CN102345021B - Method for recovering germanium from germanium smoke dust by microwave pretreatment - Google Patents
Method for recovering germanium from germanium smoke dust by microwave pretreatment Download PDFInfo
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- CN102345021B CN102345021B CN201110294835.9A CN201110294835A CN102345021B CN 102345021 B CN102345021 B CN 102345021B CN 201110294835 A CN201110294835 A CN 201110294835A CN 102345021 B CN102345021 B CN 102345021B
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- germanium
- leaching
- smoke dust
- microwave heating
- containing smoke
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 78
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000428 dust Substances 0.000 title claims abstract description 22
- 239000000779 smoke Substances 0.000 title claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 7
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 238000004821 distillation Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCOTVPPCUSAUGC-UHFFFAOYSA-N [Ge]=O.[Ge] Chemical compound [Ge]=O.[Ge] HCOTVPPCUSAUGC-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering germanium from germanium smoke dust by microwave pretreatment. The method comprises the following steps of: carrying out microwave heating pretreatment on germanium-containing smoke dust; dissolving the germanium-containing smoke dust obtained by microwave heating pretreatment with a sulfuric acid solution as a leaching agent, and stirring and leaching; and filtering and separating the solution obtained by leaching, washing three times, and discarding filter slag so as to obtain a germanium-containing liquid. By adopting the method provided by the invention, the leaching rate of germanium reaches more than 75%; and the leaching rate of germanium is improved by more than 15% as compared with direct sulfuric acid leaching. According to the invention, microwave heating pretreatment is carried out on the germanium smoke dust, so that difficult-soluble germanium is converted to easy-soluble germanium, thereby improving the leaching rate of germanium. The method provided by the invention has the advantages of simple process, short process flow, high leaching speed and high leaching rate.
Description
Technical field
The present invention relates to a kind of from germanium oxide dust Microwave Pretreatment reclaim the method for germanium, belong to chemical metallurgy technical field.
Background technology
In fields such as optical fiber, infrared optics, solar cells, germanium occupies more and more consequence at present.European and American developed countries mostly classify germanium as national defence reserved resources.
But germanium is a kind of dissipated metal, and the resource of world's germanium is poorer.China's germanium reserves position is at the forefront in the world, and germanium is generally that association is in the metallic ores such as copper, lead, zinc and colliery.Mainly be distributed in Shengli Coalfield, inner Mongolia Hong Chunquan colliery, coalfield, municipalization city, Jiutai, all mouthful of Renhua County, Guangdong plumbous zinc ore, Huidong County, Sichuan Daliangzi Pb-zn Deposit, Yunnan lead-zinc deposit and copper valley, Xinghai County, Qinghai ditch copper mine.China does not almost have independently germanium ore deposit, and germanium almost all reclaims and obtains from non-ferrous metal associated minerals and colliery.Low exploitation and the widespread use that has seriously restricted for a long time germanium of the rate of recovery of germanium.
For different germanium-containing materials, the method for the recovery germanium adopting mainly contains sulfuric acid leaching, distillation method, alkaline leaching, hydrofluoric acid method, extraction process, reduction method and Microorganism Leaching method etc. are leached in chlorination at present.Wherein zinc leaching residue and smelting zinc, lead and copper waste residue adopt the method for sulfuric acid leaching to reclaim germanium more, and sulfuric acid leaching can be divided into normal pressure sulfuric acid leaching and high pressure sulfuric acid leaching.The process of sulfuric acid leaching is generally after first germanium-containing material enriched germanium being processed, then in more than 65 ℃ temperature, with sulfuric acid leaching more than concentration 100g/L, extraction time is generally 3～5 hours.In leaching process, germanium is transferred in solution with reacting of sulphuric acid soln by germanium-containing material.Its principal reaction is as follows:
The leaching yield of germanium is generally in 50% left and right at present.Undissolved germanium is mainly with SiO
2-GeO
2form exists, and leaching process can produce Si (OH)
4polymer, the Si of generation (OH)
4more, adsorptivity is stronger, and the leaching yield of germanium is just lower.In order to improve the leaching yield of germanium, generally adopt the method that reduces silicone content in germanium-containing material, but the existing silicon technology that removes is difficult to silicone content to be reduced to below 2%.Current research shows: high pressure sulfuric acid leaching can be realized the higher germanium rate of recovery (more than 90%), and germanium removal process realizes without useless production, but the method need to be with specific installations such as corrosion resistant autoclaves, invest greatlyr, be not therefore used widely.
