CN103468977A - Method for selectively leaching germanium and gallium from complex smelting slag with germanium and gallium or ore with germanium and gallium - Google Patents
Method for selectively leaching germanium and gallium from complex smelting slag with germanium and gallium or ore with germanium and gallium Download PDFInfo
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- CN103468977A CN103468977A CN2013104688251A CN201310468825A CN103468977A CN 103468977 A CN103468977 A CN 103468977A CN 2013104688251 A CN2013104688251 A CN 2013104688251A CN 201310468825 A CN201310468825 A CN 201310468825A CN 103468977 A CN103468977 A CN 103468977A
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 105
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 93
- 239000002893 slag Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002386 leaching Methods 0.000 title claims abstract description 17
- 238000003723 Smelting Methods 0.000 title abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 13
- 239000001110 calcium chloride Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 230000001698 pyrogenic effect Effects 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 229910000906 Bronze Inorganic materials 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZTWJHWHNPLICTA-UHFFFAOYSA-N [Cu].[Fe].[Ge].[S] Chemical compound [Cu].[Fe].[Ge].[S] ZTWJHWHNPLICTA-UHFFFAOYSA-N 0.000 description 1
- 239000001887 acacia decurrens willd. var. dealbata absolute Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 selectively leaching germanium and gallium from complex smelting slag with the germanium and the gallium or ore with the germanium and the gallium, and belongs to the field of non-ferrous metal hydrometallurgy and secondary-resource recycling. The method for selectively leaching the germanium and the gallium from the complex smelting slag with the germanium and the gallium or the ore with the germanium and the gallium comprises the steps that the germanium and the gallium are selectively leached from the complex smelting slag with the germanium and the gallium or the ore with the germanium and the gallium under the conditions of high temperature, high pressure, oxygen supply and the alkalinity environment, the pH is adjusted, impurity removal is carried out, the gallium is deposited through calcium chloride, the germanium is deposited through neutralization, and the germanium and the gallium are selectively recovered. The method for selectively leaching the germanium and the gallium from the complex smelting slag with the germanium and the gallium or the ore with the germanium and the gallium can achieve the purposes that the recovery rate of the germanium reaches 98%, and the recovery rate of the gallium reaches 99%, achieve the effect of high-selectivity leaching of the germanium and the gallium, and is high in recovery rate. The method for selectively leaching the germanium and the gallium from the complex smelting slag with the germanium and the gallium or the ore with the germanium and the gallium is high in applicability of raw materials, is applicable to all types of complex pyrogenic process smelting slag with the germanium and the gallium and all types of complex wet process smelting slag with the germanium and the gallium, and can be applicable to the ore with the high-content germanium and the high-content gallium.
Description
Technical field
The present invention relates to method, genus non-ferrous metal hydrometallurgy and secondary resource recovery field that a kind of metallurgical slag from the germanic gallium of complexity or ore, selectivity leaches the germanium gallium.
Technical background
The content of germanium in the earth's crust is 7/1000000ths, and germanium disperses very much, and almost concentrated germanium ore deposit without comparison, therefore, be called by people " dissipated metal ".There are argyrodite (germanic 5-7%), germanite (germanic 10%), sulphur copper iron germanium ore deposit (germanic 7%) in the germanium ore deposit of having found.The germanium gallium all is commonly used among semi-conductor, and being used for manufacturing transistor is important semiconductor material, and growing today for electron trade, the germanium gallium more and more is applied in semicon industry.Therefore the selective recovery of germanium gallium is more and more important.At present, the comprehensive recovery of germanium gallium still be take common hydrometallurgic recovery as main, its operating procedure complexity, production cycle is long, and each valuable metal loss, do not possess highly selective, gallium germanium major part is all to adopt extraction system, and germanium is all that cost is excessive by Weibull and mimosa extract precipitation mostly.Concerning medium-sized and small enterprises, investment is large, the extraction equipment utilization ratio is low.Therefore the method for highly selective recovery germanium gallium is that the germanium gallium comprehensively reclaims the field important topic.
State's invention patent publication No. 102719679A in 10 days October in 2012, a kind of " method that reclaims gallium and germanium from carry the germanium residue " that discloses the universal invention such as female of Yunnan Province xinyuan Ge industry Co., Ltd proposed that fractionation by distillation, slag liquid by roasting, leaching, germanium separates, extraction, reextraction, hydrolytic precipitation and gallium germanium concentrate.This patent of invention is that gallium and the germanium in the residue of germanic coal flue dust after carrying out chlorination of hydrochloric acid fractionation by distillation germanium that obtain of pyrometallurgical smelting carries out effective recycling, this patent of invention has certain limitation to starting material, and adopt distillation, extraction, reextraction system, the technique practicality is not strong.Do not possess the recovery of highly selective germanium gallium yet.
