CN102787242B - Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process - Google Patents
Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process Download PDFInfo
- Publication number
- CN102787242B CN102787242B CN2012103060791A CN201210306079A CN102787242B CN 102787242 B CN102787242 B CN 102787242B CN 2012103060791 A CN2012103060791 A CN 2012103060791A CN 201210306079 A CN201210306079 A CN 201210306079A CN 102787242 B CN102787242 B CN 102787242B
- Authority
- CN
- China
- Prior art keywords
- germanium
- zinc
- leaching
- indium
- germanic
- 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
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 47
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011701 zinc Substances 0.000 title claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000003723 Smelting Methods 0.000 title claims description 5
- 238000002386 leaching Methods 0.000 claims abstract description 49
- 239000002893 slag Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- SAZXSKLZZOUTCH-UHFFFAOYSA-N germanium indium Chemical compound [Ge].[In] SAZXSKLZZOUTCH-UHFFFAOYSA-N 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 3
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RBFDCQDDCJFGIK-UHFFFAOYSA-N arsenic germanium Chemical compound [Ge].[As] RBFDCQDDCJFGIK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- -1 arsenic germanium arsenic Chemical compound 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- CRJWFQWLUGZJMK-UHFFFAOYSA-N germanium;phosphane Chemical compound P.[Ge] CRJWFQWLUGZJMK-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
Images
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering germanium and indium from the germanium-containing material, comprising the following steps: (1) neutrally leaching a part of zinc; (2) preoxidizing; and (3) oxidizing and leaching germanium and indium. Due to the adoption of the steps (1), (2) and (3), the separation of the germanium from the zinc and the separation of the germanium from the arsenic and the recovery of the germanium in the germanium-containing material are realized, and the germanium in the germanium-containing material is recovered. The method has the advantages of high recovery rate of germanium, short process flow and high leaching rate of germanium, is environmentally friendly, is easy and safe to operate, is suitable for industrial application, can replace the existing the process of leaching germanium by oxidizing by using chlorine and can be used for effectively recovering the germanium in the germanium-containing vacuum furnace slag. The method realizes the separation of the germanium from the zinc and the separation of the germanium from the arsenic and the recovery of the germanium in the germanium-containing material.
Description
Technical field
The present invention relates to reclaim in germanium-containing material in lead-zinc smelting technique the method for germanium and indium.
Background technology
In the plumbous zinc technology process of blast furnace smelting, can produce the hard zinc of the dissipated metal such as germanic indium when the refining of zinc.In the enriching and recovering hard zinc, the traditional method of rare precious metal is to adopt the muffle electric furnace to process hard zinc to reclaim germanium, its advantage is that technical process is short, equipment is simple, but also exist the germanium rate of recovery low, total yield only has 20% left and right, other valuable metal is as difficult recovery such as indiums, and electric furnace rushes the uneasy congruent shortcoming of big gun.Shaoguan Smelter is through experimental study in a few years, successfully developed the new technology that vacuum oven is processed hard zinc.Hard zinc obtains crude zinc after vacuum distilling and rich germanium slag direct yield is respectively 90% and 96.14%, but germanium indium enrichment more than 10 doubly.This germanium slag adopts unique calcium salt chlorinated distillation art breading, usings the calcium chloride solution of high density as leaching distillation system, and chlorine is made oxygenant, reduces distillment acidity, suppresses steaming of arsenic germanium arsenic is separated.Although germanic Zinc Vacuum Furnace Slag is through pre-oxidation treatment, the plumbous zinc from its XRD figure raw material still has part to exist with simple substance, and the more plumbous zinc of the standard oxidationreduction potential of germanium is high, if do not add oxygenant will be difficult to germanium is leached at leaching process.Industrial when germanium-containing material is carried out to Oxidation Leaching the oxygenant of employing mainly contain MnO
2, H
2o
2and Cl
2, adopt MnO
2make oxygenant and can bring impurity to system, will make other valuable element processes of follow-up comprehensive recovery complicated and increased the burden of removal of impurities; Adopt H
2o
2can not bring new impurity, H to system although make oxygenant
2o
2can generate H after redox reaction
2o makes liquid-solid ratio increase, simultaneously H
2o
2can decompose utilization ratio and reduce, further increased liquid-solid ratio under higher temperatures, the liquid volume of having aggravated system expands; Adopt gas Cl
2while making oxygenant, exist gas flow to be difficult to the problems such as control and operational safety.For the shortcoming of above various oxygenants, the present invention adopts a kind of solid oxidizing agent at HCl-CaCl
2-H
2germanium in the O system in the Oxidation Leaching germanium-containing material can address the above problem fully.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and provide a kind of processing method simple, germanium, indium, zinc recovery are high, germanium-arsenic good separating effect, operational safety, the environment amenable method that reclaims germanium and indium from germanium-containing material.
Technical scheme of the present invention is: the germanic hard zinc that zinc refining produces, and after processing, vacuum distilling obtains germanic Zinc Vacuum Furnace Slag, it is characterized in that, above-described germanic Zinc Vacuum Furnace Slag is that raw material extracts the germanium indium, comprises the following steps:
(1), leach acid adding in germanic Zinc Vacuum Furnace Slag is neutral, stir, control reaction end pH=4.2 ~ 5.2,70～80 ℃ of Leaching reaction temperature, obtain leached mud and leach liquor;
(2), the leached mud of (1) step gained is dried, is ground after, be placed in air and carry out preoxidized roast under 300～500 ℃;
(3), by (2) step gained oxidizing roasting slag, at HCl-CaCl
2-H
2oxidation Leaching in the O solution system, wherein HCl concentration is 4.5～5.5mol/L, CaCl
2concentration is 1.5～2.5mol/L, oxygenant is solid calcium hypochlorite, the oxygenant add-on is by 1～3 times of the required theoretical oxidant amount of germanium oxidation in material, extraction temperature is: 55～95 ℃, liquid-solid ratio is 3: 1～7: 1 L/Kg, and Oxidation Leaching completes by solid-liquid separation and obtains germanic indium leach liquor.
In described (1) step, described acid is 65～70g/LH
2sO
4, a kind of in 45～50g/LHCl.
Leaching reaction time 1～2h in described (1) step.
In described (2) step, roasting time is 1～5h, and every 20～40min stirs once.
In described (3) step, HCl concentration is 5mol/L, CaCl
2concentration is 2mol/L.
In described (3) step, extraction time is 20min～80min.
The concrete step of the present invention is:
The first step: leach separate part zinc
To the leaching agent that adds proper concn in germanic Zinc Vacuum Furnace Slag, stir, control 70～80 ℃ of solution temperatures, reaction times 1～2h, control reaction end pH=4.2 ~ 5.2, obtains leached mud and leach liquor.
Second step: pre-oxidation treatment
After the leached mud of the first step gained is dried, ground, be placed in air and carry out oxidizing roasting under 300～500 ℃, extraction time is 1～5h, and every 30min stirs once.
The 3rd step: Oxidation Leaching
By second step gained oxidizing roasting slag, at HCl-CaCl
2-H
2oxidation Leaching in the O solution system, oxygenant is solid calcium hypochlorite, add-on (quality/Kg) is by 1～3 times of the required theoretical oxidant amount of the whole oxidations of germanium in material, in system, concentration of hydrochloric acid is 5mol/L, calcium chloride concentration is 2mol/L, and liquid-solid volume (liter/L) quality (kilogram/Kg) is than being 3: 1～7: 1, and stirring velocity is preferably 300～450rpm, extraction time is 20min～80min, obtains germanic and indium leach liquor.
The present invention, owing to adopting above-mentioned processing step, in the neutral leaching process of the first step, utilizes Zn
2+be 4.5～5.0 o'clock in the pH value, can be dissolved in solution, and other metal, as insoluble still the staying in slag such as germanium, indium, realize that germanium indium-part zinc separates, and makes the germanium indium be able to enrichment, part zinc is entered neutral leach liquor by leaching and is reclaimed, and production cost is low, easily realizes suitability for industrialized production, in the second step pre-oxidation treatment, because the master metal in Zinc Vacuum Furnace Slag will exist with simple substance or intermetallic compound, reclaimed part zinc through neutral leaching of the first step, but still contain more metal simple-substance and intermetallic compound in neutral leaching residue, in order in the 3rd step Oxidation Leaching, thoroughly to leach germanium phosphide element wherein, the leached mud that the present invention generates the first step has carried out the oxidizing roasting processing, make metal simple-substance major part wherein be oxidized to metal oxide, thereby the leaching that is conducive to the valuable metals such as germanium indium in the 3rd step Oxidation Leaching improves germanium, the leaching yield of indium.In the 3rd step Oxidation Leaching process at HCl-CaCl
2-H
2be conducive to the leaching of germanium in the O solution system and reduce and leach acidity, this is conducive to reduce acid consumption and environmental protection, with the solid oxidizing agent Losantin, replace chlorine used in existing industrialization to make oxygenant simultaneously, arsenic is oxidized to high valence state, it can well be separated with germanium when distillation, improved the accuracy of oxygenant add-on and the security of operation.
In sum, processing method of the present invention is simple, and germanium, indium leaching yield are high, germanium-arsenic separator well, environmental friendliness, and the alternative technique of making oxygenant Oxidation Leaching germanium in hydrochloric acid system of chlorine that has now, be suitable for industrial applications.
The accompanying drawing explanation
Accompanying drawing 1 is schema of the present invention.
Embodiment
Embodiment 1:
1, take the germanic indium Zinc Vacuum Furnace Slag of certain factory's output is raw material, and its chemical composition is: Ge2.04%, In2.04%, Pb42.9%, Zn25.1%, Cu1.7%, Fe3.5%, Ag0.14%, As4.9%.
2, the H that above-mentioned 20g Zinc Vacuum Furnace Slag is slowly added to 120mL65g/L
2sO
4solution, constantly stir, and is warming up to 70 ℃, continues agitation leach 1h, and recording pH is 5 ~ 5.2.Soak filtration after rolling and soak supernatant liquor 142mL in obtaining, its chemical composition is (gL
-1): Ge0, In0, Zn15.74, Fe2.3.The leaching yield of zinc is 44.52%.
3, after neutral leaching residue obtained above is dried, ground, be placed in electric furnace at 300 ℃ of lower oxidizing roasting 5h.It naturally cools to normal temperature the complete relief of roasting, for Oxidation Leaching.
4, oxidizing roasting slag obtained above is moved in the 300mL beaker, toward the HCl-CaCl that wherein adds 100mL to configure
2-H
2o solution is made leaching agent (HCl:5mol/L, CaCl
2: 2mol/L), be warming up to 95 ℃, agitation leach 60min, add the oxygenant of 2 times of theoretical aequums continuously in leaching process, carry out liquid-solid separation after having leached, leached mud 9.15g, and its composition (%) is: Ge0.04, Pb38.8, Zn0.22, In0.07.Obtain leach liquor 245mL, containing Ge1.54g/L, In1.59g/L, Zn11.30g/L, Pb7.25g/L, As2.78g/L.The leaching yield of germanium indium is respectively 92.53% and 95.7%.
Embodiment 2:
1, take the germanic indium Zinc Vacuum Furnace Slag of certain factory's output is raw material, and its composition is: Ge2.06%, In1.54%, Pb37.85%, Zn25.81%, Fe7.9%, Ag0.10%, As4.18%.
2, the HCl solution that above-mentioned 20g Zinc Vacuum Furnace Slag is slowly added to 100ml49g/L, constantly stir, and is warming up to 80 ℃, continues agitation leach 2h, and recording pH is 4.2 ~ 4.5.Soak filtration after rolling and soak supernatant liquor 116mL in obtaining, its chemical composition is (gL
-1): Ge0, In0, Zn23.08, Fe1.9.The leaching yield of zinc is 51.87%.
3, after neutral leaching residue obtained above is dried, ground, be placed in electric furnace at 400 ℃ of lower oxidizing roasting 3h.It naturally cools to normal temperature the complete relief of roasting, for Oxidation Leaching.
4, oxidizing roasting slag obtained above is moved in the 300mL beaker, toward the HCl-CaCl that wherein adds 100mL to configure
2-H
2o solution is made leaching agent (HCl:5mol/L, CaCl
2: 2mol/L), be warming up to 55 ℃, agitation leach 60min, add the oxygenant of 2 times of theoretical aequums continuously in leaching process, carry out liquid-solid separation after having leached, leached mud 9.85g, and its composition (%) is: Ge0.05, Pb35.2, Zn0.3, In0.077.Obtain leach liquor 240mL, containing Ge1.60g/L, In1.19g/L, Zn10.2g/L, Pb7.66g/L, As2.21g/L.The leaching yield of germanium indium is respectively 93.20% and 92.73%.
Embodiment 3:
1, take the germanic indium Zinc Vacuum Furnace Slag of certain factory's output is raw material, and its composition is: Ge1.93%, In1.20%, Pb42.18%, Zn20.49%, Fe6.00%, Ag0.18%, As4.53%.
2, the H that above-mentioned 20g Zinc Vacuum Furnace Slag is slowly added to 120mL65g/L
2sO
4solution, constantly stir, and is warming up to 80 ℃, continues agitation leach 60min, and recording pH is 4.8 ~ 5.0.Soak filtration after rolling and soak supernatant liquor 136mL in obtaining, its chemical composition is (gL
-1): Ge0, In0, Zn16.05, Fe1.51.The leaching yield of zinc is 53.27%.
3, after neutral leaching residue obtained above is dried, ground, be placed in electric furnace at 500 ℃ of lower oxidizing roasting 1h.It naturally cools to normal temperature the complete relief of roasting, for Oxidation Leaching.
4, oxidizing roasting slag obtained above is moved in the 300mL beaker, toward the HCl-CaCl that wherein adds 100mL to configure
2-H
2o solution is made leaching agent (HCl:5mol/L, CaCl
2: 2mol/L), be warming up to 95 ℃, agitation leach 60min, add the oxygenant of 2 times of theoretical aequums continuously in leaching process, carry out liquid-solid separation after having leached, leached mud 9.35g, and its composition (%) is: Ge0.05, Pb40.0, Zn0.46, In0.077.Obtain leach liquor 215mL, containing Ge1.70g/L, In1.08g/L, Zn8.91g/L, Pb3.47g/L, As3.18g/L.The leaching yield of germanium indium is respectively 94.69% and 96.75%.
Claims (6)
1. reclaim the method for germanium indium in the germanium-containing material produced from lead-zinc smelting technique, the germanic hard zinc that zinc refining produces obtains germanic Zinc Vacuum Furnace Slag after vacuum distilling is processed, and it is characterized in that, take described germanic Zinc Vacuum Furnace Slag as raw material extracts the germanium indium, comprise the following steps:
(1), leach acid adding in germanic Zinc Vacuum Furnace Slag is neutral, stir, control reaction end pH=4.2～5.2,70～80 ℃ of Leaching reaction temperature, obtain leached mud and leach liquor;
(2), the leached mud of (1) step gained is dried, is ground after, be placed in air and carry out preoxidized roast under 300～500 ℃;
(3), by (2) step gained oxidizing roasting slag, at HCl-CaCl
2-H
2oxidation Leaching in the O solution system, wherein HCl concentration is 4.5～5.5mol/L, CaCl
2concentration is 1.5～2.5mol/L, oxygenant is solid calcium hypochlorite, the oxygenant add-on is by 1～3 times of the required theoretical oxidant amount of germanium oxidation in material, extraction temperature is: 55～95 ℃, liquid-solid ratio is 3: 1～7: 1L/kg, Oxidation Leaching completes by solid-liquid separation and obtains germanic indium leach liquor.
2. method according to claim 1, it is characterized in that: in described (1) step, described acid is 65～70g/L H
2sO
4, a kind of in 45～50g/L HCl.
3. method according to claim 1 and 2, is characterized in that: Leaching reaction time 1～2h in described (1) step.
4. method according to claim 1, it is characterized in that: in described (2) step, roasting time is 1～5h, and every 20～40min stirs once.
5. method according to claim 1, it is characterized in that: in described (3) step, HCl concentration is 5mol/L, CaCl
2concentration is 2mol/L.
6. method according to claim 1, it is characterized in that: in described (3) step, extraction time is 20min～80min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103060791A CN102787242B (en) | 2012-08-27 | 2012-08-27 | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103060791A CN102787242B (en) | 2012-08-27 | 2012-08-27 | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102787242A CN102787242A (en) | 2012-11-21 |
| CN102787242B true CN102787242B (en) | 2013-12-11 |
Family
ID=47152827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103060791A Expired - Fee Related CN102787242B (en) | 2012-08-27 | 2012-08-27 | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102787242B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105369038B (en) * | 2015-11-05 | 2017-09-12 | 昆明理工大学 | A kind of hybrid oxidant and its method using hybrid oxidant Ti recovery in phase analysis from hard zinc |
| CN108007816A (en) * | 2017-12-18 | 2018-05-08 | 清远先导材料有限公司 | The detection method of active metal simple substance in a kind of hard zinc |
| CN115404363A (en) * | 2022-08-29 | 2022-11-29 | 云南驰宏国际锗业有限公司 | Method for recovering germanium from germanium mud by utilizing germanium concentrate distillation waste hydrochloric acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525693A (en) * | 2009-04-17 | 2009-09-09 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium |
| CN101660054A (en) * | 2009-07-15 | 2010-03-03 | 中国科学院青海盐湖研究所 | Method for extracting metal indium from waste residues generated from lead and zinc smelting |
| CN102337391A (en) * | 2011-11-07 | 2012-02-01 | 云南东昌金属加工有限公司 | Process method for recovering indium, germanium and other valuable metals from indium concentrate |
| CN102392144A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Process method for recovering indium and germanium from germanium concentrate |
| CN102392138A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
| CN102586608A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing sponge indium with indium-rich slag produced in lead-zinc smelting process |
-
2012
- 2012-08-27 CN CN2012103060791A patent/CN102787242B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525693A (en) * | 2009-04-17 | 2009-09-09 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium |
| CN101660054A (en) * | 2009-07-15 | 2010-03-03 | 中国科学院青海盐湖研究所 | Method for extracting metal indium from waste residues generated from lead and zinc smelting |
| CN102586608A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing sponge indium with indium-rich slag produced in lead-zinc smelting process |
| CN102337391A (en) * | 2011-11-07 | 2012-02-01 | 云南东昌金属加工有限公司 | Process method for recovering indium, germanium and other valuable metals from indium concentrate |
| CN102392144A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Process method for recovering indium and germanium from germanium concentrate |
| CN102392138A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
Non-Patent Citations (2)
| Title |
|---|
| 李琛.韶冶真空炉富锗渣回收锗研究.《矿冶工程》.2003,第23卷(第6期),50-52. |
| 韶冶真空炉富锗渣回收锗研究;李琛;《矿冶工程》;20031231;第23卷(第6期);50-52 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102787242A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102409165B (en) | Gradient arsenic removing method for high-arsenic metallurgical wastes | |
| CN101818250B (en) | Method for processing cobalt-copper-iron alloy | |
| CN104245973A (en) | Process for extraction of rare earth elements | |
| CN102766765A (en) | Zinc oxide powder recycling method | |
| CN102443701A (en) | Clean metallurgical comprehensive utilization method of jarosite slag | |
| CN103757420A (en) | Method for recovering lead and silver from zinc leaching residues | |
| CN104278165A (en) | Method for recovering thorium, uranium and rare earth from monazite smelting acid-insoluble slag | |
| CN103667720A (en) | Method for recovering zinc, indium, iron, and lead from high-iron zinc oxide mixture smelted with zinc | |
| CN106048265B (en) | A kind of extracting method of bastnaesite rare earth elements | |
| CN104060106B (en) | From bismuth-containing solution, extract bismuth with solvent extration and prepare the method for bismuth oxide | |
| CN102787242B (en) | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process | |
| CN107447107B (en) | A kind of method that wealth and rank antimony control current potential is separated and recovered from base metal | |
| CN103173624B (en) | Method for recovery germanium from germanium-containing flue dust | |
| CN104726717A (en) | Method for recovering cobalt from inverse antimony purified cobalt residue | |
| CN104388711A (en) | Method for recovering rare earth by leaching rare earth oxide molten slag | |
| CN103160688A (en) | Method for preparing germanium concentrate from germanium-containing leachate through utilizing zinc powder replacement method | |
| CN106337134A (en) | Technique for recovering indium from indium-containing soot | |
| CN101525696B (en) | Method for leaching indium from leaching residue containing indium | |
| CN106222454A (en) | A kind of from the method containing indium flue dust recovery indium | |
| CN103509948A (en) | Method for enriching germanium from zinc hydrometallurgy leaching solution | |
| CN109280772B (en) | Method for leaching and gradient separating enriched antimony, bismuth and arsenic from copper anode slime | |
| CN113186399B (en) | Method for extracting tantalum and niobium | |
| CN102787243A (en) | Method for recycling germanium from zinc distillation residues | |
| CN104109762B (en) | Environment-friendly nontoxic gold extractant, and preparation method and gold extraction method thereof | |
| CN101817563A (en) | Process for preparing high-purity ferrous sulfate by adopting pyrite smelting slag |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131211 |