Chlorination is leached distillation method and is applicable to processing the germanium-containing material that ge content is greater than 2%, and germanium is the following reaction of main generation in HCl solution:
（5）
Due to the GeCl generating
4boiling point lower than general muriatic boiling point, so can adopt the method for distillation to make germanium separated with other impurity.Leach liquid-solid ratio and be about 3, HCl strength of solution and be generally greater than 7mol/L, distillation temperature is 110 ℃ of left and right, distillation time about half an hour.
Alkaline leaching is that germanium-containing material is leached with sodium hydroxide solution, and following reaction mainly occurs leaching process:
Alkaline leaching processing unit is simple, equipment cost is low.But because basicity is high, cause follow-up solid-liquid separation process difficulty, and the germanium rate of recovery is not generally higher than 85%.
Because germanium-containing material has complex structure diversity, so the recovery method of germanium is also varied.But these recovery methods have weak point separately: method germanium rate of recovery method cost low, that the germanium rate of recovery is high that cost is low is higher maybe cannot realize industrialization.In germanium-containing material, the taste of germanium is low, silicone content is high and germanium is major causes that the germanium rate of recovery is low by other mineral parcels.Conventional preparation of ore technology is difficult to meet the needs of actual production, therefore can adopt unconventional method to process germanium-containing material.
Summary of the invention
For improving the leaching yield of germanium, thereby improve the germanium rate of recovery, the invention provides a kind of from germanium oxide dust Microwave Pretreatment reclaim the method for germanium, by following technical proposal, realize.
From germanium oxide dust, Microwave Pretreatment reclaims a method for germanium, following each step of process:
A. germanium-containing smoke dust is carried out to microwave heating pre-treatment;
B. use sulphuric acid soln as leaching agent, dissolving step A gained germanium-containing smoke dust, carries out agitation leach;
C. the solution after again step B gained being leached carries out filtering separation, washs after three times, discards filter residue, obtains germanic liquid.
The germanium-containing smoke dust of described steps A is the germanium oxide dust that germanic mass percent is 0.04～1%.
The pretreated frequency of microwave heating of described steps A is that 2450MHz, temperature are 200～500 ℃, processes 1～30min.
The sulphuric acid soln concentration of described step B is 6～15mol/L.
Sulphuric acid soln and germanium-containing smoke dust in described step B are that 2～8 ︰ 1 carry out mixed dissolution by liquid-solid ratio.
The agitation leach temperature of described step B is 50～90 ℃, agitation leach 0.5～5 hour.
Effect of the present invention and advantage: adopt the leaching yield of the method germanium to reach more than 75%; The leaching yield of germanium improves more than 15% than direct sulfuric acid leaching; The present invention through microwave heating pre-treatment, makes the germanium of indissoluble change to easily molten germanium germanium oxide dust, improve the leaching yield of germanium, and technique is simple, flow process is short, leaching velocity is fast, leaching yield is high.
Embodiment
Below in conjunction with embodiment, further illustrate content of the present invention, but these examples do not limit the scope of the invention.
Embodiment 1
A. the germanium-containing smoke dust (Ge0.04%, Zn:1.56%, Fe:1.89%, Si:2.15%) that is 0.04% to the germanic mass percent of 800g is that 2450MHz, temperature are at 200 ℃, to carry out microwave heating pre-treatment 1min in frequency;
B. the sulphuric acid soln that is 10mol/L by 1600mL concentration, as leaching agent, is 2 ︰ 1 dissolving step A gained germanium-containing smoke dusts by liquid-solid ratio, in temperature, is agitation leach 0.8 hour at 70 ℃;
C. the solution after again step B gained being leached carries out filtering separation, washs after three times, discards filter residue, obtains germanic liquid, and the leaching yield of germanium is 80.13%.