Summary of the invention
The object of the invention is to provide the method for selectivity leaching germanium gallium a kind of metallurgical slag from the germanic gallium of complexity or ore, can realize that the germanium rate of recovery is up to 98%, and the gallium rate of recovery is up to gallium 99%; Reached the effect of highly selective leaching germanium gallium, and the rate of recovery is high.Adaptability to raw materials of the present invention is strong, not only is applicable to pyrogenic process, the hydrometallurgy slag of the germanic gallium of various complexity, can also be applicable to the ore of high germanic gallium.
The technical scheme that the present invention deals with problems is: a kind of metallurgical slag from the germanic gallium of complexity or ore, selectivity leaches the method for germanium gallium, make metallurgical slag or ore selectivity under the logical oxonium base condition of High Temperature High Pressure of complicated germanic gallium leach germanium, gallium, after overregulating the removal of impurities of pH value, successively with the heavy gallium of calcium chloride, the heavy germanium of neutralization, obtain respectively high enrichment gallium slag and high enriched germanium slag; Make germanium, gallium obtain selective recovery;
Technology condition of the present invention is as follows:
(1) ore grinding requires: raw material ball is milled to below granularity 300 orders;
(2) selectivity leaches: after getting ball milling, raw material is contained in the autoclave of use for laboratory, adds sodium hydroxide; Liquid-solid volume mass is than being 5-8:1, the L/kg of unit; The concentration that selectivity leaches agent sodium hydroxide is 100-150 g/L, and pressure is at 0.8-1.6MPa, and temperature is controlled at 130-180 ℃, in the situation that pass into the oxygen reaction times, is 3-6 hour; Separate the slag charge and the selective leaching fluid that obtain after selectivity leaches the germanium gallium; Selectivity leaches slag charge after the germanium gallium can enter the valuable metals such as lead wherein of pyrogenic process system recoveries, copper, bismuth;
(3) in and impurity removal process: in the selective leaching fluid, add the sulfuric acid of 1-3mol/L to adjust pH=13-14, filter after removal of impurities, the filter residue circulation is back to selective leaching and goes out operation;
(4) heavy gallium technique: in and after removal of impurities liquid add calcium chloride to sink gallium, calcium chloride adds weight ratio to be: calcium chloride: germanium=15-30: 1, temperature is controlled at 70-90 ℃, the reaction times is 1-2 hour, obtains the gallium slag of high enrichment after filtration;
(5) heavy germanium technique: after heavy gallium, liquid adds the hydrochloric acid of 1-2mol/L to regulate pH=5.0-7.0, and temperature is controlled at 80-90 ℃, and sedimentation time is 2-3 hour, then adds flocculation agent 1 ‰ standing 2-7 hour, filters the germanium slag that obtains high enrichment.
The metallurgical slag of the germanic gallium of described complexity or the main component of ore are: leaded 5%-20%, and cupric 2%-15%, bismuth-containing 3%-20%, germanic 0.1%-10%, containing gallium 0.1%-10%.
Described flocculation agent is specially polyacrylamide.
The present invention has following advantage:
(1) the inventive method adaptability to raw material is very wide, the applicable metallurgical slag from the high germanic gallium of various complexity and ore, through High Temperature High Pressure, leads under oxygen condition with sodium hydroxide selective extraction germanium, gallium; Disposable selectivity leaching and germanium gallium leaching yield are respectively up to more than 98% and 99%;
(2) during the present invention creatively is provided with and impurity removal process, make impurity in leach liquor particularly lead removed, for further precipitation separation obtains high enrichment gallium slag and high enriched germanium slag is made preparation, and be more conducive to improve the grade of gallium slag and germanium slag;
(3) produce non-environmental-pollution, water system recycles, and without solid waste, selectivity leaches slag charge after the germanium gallium can enter the valuable metals such as lead wherein of pyrogenic process system recoveries, copper, bismuth.
The accompanying drawing explanation
Accompanying drawing is in conjunction with concrete process implementing mode, detailed explanation the technique trend.
