CN102787243A - Method for recycling germanium from zinc distillation residues - Google Patents
Method for recycling germanium from zinc distillation residues Download PDFInfo
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- CN102787243A CN102787243A CN2012103303596A CN201210330359A CN102787243A CN 102787243 A CN102787243 A CN 102787243A CN 2012103303596 A CN2012103303596 A CN 2012103303596A CN 201210330359 A CN201210330359 A CN 201210330359A CN 102787243 A CN102787243 A CN 102787243A
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- hydrochloric acid
- germanium
- zinc
- oxidation
- distillation residue
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of wet metallurgy, in particular to a technology of recycling germanium from zinc vacuum distillation residues. The technology comprises steps as follows: leaching active metal elements from the zinc distillation residue by a hydrochloric acid solution, then using hydrogen peroxide as an oxidant to oxidize, dissolve and leach chemical elements hardly reactive to the hydrochloric acid from the zinc distillation residues; adding sodium chlorate to the treated solution to further oxidize the chemical elements incompletely oxidized by the hydrogen peroxide; then extracting the germanium by hydrochloric acid distillation. The process provided by the invention is short in process, the requirement on equipment is simple, the process is easy to control, and the cost is low; because of avoiding using poisonous chlorine, the oxidizing roasting is avoided, the chlorinating and roasting loss on the germanium is reduced, the yield rate is high, and the safety is rather high; and processing wastewater can be discharged up to the standard after neutralization so as to avoid the influence on the environment.
Description
Technical field
The present invention relates to technical field of wet metallurgy, specifically a kind of technology that from the zinc short residuum, reclaims germanium.
Background technology
All can the output distillation residue behind the zinc smeltery vacuum distilling hard zinc; The zinc distillation residue belongs to complicated unmanageable many metals waste residue, and it is all higher that it contains rare metal germanium, indium, has very high comprehensive reutilization and is worth; But because its complicated component is changeable; Valuable element and harmful element arsenic content are all higher, and mostly exist with metallic state and semi-metal attitude form, the comprehensive difficulty that reclaims; Therefore a kind of method such as germanium indium that reclaims is efficiently sought in research, and is very necessary for the recovery that solves valuable metals such as germanium indium in this type of waste residue.
Germanium recovery technology in the zinc distillation residue generally is that the method that adopts " wet ball-milling-sulfuric acid leaching-oxidizing roasting-chlorinated distillation " reclaims (Lan Zongying, " the comprehensive germanium indium silver that reclaims from the vacuum slag ", non-ferrous metal (smelting part) at present; 2003 5 phases); Adopt sulfuric acid to leach a part of zinc earlier and directly send chlorinated distillation to extract germanium after the roasting again, from vinasse, reclaim indium with the P204-TBP combined extraction again, generally need a straight-through chlorine in the still-process of germanium with elements such as germanium oxide, indium, lead, zinc, arsenic; Exist the liquid chlorine consumption big; Estimate that one ton of material of every processing needs the liquid chlorine of 1-1.5 ton, tail gas absorbs the also significantly increase of alkali lye amount of usefulness simultaneously, and liquid chlorine belongs to high poison dangerization article; Handling 800 tons material needs the liquid chlorine of 800-1200 ton approximately, and this is difficult to control in safety in production.Simultaneously also someone's method of having proposed employing " alkali fusion (separation of lead silver)-alkali soaks (separation SiGe)-chlorinated distillation (separating Ge)-tannin extract (neutralization) and precipitates (germanium concentrate)-salt acid distillation " reclaims (Lin Xingming; " the vacuum oven slag for comprehensive reclaims the alkali fusion experimental study of metals such as germanium indium silver "; Coloured mining and metallurgy; In June, 2004, the 20th the 3rd phase of volume).But above two methods all exist the germanium direct yield lower, and chlorine-hydrochloric acid distillation method germanium direct yield is about 80%, alkali fusion direct yield about 81.9%; Reaction process is restive; Cost recovery is high, and environmental pollution is serious, and alkali fusion-alkaline leaching is on the existing installation basis; Need increase equipment such as liquate, leaching and deposition newly, the input of fixed capital is bigger.
Summary of the invention
The object of the present invention is to provide that a kind of recovery is high, cost recovery is low, the process method that from the zinc distillation residue, reclaims germanium of environmental protection more.