Embodiment 2
A. the germanium-containing smoke dust (Ge:0.12%, Zn:5.66%, Fe:3.89%, Si:1.85%) that is 0.12% to the germanic mass percent of 100kg is that 2450MHz, temperature are at 300 ℃, to carry out microwave heating pre-treatment 30min in frequency;
B. the sulphuric acid soln that is 6mol/L by 400L concentration, as leaching agent, is 4 ︰ 1 dissolving step A gained germanium-containing smoke dusts by liquid-solid ratio, in temperature, is agitation leach 0.5 hour at 90 ℃;
C. the solution after again step B gained being leached carries out filtering separation, washs after three times, discards filter residue, obtains germanic liquid, and the leaching yield of germanium is 82.88%.
Embodiment 3
A. the germanium-containing smoke dust (Ge:1%, Zn:3.26%, Fe:2.12%, Si:1.65%) that is 1% to the germanic mass percent of 300g is that 2450MHz, temperature are at 500 ℃, to carry out microwave heating pre-treatment 8min in frequency;
B. the sulphuric acid soln that is 15mol/L by 2400mL concentration, as leaching agent, is 8 ︰ 1 dissolving step A gained germanium-containing smoke dusts by liquid-solid ratio, in temperature, is agitation leach 5 hours at 50 ℃;
C. the solution after again step B gained being leached carries out filtering separation, washs after three times, discards filter residue, obtains germanic liquid, and the leaching yield of germanium is 86.52%.
Claims (2)
1. from germanium oxide dust, Microwave Pretreatment reclaims the method for germanium, it is characterized in that through following each step:
A. germanium-containing smoke dust be take to frequency and carry out microwave heating pre-treatment 1～30min as 2450MHz, the pretreated temperature of microwave heating is 200～500 ℃;
B. the sulphuric acid soln that is 6～15mol/L by concentration, as leaching agent, is 2～8 ︰ 1 dissolving step A gained germanium-containing smoke dusts by liquid-solid ratio, in temperature, is at 50～90 ℃, to carry out agitation leach 0.5～5 hour;
C. the solution after again step B gained being leached carries out filtering separation, washs after three times, discards filter residue, obtains germanic liquid.
2. method according to claim 1, is characterized in that: the germanium-containing smoke dust of described steps A is the germanium oxide dust that germanic mass percent is 0.04～1%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110294835.9A CN102345021B (en) | 2011-10-08 | 2011-10-08 | Method for recovering germanium from germanium smoke dust by microwave pretreatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110294835.9A CN102345021B (en) | 2011-10-08 | 2011-10-08 | Method for recovering germanium from germanium smoke dust by microwave pretreatment |
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| CN102345021A CN102345021A (en) | 2012-02-08 |
| CN102345021B true CN102345021B (en) | 2014-02-12 |
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-
2011
- 2011-10-08 CN CN201110294835.9A patent/CN102345021B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267738A (en) * | 1999-03-18 | 2000-09-27 | 电子科技大学 | Pretreatment microwave technology for coated composite platinum-palladium ore |
| WO2002099145A1 (en) * | 2001-06-07 | 2002-12-12 | Elcogas, S.A. | Method for recovering metals from the flying ashes generated in an integrated gasification combined cycle-type (igcc) thermal station |
| UA15687U (en) * | 2006-01-03 | 2006-07-17 | Ozaporizhia Titanium And Magne | A method for withdrawing germanium from the flue ash |
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| UA31484U (en) * | 2007-12-10 | 2008-04-10 | Казенное Предприятие "Запорожский Титано-Магниевый Комбинат" | Method for germanium recovery from fly ash |
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