CN103468977B - The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium - Google Patents
The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium Download PDFInfo
- Publication number
- CN103468977B CN103468977B CN201310468825.1A CN201310468825A CN103468977B CN 103468977 B CN103468977 B CN 103468977B CN 201310468825 A CN201310468825 A CN 201310468825A CN 103468977 B CN103468977 B CN 103468977B
- Authority
- CN
- China
- Prior art keywords
- gallium
- germanium
- slag
- germanic
- ore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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 present invention relates to the method for Selectively leaching germanium gallium a kind of metallurgical slag from the germanic gallium of complexity or ore, belong to non-ferrous metal hydrometallurgy and secondary resource reclaim field.The present invention be under High Temperature High Pressure leads to oxygen alkaline condition from the metallurgical slag of the germanic gallium of complexity or ore Selectively leaching germanium, gallium, after adjust ph removal of impurities, sink gallium with calcium chloride successively, the heavy germanium of neutralization, make germanium, gallium obtains selective recovery.The present invention can realize the germanium rate of recovery up to 98%, and the gallium rate of recovery is up to 99%; Reach the effect that highly selective leaches germanium gallium, and the rate of recovery is high.Adaptability to raw materials of the present invention is strong, is not only applicable to the pyrogenic process of the germanic gallium of various complexity, hydrometallurgy slag, can also be applicable to the ore of high germanic gallium.
Description
Technical field
The present invention relates to the method for Selectively leaching germanium gallium a kind of metallurgical slag from the germanic gallium of complexity or ore, belong to non-ferrous metal hydrometallurgy and secondary resource reclaim field.
Technical background
The content of germanium in the earth's crust is 7/1000000ths, and germanium disperses very much, and the germanium ore deposit of almost relatively not concentrating, therefore, is called " dissipated metal " by people.There are argyrodite (germanic 5-7%), germanite (germanic 10%) in the germanium ore deposit found, sulphur copper iron germanium ore deposit (germanic 7%).Germanium gallium is all commonly used among semi-conductor, and being used for manufacturing transistor is important semiconductor material, and for today that electron trade is growing, germanium gallium is more and more applied in semicon industry.Therefore the selective recovery of germanium gallium is more and more important.At present, germanium gallium synthetical recovery is still recovered as master with normal wet, and its operating procedure is complicated, production cycle is long, and each valuable metal loss, does not possess highly selective, gallium germanium major part is all 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, extraction equipment utilization ratio is low.Therefore the method for highly selective Ti recovery gallium is germanium gallium synthetical recovery field important topic.
On October 10th, 2012 Chinese invention patent publication No. 102719679A, " a kind of from putting forward germanium residue the method reclaiming gallium and germanium " of disclosing the universal invention such as female of Yunnan Province xinyuan Ge industry Co., Ltd propose be separated by the fractionation by distillation of roasting, leaching, germanium, slag liquid, extract, strip, hydrolytic precipitation and gallium germanium concentrate.This patent of invention is that gallium in the residue of the germanic coal flue dust that obtains of pyrometallurgical smelting after carrying out chlorination of hydrochloric acid fractionation by distillation germanium and germanium carry out effective recycling, this patent of invention has certain limitation to starting material, and adopting distillation, extraction, reextraction system, technique practicality is not strong.The recovery of highly selective germanium gallium is not possessed yet.