The invention discloses a kind of process method that from the zinc distillation residue, reclaims germanium; It is characterized in that adopting hydrochloric acid soln to leach the active metal element in the zinc distillation residue earlier; Adopt the chemical element of hydrogen peroxide then as difficult in the oxygenant oxidation dissolving leaching zinc distillation residue and hydrochloric acid reaction; Solution after handling is added the further oxidation hydrogen peroxide of VAL-DROP again fail the chemical element of complete oxidation, carry out hydrochloric acid distillation extraction germanium then, the practical implementation step is following:
The 1st step, dissolving with hydrochloric acid
Get the zinc distillation residue; 1-1.5 by its weight extraordinarily goes into water-wet; Extraordinarily go into the technical hydrochloric acid of 10 mol/L by the 0.8-1.5 of zinc distillation residue weight, fully react 1-1.5 h, end when no longer producing bubble; Stirring velocity is 115 rev/mins, and the hydrochloric acid acidity control was at 3-4 mol/L after temperature of reaction 50-65 ℃ of reaction accomplished;
The 2nd step, hydrogen peroxide oxidation
Adding the quality percentage composition by the 1.5-3 of zinc distillation residue weight amount doubly is in 50% the solution of hydrogen peroxide after step 1 dissolving; Adding speed is PM 20-100 ml; The controlled oxidation temperature of reaction is 55-70 ℃, and stirring velocity is 115 rev/mins, reaction times 1-2 h;
The 3rd step, the VAL-DROP oxidation
0.2-0.5 amount doubly by the zinc distillation residue weight adds VAL-DROP in through the solution after step 2 oxidation, and the controlled oxidation temperature of reaction is 50-60 ℃, and stirring velocity is 115 rev/mins, reaction times 1-2 h;
In the 4th step, the salt acid distillation adds the technical hydrochloric acid of 10 mol/L by the 5.0-6.0 of zinc distillation residue weight amount doubly, and the distillation initial acidity is controlled at 6.6-7.5 mol/L, and the vinasse acidity control is at 6.0-6.5 mol/L; After stirring, add thermal distillation and obtain germanium tetrachloride, germanium tetrachloride can prepare germanium dioxide after the technology rectification and purification hydrolysis of routine.
The reaction formula that relates in above-mentioned each step is following:
(1) hydrochloric acid leaches
Zn+2HCl=ZnCl
2+H
2↑
ZnO+2HCl=ZnCl
2+H
2O
Fe+2HCl=FeCl
2+H
2↑
Sn+2HCl=SnCl
2+H
2↑
(2) hydrogen peroxide oxidation
Ge+2H
2O
2+4HCl=GeCl
4+4H
2O
2In+3H
2O
2+6HCl=2InCl
3+6H
2O
2FeCl
2+H
2O
2+2HCl=2FeCl
3+2H
2O
2As+6HCl+3H
2O
2=2AsCl
3+6H
2O
AsCl
3+2HCl+H
2O
2?=AsCl
5+2H
2O
Pb+2HCl+H
2O
2=PbCl
2+2H
2O
Cu+2HCl+H
2O
2=CuCl
2+2H
2O
SnCl
2+2HCl+H
2O
2=SnCl
4+2H
2O
(3) VAL-DROP oxidation
2AsCl
3?+2HCl+NaClO
3?=2AsCl
5+NaClO+H
2O
Ge+4HCl+NaClO
3?=GeCl
4+NaClO+2H
2O
2Pb+4HCl+NaClO
3?=2PbCl
2+NaClO+2H
2O
Cu+4HCl+NaClO
3=CuCl
2+NaClO+2H
2O
(4) salt acid distillation
Ge
4++4Cl
-=GeCl
4↑.
In the method for the invention, earlier behind the zinc distillation residue water dispersion moistening, adopt 4-5 mol.L again
-1Dissolving with hydrochloric acid leach, make part active metal such as zinc, iron, tin etc. and hydrochloric acid reaction get into solution, to generating positively charged ion at a low price, the insoluble part of hydrochloric acid adopts hydrogen peroxide to leach as oxygenant oxidation dissolving again, promptly at 3-4 mol.L
-1Hydrochloric acid soln in the zinc distillation residue is added hydrogen peroxide carry out oxidation and leach and handle; Make the difficult chemical element of metallic state in hydrochloric acid soln, be oxidized to the high valence ion attitude and get in the solution like lead, germanium, indium, arsenic, copper etc. with hydrochloric acid reaction; The iron of the lower valency that generates with hydrochloric acid reaction simultaneously, tin etc. also further have been oxidized to the high-valence cationic attitude and have got into solution; And silicon-dioxide etc. not with hydroperoxidation; Remain in the slag, the solution after handling being added again hydrogen peroxide such as the further arsenic oxide arsenoxide of VAL-DROP, to fail the composition of complete oxidation be high valence state, with the consumption that reduces hydrogen peroxide and the consumption of hydrochloric acid; Because of a large amount of water is arranged in the hydrogen peroxide, leach after handling and to adjust to 6.5-7.0 mol.L to the initial acidity of handling back liquid
-1, add excessive water the consumption of hydrochloric acid is significantly increased, therefore adopt part VAL-DROP to replace hydrogen peroxide, handle the back well and add technical hydrochloric acid, regulating acidity is 6.5-7.0 mol.L
-1, carry out fractionation by distillation germanium then, to vinasse adopt in sodium hydroxide and the yellow soda ash and after, the sulfuric acid leaching.