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
Material component: lead: 7.82%, copper: 5.18%, bismuth: 13.54%, germanium: 2.64%, gallium: 3.09%.
This material embodiment adopts Production Flow Chart as Fig. 1, through being milled to 300 orders, get the 500g material at naoh concentration 110g/L, in the autoclave of 5L use for laboratory, liquid-solid volume mass compares 5:1, pressure controls 1.0 MPa, temperature is at 150 ℃, pass into the 4h of lower reaction times of condition of oxygen, having reacted rear cooling filters, extract reaction solution the sulfuric acid that slowly adds 3mol/L and adjust pH=13, after stirring 0.5h, filtration obtains enriched germanium gallium liquid, get enriched germanium gallium liquid and add the calcium chloride weight ratio: calcium chloride: germanium=20:1, temperature is controlled at 80 ℃, reaction times is 1 hour, obtain the gallium slag of high enrichment after filtration, after getting heavy gallium, liquid adds the hydrochloric acid of 1.5mol/L to regulate pH=6.0, temperature is controlled at 85 ℃, sedimentation time is 2 hours, then add the flocculation agent thousandth also standing 4 hours, filtration obtains the germanium slag of high enrichment.Obtain respectively lead bronze bismuth slag, enrichment gallium slag, the enriched germanium slag, its elemental composition and direct yield are as following table 1.(slag specimen is all dry weight.）
Table 1
| Title | Weight | Plumbous % | Copper % | Bismuth % | Germanium % | Gallium % | Direct yield % |
| Lead bronze bismuth slag | 457.1g | 8.45 | 5.61 | 14.7 | 0.0137 | 0.0022 | ? |
| The gallium slag | 34.75g | ? | ? | ? | ? | 44.18 | Gallium direct yield: 99.37 |
| The germanium slag | 42.69g | ? | ? | ? | 30.33 | ? | Germanium direct yield: 98.09 |
Embodiment 2
Material component: lead: 16.39%, copper: 9.83%, bismuth: 16.27%, germanium: 3.07%, gallium: 4.94%.
This material embodiment adopts Production Flow Chart as Fig. 1, through being milled to 300 orders, get the 500g material at naoh concentration 130g/L, in the autoclave of 5L use for laboratory, liquid-solid volume mass compares 6:1, pressure controls 1.2 MPa, temperature is at 170 ℃, pass into the 5h of lower reaction times of condition of oxygen, having reacted rear cooling filters, extract reaction solution the sulfuric acid that slowly adds 1.5mol/L and adjust pH=14, after stirring 0.5h, filtration obtains enriched germanium gallium liquid, get enriched germanium gallium liquid and add the calcium chloride weight ratio: calcium chloride: germanium equals 25:1, temperature is controlled at 90 ℃, reaction times is 1 hour, obtain the gallium slag of high enrichment after filtration, after getting heavy gallium, liquid adds the hydrochloric acid of 1.2mol/L to regulate pH=5.5, temperature is controlled at 90 ℃, sedimentation time is 2 hours, then add the flocculation agent thousandth also standing 5 hours, filtration obtains the germanium slag of high enrichment.Obtain respectively lead bronze bismuth slag, enrichment gallium slag, the enriched germanium slag, its elemental composition and direct yield are as following table 2.(slag specimen is all dry weight.）
Table 2
| Title | Weight | Plumbous % | Copper % | Bismuth % | Germanium % | Gallium % | Direct yield % |
| Lead bronze bismuth slag | 441.7g | 18.3 | 10.9 | 18.1 | 0.011 | 0.0032 | ? |
| The gallium slag | 41.59g | ? | ? | ? | ? | 59.12 | Gallium direct yield: 99.54 |
| The germanium slag | 57.47g | ? | ? | ? | 26.28 | ? | Germanium direct yield: 98.36 |
Claims (3)
1. the metallurgical slag from the germanic gallium of complexity or ore, selectivity leaches the method for germanium gallium, it is characterized in that: make the metallurgical slag of complicated germanic gallium or ore selectivity under the logical oxonium base condition of High Temperature High Pressure leach germanium, gallium, after overregulating the removal of impurities of pH value, successively with the heavy gallium of calcium chloride, the heavy germanium of neutralization, obtain respectively high enrichment gallium slag and high enriched germanium slag; Make germanium, gallium obtain selective recovery;
Technology condition of the present invention is as follows:
(1) ore grinding requires: raw material ball is milled to below granularity 300 orders;
