand-by to concentrate post neutralization as alkaline purification, divides the washing filter residue three times with 75mL boiling water, clean back filter solid carbon dioxide branch, will clean filter residue then and be transferred in the former triangular flask.
Second step: triangular flask is placed on the temperature control electric furnace, add the sodium hydroxide of 100g and the tap water of 1250mL, start mechanical stirrer, stirring velocity per minute 120 changes, and after stirring, is heated to 85～90 ℃, stir process 1.5h, the solution after the formation alkaline purification.
The 3rd step: the solution after the alkaline purification is placed on the temperature control electric furnace, and heat temperature raising evaporates 1.25h to boiling, and being concentrated into mixeding liquid volume is 490mL, and its cooling is stand-by.
The 4th step: filtrate 990mL stand-by in the above-mentioned the first step joined among the 3rd solid-liquid mixed solution 490mL that obtain of step neutralize, after treating that neutralization is finished, again with after the wash water regulator solution pH value to 3.7, add the 10g sodium chlorate, the technical hydrochloric acid of 1000g magnesium chloride and 3500mL, it is 6.00mol/L that adjusting makes the preceding solution acidity of distillation, after stirring, be heated to 67.5 ℃, carried out oxidizing reaction 60 minutes, heat up then and distill, the volume of control distillate is per minute 12～15mL, distillation time is 70min, after distillation is finished, isolates germanium tetrachloride with separating funnel from distillate, obtaining germanium tetrachloride metal 5.429g, is 89.73% from carrying the germanium residue to the rate of recovery of germanium tetrachloride.
The 5th step: the germanium tetrachloride that obtains after traditional multiple steaming, rectifying, hydrolysis and oven dry, can be prepared high-purity germanium dioxide.
Test control condition among the embodiment 1,2,3 and the results are shown in the following table 2.
Table 2
| Test | Embodiment one | Embodiment two | Embodiment three |
| Carry germanium residue wet slag consumption, g | 500 | 500 | 500 |
| Carry germanium residue moisture, % | 52.40 | 56.12 | 54.10 |
| Carry the wet ge content of germanium residue, % | 0.26 | 0.68 | 1.21 |
| The germanium amount of metal, g | 1.300 | 3.400 | 6.050 |
| The wash water consumption, mL | 1000 | 1250 | 1500 |
| Wash temperature, ℃ | 80～85 | 80～85 | 85～90 |
| The wash agitation time, min | 30 | 40 | 45 |
| The washings volume, mL | 950 | 980 | 990 |
| The quality that adds sodium hydroxide, g | 75.0 | 87.5 | 100.0 |
| Add volume of water, mL | 1000 | 1100 | 1250 |
| The alkaline purification time, h | 1.00 | 1.25 | 1.50 |
| Evaporation back mixed concentrated liquid volume, mL | 450 | 480 | 490 |
| Magnesium chloride adds quality, g | 500 | 750 | 1000 |
| 10mol/L technical hydrochloric acid add-on, g | 2000 | 2200 | 3500 |
| Liquid acidity before the distillation, mol/L | 5.20 | 5.56 | 6.00 |
| The sodium chlorate add-on, g | 5 | 7.5 | 10 |
| The germanium tetrachloride distillation speed, mL/min | 10～12 | 12～15 | 12～15 |
| Distillation time, min | 60 | 65 | 70 |
| Steam the germanium tetrachloride amount of metal, g | 0.977 | 2.743 | 5.429 |
| The germanium rate of recovery, % | 75.12 | 80.67 | 89.73 |
Claims (3)
1. method that reclaims germanium from carry the germanium residue is characterized in that this method is to realize by following step:
The first step, washing is carried the germanium residue and is carried out depickling:
In carrying the germanium residue, add the water of weight for 2 ~ 3 times of its weight, be heated to 80～90 ℃, agitator treating 30～45min under this temperature, filter then, filtrate is stand-by, be that the boiling water of the filter residue weight 1/10 ~ 3/20 after filtering washs with weight again, clean back filter solid carbon dioxide branch, the filter residue that obtains cleaning;
Second step, the sodium hydroxide heat pre-treatment:
Filter residue is put into container, and to add weight be to carry the water of 2～2.5 times of the sodium hydroxide of germanium residue weight 3/20～1/5 and germanium residue weight, be heated to 80～85 ℃, stir process 1～1.5h forms the solution after the alkaline purification;
In the 3rd step, concentrate alkaline purification solution:
With the solution heat temperature raising after the alkaline purification to boiling, and evaporate 1～3h to its volume be after the former alkaline purification liquor capacity 2/5～9/20, its cooling is stand-by;
The 4th step, sodium chlorate oxidation-hydrochloric acid fractionation by distillation germanium:
Filtrate stand-by in the above-mentioned the first step joined in the 3rd solid-liquid mixed solution that obtain of step neutralize, wait to neutralize and finish, wash with water or pH value that acid solution is regulated this liquid to less than after 4, add weight again and be 1/100～1/50 the sodium chlorate of putting forward the germanium residue weight, carry 1～2 times the magnesium chloride and the technical hydrochloric acid of putting forward 4～7 times of germanium residue weight of germanium residue weight, making the preceding solution acidity of distillation is 5～6mol/L, stir and be heated to 60～70 ℃, oxidation is germanium at a low price, oxidization time is 45～60 minutes, heat up then and distill, distillation distilled liquid volume is per minute 10～15mL, time is 20～30min, the distillation finish after, from distilled liquid with isolating germanium tetrachloride;
The 5th step, the germanium dioxide preparation:
Germanium tetrachloride is made high-purity germanium dioxide by multiple steaming, rectifying, hydrolysis and oven dry.