Because existing process method all can not satisfy the needs of high efficiente callback germanium, the process method of other high-efficiency environment friendly of research employing is handled this type of zinc distillation residue and is just seemed very necessary.After process a large amount of investigative test and expanding test, we have found a kind of efficient and economic process method of ten minutes that reclaims germanium in this type of zinc distillation residue, promptly are employed in 4.0-5.0 mol.L
-1About hydrochloric acid soln in active metals such as hydrogen peroxide oxidation germanium, indium, zinc, lead, tin, copper, arsenic; Make it dissolving and enter into solution, and then adding VAL-DROP, to carry out element such as the abundant arsenic oxide arsenoxide of secondary be high valence state, in case distillation arsenic overflows the pollution germanium tetrachloride; Carry out fractionation by distillation with hydrochloric acid more at last and reclaim germanium; The germanium distillation recovery can reach more than 97%, and distillation residue are germanic below 0.03%, and the lead content in the residue reaches 45-49%; Zinc all gets in the raffinate, and content is less than 0.1% in the residue.Compare with the recovery method of " alkali fusion-alkali soaks-chlorinated distillation-tannin extract deposition-salt acid distillation " with " wet ball-milling-sulfuric acid leaching-oxidizing roasting-chlorinated distillation ", this technology process flow process is brief, and equipment requirements is simple; Technological process is easy to control, and cost is lower, owing to avoided using the chlorine of severe toxicity; Avoided oxidizing roasting; Thereby also reduced the chlorination and the loss by roasting of germanium, so the recovery is higher, security simultaneously is also higher; But the qualified discharge after neutralization that disposes waste liquid, thereby avoided influence to environment.
Embodiment
Embodiment 1:
Get 400g zinc distillation residue, ge content is 2.03%, and indium content is 1.76%, and in 5000 mL Erlenmeyer flasks, it is wetting to add 500 mL tap water, adds 10 mol.L
-1Technical hydrochloric acid 400 mL, after stirring, add the quality percentage composition and be 50% hydrogen peroxide 600 mL; Adding speed is PM 20 mL, and oxidizing reaction temperature is controlled at 50-70 ℃, 115 rev/mins of stirring velocitys; Reaction times 1h; And then add in the solution of 120 g VAL-DROP after oxidation, reaction 0.5h adds 10 mol.L then
-1Technical hydrochloric acid 2000 mL, after stirring, add thermal distillation and obtain germanium tetrachloride 23.28 g, the germanium recovery is 96.97%; Germanium tetrachloride can prepare germanium dioxide after the rectification and purification hydrolysis, to vinasse adopt in sodium hydroxide and the yellow soda ash and after, carry out liquid-solid separation; With the back qualified discharge, indium remains in the slag in the raffinate, uses P204 extracting and separating indium again behind the employing sulfuric acid leached mud; After back extraction purification and reduction founding, prepare thick indium 6.24 g, indium recovery is 88.6%.
Embodiment 2:
Get 400 g zinc distillation residues, ge content is 2.37%, and indium content is 1.87%, and in 5000 mL Erlenmeyer flasks, it is wetting to add 600 mL tap water, adds 10 mol.L
-1Technical hydrochloric acid 500 mL, after stirring, add the quality percentage composition and be 50% hydrogen peroxide 800 mL; Adding speed is PM 30 mL, and oxidizing reaction temperature is controlled at 60-70 ℃, 115 rev/mins of stirring velocitys; Reaction times 1.5 h; And then add in the solution of 160 g VAL-DROP after oxidation, react 1.0 h, add 10 mol.L then
-1Technical hydrochloric acid 2400 mL, after stirring, add thermal distillation and obtain germanium tetrachloride 27.32 g, the germanium recovery is 96.97%; Germanium tetrachloride can prepare germanium dioxide after the rectification and purification hydrolysis, to vinasse adopt in sodium hydroxide and the yellow soda ash and after, carry out liquid-solid separation; With the back qualified discharge, indium remains in the slag in the raffinate, uses P204 extracting and separating indium again behind the employing sulfuric acid leached mud; After back extraction purification and reduction founding, prepare thick indium 6.81 g, indium recovery is 91.03%.