(2) selectivity leaches: after getting ball milling, raw material is contained in the autoclave of use for laboratory, adds sodium hydroxide; Liquid-solid volume mass is than being 5-8:1, and the concentration that selectivity leaches agent sodium hydroxide is 100-150 g/L, and pressure is at 0.8-1.6MPa, and temperature is controlled at 130-180 ℃, in the situation that pass into the oxygen reaction times, is 3-6 hour; Separate the slag charge and the selective leaching fluid that obtain after selectivity leaches the germanium gallium; Selectivity leaches slag charge after the germanium gallium can enter the valuable metals such as lead wherein of pyrogenic process system recoveries, copper, bismuth;
(3) in and impurity removal process: in the selective leaching fluid, add the sulfuric acid of 1-3mol/L to adjust pH=13-14, filter after removal of impurities, the filter residue circulation is back to selective leaching and goes out operation;
(4) heavy gallium technique: in and after removal of impurities liquid add calcium chloride to sink gallium, calcium chloride adds weight ratio to be: calcium chloride: germanium=15-30: 1, temperature is controlled at 70-90 ℃, the reaction times is 1-2 hour, obtains the gallium slag of high enrichment after filtration;
(5) heavy germanium technique: after heavy gallium, liquid adds the hydrochloric acid of 1-2mol/L to regulate pH=5.0-7.0, and temperature is controlled at 80-90 ℃, and sedimentation time is 2-3 hour, then adds flocculation agent 1 ‰ standing 2-7 hour, filters the germanium slag that obtains high enrichment.
2. the metallurgical slag from the germanic gallium of complexity according to claim 1 or ore, selectivity leaches the method for germanium gallium, it is characterized in that: the metallurgical slag of the germanic gallium of described complexity or the main component of ore are: leaded 5%-20%, cupric 2%-15%, bismuth-containing 3%-20%, germanic 0.1%-10%, containing gallium 0.1%-10%.
3. the metallurgical slag from the germanic gallium of complexity according to claim 1 or ore, selectivity leaches the method for germanium gallium, and it is characterized in that: described flocculation agent is specially polyacrylamide.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108300876A (en) * | 2018-01-31 | 2018-07-20 | 广东省稀有金属研究所 | A method of leaching gallium and germanium from zinc replacement slag |
| CN109182787A (en) * | 2018-11-01 | 2019-01-11 | 中南大学 | A method of improving germanium, gallium leaching rate in germanic, gallium material |
| CN110922006A (en) * | 2019-12-18 | 2020-03-27 | 云南驰宏国际锗业有限公司 | Germanium mud pretreatment method |
| CN110938754A (en) * | 2018-09-21 | 2020-03-31 | 日立金属株式会社 | Gallium recovery method |
| CN111440955A (en) * | 2020-05-15 | 2020-07-24 | 广东先导稀材股份有限公司 | A method for extracting gallium from gallium-containing smelting slag |
| CN111647760A (en) * | 2020-06-16 | 2020-09-11 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN113430399A (en) * | 2021-06-29 | 2021-09-24 | 红河学院 | Method for recovering germanium and floating leached residues to co-produce high-quality coal in pressurized oxygen germanium leaching coal mine |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300876A (en) * | 2018-01-31 | 2018-07-20 | 广东省稀有金属研究所 | A method of leaching gallium and germanium from zinc replacement slag |
| CN110938754A (en) * | 2018-09-21 | 2020-03-31 | 日立金属株式会社 | Gallium recovery method |
| CN109182787A (en) * | 2018-11-01 | 2019-01-11 | 中南大学 | A method of improving germanium, gallium leaching rate in germanic, gallium material |
| CN109182787B (en) * | 2018-11-01 | 2020-07-31 | 中南大学 | Method for improving leaching rate of germanium and gallium in material containing germanium and gallium |
| CN110922006A (en) * | 2019-12-18 | 2020-03-27 | 云南驰宏国际锗业有限公司 | Germanium mud pretreatment method |
| CN111440955A (en) * | 2020-05-15 | 2020-07-24 | 广东先导稀材股份有限公司 | A method for extracting gallium from gallium-containing smelting slag |
| CN111647760A (en) * | 2020-06-16 | 2020-09-11 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN111647760B (en) * | 2020-06-16 | 2021-03-23 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN113430399A (en) * | 2021-06-29 | 2021-09-24 | 红河学院 | Method for recovering germanium and floating leached residues to co-produce high-quality coal in pressurized oxygen germanium leaching coal mine |
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