Summary of the invention
The object of the invention is the method providing Selectively leaching germanium gallium a kind of metallurgical slag from the germanic gallium of complexity or ore, and can realize the germanium rate of recovery up to 98%, the gallium rate of recovery is up to gallium 99%; Reach the effect that highly selective leaches germanium gallium, and the rate of recovery is high.Adaptability to raw materials of the present invention is strong, is not only applicable to the pyrogenic process of the germanic gallium of various complexity, hydrometallurgy slag, 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 method of Selectively leaching germanium gallium metallurgical slag from the germanic gallium of complexity or ore, make metallurgical slag or ore Selectively leaching germanium, gallium under High Temperature High Pressure leads to oxygen alkaline condition of complicated germanic gallium, after adjust ph removal of impurities, gallium is sunk successively with calcium chloride, the heavy germanium of neutralization, obtains high enrichment gallium slag and high enriched germanium slag respectively; Make germanium, gallium obtains selective recovery;
Technology condition of the present invention is as follows:
(1) ore grinding requires: raw material ball is milled to below granularity 300 order;
(2) Selectively leaching: 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, unit L/kg; The concentration of Selectively leaching agent sodium hydroxide is 100-150 g/L, and pressure is at 0.8-1.6MPa, and temperature controls at 130-180 DEG C, and when passing into oxygen, the reaction times is 3-6 hour; Be separated the slag charge after obtaining Selectively leaching germanium gallium and selective leaching fluid; Slag charge after Selectively leaching germanium gallium can enter the valuable metals such as pyrogenic process system recoveries lead wherein, copper, bismuth;
(3), in and impurity removal process: the sulfuric acid adding 1-3mol/L in selective leaching fluid adjusts pH=13-14, filters after removal of impurities, filter residue circulation is back to Selectively leaching operation;
(4) heavy gallium technique: in and after removal of impurities liquid add calcium chloride and sink gallium, calcium chloride adds weight ratio and is: calcium chloride: germanium=15-30: 1, and temperature controls at 70-90 DEG C, and 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 adjustment pH=5.0-7.0 of 1-2mol/L, and temperature controls at 80-90 DEG C, and sedimentation time is 2-3 hour, then adds flocculation agent 1 ‰ and leaves standstill 2-7 hour, filtering the germanium slag obtaining high enrichment.
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%.
Described flocculation agent is specially polyacrylamide.
The present invention has following advantage:
(1) the inventive method adaptability to raw material is very wide, is suitable for and under High Temperature High Pressure leads to oxygen condition, uses sodium hydroxide selective extraction germanium, gallium from the metallurgical slag and ore of the high germanic gallium of various complexity; Disposable Selectively leaching and germanium gallium leaching yield are respectively up to more than 98% and 99%;
(2) during the present invention is creatively provided with and impurity removal process, make the impurity in leach liquor particularly lead removed, obtain high enrichment gallium slag for further precipitation separation and high enriched germanium slag makes preparation, and be more conducive to the grade improving gallium slag and germanium slag;
(3) produce non-environmental-pollution, water system recycles, and without solid waste, the slag charge after Selectively leaching germanium gallium can enter the valuable metals such as pyrogenic process system recoveries lead wherein, copper, bismuth.
Accompanying drawing explanation
Accompanying drawing is in conjunction with concrete process embodiment, specifically understands technique trend.
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