Claims (1)
1. process method that from the zinc distillation residue, reclaims germanium; It is characterized in that adopting hydrochloric acid soln to leach the active metal element in the zinc distillation residue earlier; Adopt the chemical element of hydrogen peroxide then as difficult in the oxygenant oxidation dissolving leaching zinc distillation residue and hydrochloric acid reaction; Solution after handling is added the further oxidation hydrogen peroxide of VAL-DROP again fail the chemical element of complete oxidation, carry out hydrochloric acid distillation extraction germanium then, the practical implementation step is following:
The 1st step, dissolving with hydrochloric acid
Get the zinc distillation residue; 1-1.5 by its weight extraordinarily goes into water-wet; Extraordinarily go into the technical hydrochloric acid of 10 mol/L by the 0.8-1.5 of zinc distillation residue weight, fully react 1-1.5 h, end when no longer producing bubble; Stirring velocity is 115 rev/mins, and the hydrochloric acid acidity control was at 3-4 mol/L after temperature of reaction 50-65 ℃ of reaction accomplished;
The 2nd step, hydrogen peroxide oxidation
Adding the quality percentage composition by the 1.5-3 of zinc distillation residue weight amount doubly is in 50% the solution of hydrogen peroxide after step 1 dissolving; Adding speed is PM 20-100 ml; The controlled oxidation temperature of reaction is 55-70 ℃, and stirring velocity is 115 rev/mins, reaction times 1-2 h;
The 3rd step, the VAL-DROP oxidation
0.2-0.5 amount doubly by the zinc distillation residue weight adds VAL-DROP in through the solution after step 2 oxidation, and the controlled oxidation temperature of reaction is 50-60 ℃, and stirring velocity is 115 rev/mins, reaction times 1-2 h;
In the 4th step, the salt acid distillation adds the technical hydrochloric acid of 10 mol/L by the 5.0-6.0 of zinc distillation residue weight amount doubly, and the distillation initial acidity is controlled at 6.6-7.5 mol/L, and the vinasse acidity control is at 6.0-6.5 mol/L; After stirring, add thermal distillation and obtain germanium tetrachloride, germanium tetrachloride prepares germanium dioxide after the technology rectification and purification hydrolysis of routine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104164577A (en) * | 2014-07-25 | 2014-11-26 | 武汉云晶飞光纤材料有限公司 | Method for recovering germanium from tail gas generated by distillation of germanium tetrachloride |
| CN104789777A (en) * | 2014-01-16 | 2015-07-22 | 汉能新材料科技有限公司 | Method for recovering germanium and bismuth from bismuth germinate crystal processing wastes |
| CN104911363A (en) * | 2015-06-24 | 2015-09-16 | 上海交通大学 | Method for recovering germanium in lignite smoke |
| CN115404364A (en) * | 2022-09-24 | 2022-11-29 | 昆明理工大学 | Method for preparing germanium hydroxide from zinc hydrometallurgy inorganic germanium slag |
| CN115611304A (en) * | 2022-09-28 | 2023-01-17 | 昆明理工大学 | Method for preparing germanium tetrachloride from zinc hydrometallurgy inorganic germanium slag |
| CN116640928A (en) * | 2023-07-27 | 2023-08-25 | 昆明理工大学 | Method for co-treatment of germanium chloride distillation residues and lead-zinc smelting acid wastewater |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789777A (en) * | 2014-01-16 | 2015-07-22 | 汉能新材料科技有限公司 | Method for recovering germanium and bismuth from bismuth germinate crystal processing wastes |
| CN104164577A (en) * | 2014-07-25 | 2014-11-26 | 武汉云晶飞光纤材料有限公司 | Method for recovering germanium from tail gas generated by distillation of germanium tetrachloride |
| CN104164577B (en) * | 2014-07-25 | 2015-11-25 | 武汉云晶飞光纤材料有限公司 | A kind of method of Ti recovery from the tail gas that rectifying germanium tetrachloride produces |
| CN104911363A (en) * | 2015-06-24 | 2015-09-16 | 上海交通大学 | Method for recovering germanium in lignite smoke |
| CN115404364A (en) * | 2022-09-24 | 2022-11-29 | 昆明理工大学 | Method for preparing germanium hydroxide from zinc hydrometallurgy inorganic germanium slag |
| CN115611304A (en) * | 2022-09-28 | 2023-01-17 | 昆明理工大学 | Method for preparing germanium tetrachloride from zinc hydrometallurgy inorganic germanium slag |
| CN116640928A (en) * | 2023-07-27 | 2023-08-25 | 昆明理工大学 | Method for co-treatment of germanium chloride distillation residues and lead-zinc smelting acid wastewater |
| CN116640928B (en) * | 2023-07-27 | 2023-10-20 | 昆明理工大学 | Method for co-treatment of germanium chloride distillation residues and lead-zinc smelting acid wastewater |
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Application publication date: 20121121 |