2. a kind of method that reclaims germanium from carry the germanium residue as claimed in claim 1 is characterized in that described germanium dioxide obtains distinguishing molten germanium after reduction, and the residue of chlorinated distillation is then in lime and the press filtration reduction processing of back.
3. a kind of method that reclaims germanium from carry the germanium residue as claimed in claim 1 is characterized in that the described the first step and in second step, the speed setting of stirring is that per minute 115～120 changes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102664144A (en) * | 2012-05-18 | 2012-09-12 | 北京大学 | Interface processing method for germanium-base device |
| CN103160688A (en) * | 2013-04-17 | 2013-06-19 | 昆明奥赛美科技有限公司 | Method for preparing germanium concentrate from germanium-containing leachate through utilizing zinc powder replacement method |
| CN106498163A (en) * | 2016-10-08 | 2017-03-15 | 广东先导稀材股份有限公司 | Method from Ti recovery in residual acid is distilled |
| CN110938752A (en) * | 2019-11-07 | 2020-03-31 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Extraction process for improving recovery rate of germanium |
| CN115491524A (en) * | 2022-10-31 | 2022-12-20 | 广西誉升锗业高新技术有限公司 | Process method for recovering germanium from germanium-rich zinc concentrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063200B1 (en) * | 1999-06-23 | 2005-03-30 | Lucent Technologies Inc. | Process for the direct production of germanium tetrachloride from hydrated germanate-containing solids using gaseous hydrogen chloride |
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
| CN101418373A (en) * | 2008-09-16 | 2009-04-29 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium from chlorinated distillation slag |
-
2011
- 2011-04-26 CN CN2011101039471A patent/CN102181649B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063200B1 (en) * | 1999-06-23 | 2005-03-30 | Lucent Technologies Inc. | Process for the direct production of germanium tetrachloride from hydrated germanate-containing solids using gaseous hydrogen chloride |
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
| CN101418373A (en) * | 2008-09-16 | 2009-04-29 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium from chlorinated distillation slag |
Non-Patent Citations (2)
| Title |
|---|
| 《材料研究与应用》 20080630 普世坤等 从氯化蒸馏残渣中回收锗的研究 145-147 1-3 第2卷, 第2期 * |
| 《韶关学院学报（自然科学版）》 20030331 易飞鸿等 从中和渣提取锗的研究 89-92 1-3 第24卷, 第3期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102664144A (en) * | 2012-05-18 | 2012-09-12 | 北京大学 | Interface processing method for germanium-base device |
| CN102664144B (en) * | 2012-05-18 | 2015-04-15 | 北京大学 | Interface processing method for germanium-base device |
| CN103160688A (en) * | 2013-04-17 | 2013-06-19 | 昆明奥赛美科技有限公司 | Method for preparing germanium concentrate from germanium-containing leachate through utilizing zinc powder replacement method |
| CN103160688B (en) * | 2013-04-17 | 2015-08-05 | 昆明奥赛美科技有限公司 | Zinc replacement prepares the method for germanium concentrate from germanic leach liquor |
| CN106498163A (en) * | 2016-10-08 | 2017-03-15 | 广东先导稀材股份有限公司 | Method from Ti recovery in residual acid is distilled |
| CN110938752A (en) * | 2019-11-07 | 2020-03-31 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Extraction process for improving recovery rate of germanium |
| CN115491524A (en) * | 2022-10-31 | 2022-12-20 | 广西誉升锗业高新技术有限公司 | Process method for recovering germanium from germanium-rich zinc concentrate |
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| CN102181649B (en) | 2012-08-15 |
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