Material component: plumbous: 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 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 DEG C, pass into the condition lower reaction times 4h of oxygen, react rear cooling to filter, extract reaction solution the sulfuric acid slowly adding 3mol/L and adjust pH=13, filter after stirring 0.5h and obtain enriched germanium gallium liquid, get enriched germanium gallium liquid and add calcium chloride weight ratio: calcium chloride: germanium=20:1, temperature controls at 80 DEG C, reaction times is 1 hour, the gallium slag of high enrichment is obtained after filtration, after getting heavy gallium, liquid adds the hydrochloric acid adjustment pH=6.0 of 1.5mol/L, temperature controls at 85 DEG C, sedimentation time is 2 hours, then add flocculation agent thousandth and leave standstill 4 hours, filter the germanium slag obtaining high enrichment.Obtain lead bronze bismuth slag respectively, enrichment gallium slag, 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 | |
| Gallium slag | 34.75g | 44.18 | Gallium direct yield: 99.37 | ||||
| Germanium slag | 42.69g | 30.33 | Germanium direct yield: 98.09 |
Embodiment 2
Material component: plumbous: 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 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 DEG C, pass into the condition lower reaction times 5h of oxygen, react rear cooling to filter, extract reaction solution the sulfuric acid slowly adding 1.5mol/L and adjust pH=14, filter after stirring 0.5h and obtain enriched germanium gallium liquid, get enriched germanium gallium liquid and add calcium chloride weight ratio: calcium chloride: germanium equals 25:1, temperature controls at 90 DEG C, reaction times is 1 hour, the gallium slag of high enrichment is obtained after filtration, after getting heavy gallium, liquid adds the hydrochloric acid adjustment pH=5.5 of 1.2mol/L, temperature controls at 90 DEG C, sedimentation time is 2 hours, then add flocculation agent thousandth and leave standstill 5 hours, filter the germanium slag obtaining high enrichment.Obtain lead bronze bismuth slag respectively, enrichment gallium slag, 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 | |
| Gallium slag | 41.59g | 59.12 | Gallium direct yield: 99.54 | ||||
| Germanium slag | 57.47g | 26.28 | Germanium direct yield: 98.36 |
Claims (3)
1. the method for Selectively leaching germanium gallium the metallurgical slag from the germanic gallium of complexity or ore, it is characterized in that: the metallurgical slag or ore Selectively leaching germanium, the gallium under High Temperature High Pressure leads to oxygen alkaline condition that make complicated germanic gallium, after adjust ph removal of impurities, gallium is sunk successively with calcium chloride, the heavy germanium of neutralization, obtains high enrichment gallium slag and high enriched germanium slag respectively; Make germanium, gallium obtains selective recovery;
Technology condition of the present invention is as follows:
(1) ore grinding requires: raw material ball is milled to below granularity 300 order;
(2) Selectively leaching: 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 of Selectively leaching agent sodium hydroxide is 100-150 g/L, and pressure is at 0.8-1.6MPa, and temperature controls at 130-180 DEG C, and when passing into oxygen, the reaction times is 3-6 hour; Be separated the slag charge after obtaining Selectively leaching germanium gallium and selective leaching fluid; Slag charge after Selectively leaching germanium gallium can enter pyrogenic process system recoveries lead wherein, copper, bismuth valuable metal;
(3), in and impurity removal process: the sulfuric acid adding 1-3mol/L in selective leaching fluid adjusts pH=13-14, filters after removal of impurities, filter residue circulation is back to Selectively leaching operation;
(4) heavy gallium technique: in and after removal of impurities liquid add calcium chloride and sink gallium, calcium chloride adds weight ratio and is: calcium chloride: germanium=15-30: 1, and temperature controls at 70-90 DEG C, and 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 adjustment pH=5.0-7.0 of 1-2mol/L, and temperature controls at 80-90 DEG C, and sedimentation time is 2-3 hour, then adds flocculation agent 1 ‰ and leaves standstill 2-7 hour, filtering the germanium slag obtaining high enrichment.
2. the method for Selectively leaching germanium gallium the metallurgical slag from the germanic gallium of complexity according to claim 1 or ore, 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 method for Selectively leaching germanium gallium the metallurgical slag from the germanic gallium of complexity according to claim 1 or ore, is characterized in that: described flocculation agent is specially polyacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310468825.1A CN103468977B (en) | 2013-10-10 | 2013-10-10 | The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310468825.1A CN103468977B (en) | 2013-10-10 | 2013-10-10 | The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103468977A CN103468977A (en) | 2013-12-25 |
| CN103468977B true CN103468977B (en) | 2015-08-19 |
Family
ID=49794015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310468825.1A Expired - Fee Related CN103468977B (en) | 2013-10-10 | 2013-10-10 | The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103468977B (en) |
Families Citing this family (7)
| 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 |
| 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 |
| CN111440955B (en) * | 2020-05-15 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for extracting gallium from gallium-containing smelting slag |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069524A (en) * | 1991-08-22 | 1993-03-03 | 沈阳冶炼厂 | A kind of method that from offscum containing germanium, reclaims germanium |
| CN101407864A (en) * | 2008-12-01 | 2009-04-15 | 云南蓝湾矿业有限公司 | Method for secondarily extracting gallium and germanium from fly ash |
| 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 |
| CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
| CN102560133A (en) * | 2012-02-29 | 2012-07-11 | 北京矿冶研究总院 | Method for extracting gallium and germanium from zinc smelting slag |
| CN102634659A (en) * | 2012-03-20 | 2012-08-15 | 临沧师范高等专科学校 | Process for recycling gallium from gallium and germanium contained concentrate |
-
2013
- 2013-10-10 CN CN201310468825.1A patent/CN103468977B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069524A (en) * | 1991-08-22 | 1993-03-03 | 沈阳冶炼厂 | A kind of method that from offscum containing germanium, reclaims germanium |
| 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 |
| CN101407864A (en) * | 2008-12-01 | 2009-04-15 | 云南蓝湾矿业有限公司 | Method for secondarily extracting gallium and germanium from fly ash |
| CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
| CN102560133A (en) * | 2012-02-29 | 2012-07-11 | 北京矿冶研究总院 | Method for extracting gallium and germanium from zinc smelting slag |
| CN102634659A (en) * | 2012-03-20 | 2012-08-15 | 临沧师范高等专科学校 | Process for recycling gallium from gallium and germanium contained concentrate |
Non-Patent Citations (1)
| Title |
|---|
| 从锌浸渣中回收镓和锗的研究及实践;蔡江松;《矿产保护与利用》;20021031;参见其第34-37页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103468977A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103468977B (en) | The method of Selectively leaching germanium gallium from the metallurgical slag or ore of complexity germanic gallium | |
| CN103526024B (en) | Novel clean environment-friendly comprehensive recovery process for high-indium high-iron zinc concentrate | |
| CN102851693B (en) | Technology for recovering production of electrolytic copper and zinc from smelting ash | |
| CN103540765B (en) | Zinc smelting technology | |
| CN102766765B (en) | Zinc oxide powder recycling method | |
| CN102051478B (en) | Wet process for treating lead copper matte | |
| CN102618719A (en) | Method for directly leaching zinc and recovering gallium, germanium and indium from zinc sulfide concentrate | |
| CN106435213B (en) | A method of the synthetical recovery zinc-nickel-cadmium from copper-cadmium slag | |
| CN105274348A (en) | Method for extracting rhenium from copper smelting flue gas wet dust collecting liquid | |
| CN103966421A (en) | Comprehensive recovery method of ferrous metallurgical solid wastes | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN106755996A (en) | A kind of lead copper matte synthetical recovery processing method | |
| CN104073650B (en) | One reclaims zinc technology from tin metallurgy electric furnace dust | |
| CN105567983A (en) | Soot treatment process in copper smelting process | |
| CN108950199A (en) | A method of it being used for the nickel and cobalt solution of synthesis of ternary presoma using the preparation of nickel sulfide cobalt ore | |
| CN103468959B (en) | Method for treating high-arsenic, high-selenium and high-tellurium anode mud through oxygen pressure | |
| CN102373336B (en) | Method for separating copper and silver from dross produced by producing copper from smelting lead | |
| CN102453807B (en) | Technology for processing black copper slag and producing electrodeposited copper through cyclone electrolysis technology | |
| CN112501452B (en) | Method for purifying zinc mineral material leaching solution | |
| CN105366728B (en) | A kind of method that iron vitriol slag prepares iron oxide red | |
| CN105385858B (en) | A kind of iron vitriol slag prepares iron oxide red and the method for reclaiming silver | |
| CN102560130A (en) | Selective leaching technology of copper and zinc in scrap copper smelting slag | |
| CN102925714A (en) | Method for selectively recycling gold and silver from copper anode slime | |
| CN107099673A (en) | A kind of wet high-effective reclaims the metallurgical slag processing method of valuable metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150819 Termination date: 20201010 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |