CN101525693B - Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium - Google Patents
Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium Download PDFInfo
- Publication number
- CN101525693B CN101525693B CN2009100388232A CN200910038823A CN101525693B CN 101525693 B CN101525693 B CN 101525693B CN 2009100388232 A CN2009100388232 A CN 2009100388232A CN 200910038823 A CN200910038823 A CN 200910038823A CN 101525693 B CN101525693 B CN 101525693B
- Authority
- CN
- China
- Prior art keywords
- indium
- germanium
- zinc
- arsenic
- lead
- 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.)
- Active
Links
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
Abstract
The invention relates to a method for the vulcanization, the reducing oxidation and the enrichment of a low-grade material containing arsenic, indium and germanium. The method comprises the following steps: compounding a certain amount of coal dust in a raw material containing indium, germanium, lead, zinc and arsenic as a reducer; meanwhile, adding elemental sulfur and a caking agent for briquetting by the weight ratio that the raw material containing the indium, the germanium, the lead, the zinc and the arsenic to lime to sulfur is equal to 100:20-40:5-10:2-4; making the material into a coalball or briquette shape, vulcanizing and volatilizing in a shaft furnace; controlling temperature to be below 1000 DEG C to 1200 DEG C and vulcanization volatilizes time to be from 1 hour to 3 hours under a certain oxidation reduction atmosphere, and the content of the lead and the zinc in slag to be less than 2 percent, and decreasing the content of the indium and the germanium to be 30 to 300 g/ton; leaching flue dust when a sulfur terminal has a pH value of 0.5 and replacing zinc powder for leaching liquid into indium-germanium concentrate ore. The method can take lower production cost to enrich valuable metals, such as indium, germanium, lead, zinc, silver and the like without drainage, the germanium, the indium and the zinc obtained in the flue dust can be leached by 95 percent when the pH value is 0.5, hydrogen arsenide can be separately treated, and the valuable metals of the lead, the zinc and the silver can be fully recycled.
Description
[technical field]
The invention belongs to the extraction and the beneficiation technologies field of coloured scattered metals indium germanium low-grade material, relate to and a kind of the arsenic that contains in the arsenic indium germanium low-grade material being separated, simultaneously valuable metals such as arsenic indium germanium are carried out enrichment, so that in subsequent technique, extract the sulfuration and the reducing oxidation and enrichment method that contain arsenic indium germanium low-grade material of valuable metal.
[background technology]
Title is explained: the formal name used at school of P204 is a di (isooctyl) phosphate, it is a kind of phosphorus type acidic extractant, this product is mainly used in the extracting and separating of rare metal in hydrometallurgy such as nickel, cobalt, rare earth, also can be used for industries such as medicine, printing and dyeing, petrochemical wastewater processing, also can make the starting material of wetting agent and tensio-active agent.
At present, the extraction process of low-grade scattered metals indium is directly to leach with sulfuric acid, and then with P204 extraction or neutralization precipitation (or displacement) enrichment, will produce a large amount of waste water like this, and for some difficult materials that leach also have extraction inadequately thoroughly and extraction cost too high, other metal is difficult to problems such as wastes such as recoverys simultaneously.
The extraction of low-grade dissipated metal germanium mainly is acidleach, the heavy germanium of tannin extract (tannin) then, and heavy germanium slag roasting obtains high-grade germanium concentrate, and germanium concentrate chlorinated distillation again extracts germanium dioxide, so just has long flow path, and the rate of recovery is low, the problem that wastewater flow rate is big.
When containing arsenic in the material, just have the dearsenification difficulty, and produce the hypertoxic gas of hydrogen arsenide, the problem of the bad processing of arsenic slag of generation.
The extraction and the process of enriching of above-mentioned traditional coloured scattered metals indium germanium low-grade material, the material that every processing is one ton, its production cost is higher, will arrange 5 tons simultaneously and contain the very acid of high density and the waste water of arsenic, and other valuable metal lead, zinc, silver also are difficult to reclaim.
[summary of the invention]
In order to overcome the above-mentioned shortcoming of prior art, the invention provides a kind of under the lower situation of relative cost, disposable with dissipated metal germanium and indium enrichment, lead, zinc, silver and the arsenic etc. in addition of enrichment simultaneously, arsenic enters flue dust mutually with the thing of red arsenic, because red arsenic are not leached in acidic medium, separate harmful element arsenic simultaneously so that in subsequent technique, comparatively simply reclaim valuable metal, have that technical process is simple, cost of manufacture is low and process environments close friend's the sulfuration and the reducing oxidation and enrichment method that contain arsenic indium germanium low-grade material.
The technical solution adopted for the present invention to solve the technical problems is: a kind of sulfuration and reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material, in containing the plumbous zinc arsenic raw material of indium germanium, allocate a certain amount of coal dust into as reductive agent, add elemental sulfur simultaneously, and add binding agent and carry out briquetting, its weight proportion is the plumbous zinc arsenic material of indium germanium: lime: coal dust: sulphur=100: 20～40: 5～10: 2～4; Make coal briquette or group's form and in shaft furnace, carry out sulfiding volatilization, controlled temperature is under 1000～1200 ℃ condition, in certain redox condition, the sulfiding volatilization time is 1～3 hour, plumbous zinc in the slag is below 2%, the content of indium germanium drops to 30～300 gram/tons, and flue dust leaches during for pH0.5 at the sulfuric acid terminal point, leach liquor with zinc dust precipitation to the indium germanium concentrate.
Indium germanium concentrate chlorinated distillation is obtained germanium dioxide, be not less than 2 hours 500 ℃ of oxidizing roastings, in the germanium indium concentrate input still kettle with oxidation, allocate the HCl of 9mol into, logical chlorine under 100～110 ℃ carries out chlorinated distillation germanium, the GeCl of gained
4Under-5～-10 ℃ condition, absorb, to GeCl with 7～9molHCl
4Add 4～6 times, the conductivity water of 5～10M Ω be hydrolyzed pure GeO
2
The processing condition that indium is extracted in vinasse extraction are: vinasse is with the kerosene of secondary octanol+30% of 60% TBP+10%, O/A=1: 1 extraction, with the back extraction of 0.8N hydrochloric acid, O/A=1: 2, the extraction of one-level and back extraction are all more than 79%, 4 grades of extractions and 4 grades of back extractions, the rate of recovery of indium is more than 99% in the vinasse, strip liquor obtains the sponge indium after replacing with aluminium sheet, 300～400 ℃ of meltings under alkali covers obtain 99.5% thick indium through the group of pressure, be mixed with again and contain In80～100g/l, the electrolytic solution of NaCl80～100g/l, employing current density 50～100A/M
2, electrolysis obtains 99.99% indium under the condition of groove pressure 0.20～0.35V.
The invention has the beneficial effects as follows: can be with lower production cost with enrichments such as valuable metal indium, germanium, lead, zinc and silver, without draining, cost of manufacture is relatively low, germanium in the flue dust that obtains, indium, zinc just can leach 95% at pH0.5, and arsenic can not be leached, hydrogen arsenide can be handled in addition, and valuable metal lead, zinc, silver can comprehensively reclaim.
[description of drawings]
Fig. 1 is a technical process block diagram of the present invention.
[embodiment]
The present invention is further described below in conjunction with drawings and Examples:
Referring to Fig. 1, a kind of sulfuration and reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material, the plumbous zinc arsenic material of indium germanium be will contain and a certain amount of elemental sulfur and pulverized anthracite allocated into, its proportioning is to contain arsenic indium germanium low-grade material: lime: coal dust: sulphur=100: 20: 10: 2, make the coal briquette form, add binding agent simultaneously and carry out briquetting, in shaft furnace, carry out sulfiding volatilization, controlled temperature is under 1000～1200 ℃ condition, in certain redox condition, the sulfiding volatilization time is 2 hours, and the plumbous zinc in the slag is below 2%, and the content of indium germanium can drop to about 30～300 gram/tons, flue dust leaches during for pH0.5 at the sulfuric acid terminal point, to the indium germanium concentrate, indium germanium concentrate chlorinated distillation obtains germanium dioxide to leach liquor with zinc dust precipitation, and indium is extracted in the vinasse extraction.
Contain the plumbous zinc arsenic material of indium germanium in the example and select the cadmia leached mud for use, the Chemical Composition and the content thereof of cadmia leached mud are respectively: germanic and indium 0.8～1.2%, leadedly be 25～35%, the material of zinc 10～20%, arsenic 1～3%, silver 0.03～0.05%, when tradition leaches, have only the leaching yield about 30%.
Raw coal, elemental sulfur and a certain amount of binding agent are gone back in the adding of cadmia leached mud carried out the briquetting processing, the sulfiding volatilization condition is in shaft furnace: temperature is 1150 ℃, time is 1.5 hours, the slag rate is 30%, and plumbous in the slag, zinc content is less than 2%, and in the slag indium, germanium less than 0.01%, the evaporation rate of indium, germanium is greater than 98%, 2 times of the indium of flue dust, germanium enrichments, the evaporation rate of lead, zinc, arsenic are more than 98%, and the evaporation rate of silver also reaches 75%.The Chemical Composition and the content thereof of flue dust are respectively: the Chemical Composition and the content thereof of Ge1～2%, In0.5～1.5%, Pb 55～65%, Zn15～25%, As 2～5%, Ag0.04～0.06%, slag are respectively: Ge0.004～0.009%, In0.03～0.05%, Pb 1.0～3.0%, Zn0.3～0.5%, As＜0.1%, Ag0.01～0.02%.
Processing condition when flue dust is leached processing are: adopt sulfuric acid to leach, normal temperature, pH are 0.5, the time is 30min, the leaching yield of Zn is 70～80%, the leaching yield of In is 95～98%, the leaching yield of Ge is 93～95%, Chemical Composition and content thereof in the leach liquor are respectively: Ge2～3g/l, In0.8～1.5g/l, Pb0.01～0.02g/l, Zn25～35g/l, As 0.05～0.09g/l, Chemical Composition and content thereof in the leached mud are respectively: Ge0.05～0.07%, In0.005～0.008, Pb5 5～65%, Zn 3～5%, As3～6%.
Leach liquor adds the zinc powder of 3 times of theoretical amount and replaces, processing condition are: add Cu0.2g/l, temperature is 50 ℃, stir 30min, the rate of displacement of In is 99.8%, and the rate of displacement of Ge is 99.5%, and Chemical Composition and content thereof in the replacement slag are respectively: Ge10～20%, In5～10%, Pb1.5～3.5%, Zn 30～50%, As0.2～0.5%, Cu3～7%, behind the replacement slag distillation germanium, indium is carried in extraction again; Displaced liquid can remove to be made into zn cpdss such as zinc sulfate.
The present invention and traditional technology ratio, the rate of recovery of indium, germanium can improve 60%.As year handling 250 tons of cadmia leached muds, the germanium that year fecund is 900 kilograms, the indium that fecund is 450 kilograms.
Claims (4)
1. a sulfuration and reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material, it is characterized in that: in containing the plumbous zinc arsenic raw material of indium germanium, allocate a certain amount of coal dust into as reductive agent, add elemental sulfur simultaneously, and add binding agent and carry out briquetting, its weight proportion is the plumbous zinc arsenic material of indium germanium: lime: coal dust: sulphur=100: 20～40: 5～10: 2～4; Make coal briquette or group's form and in shaft furnace, carry out sulfiding volatilization, controlled temperature is under 1000～1200 ℃ condition, in certain redox condition, the sulfiding volatilization time is 1～3 hour, plumbous zinc in the slag is below 2%, the content of indium germanium drops to 30～300 gram/tons, and flue dust leaches during for pH0.5 at the sulfuric acid terminal point, leach liquor with zinc dust precipitation to the indium germanium concentrate.
2. sulfuration and the reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material as claimed in claim 1, it is characterized in that: indium germanium concentrate chlorinated distillation is obtained germanium dioxide, be not less than 2 hours 500 ℃ of oxidizing roastings, the germanium indium concentrate of oxidation is dropped in the still kettle, allocate the HCl of 9mol into, logical chlorine carries out chlorinated distillation germanium, the GeCl of gained under 100～110 ℃ condition
4Under-5～-10 ℃ condition, absorb, to GeCl with 7～9molHCl
4Add 4～6 times, the conductivity water of 5～10M Ω be hydrolyzed pure GeO
2
3. sulfuration and the reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material as claimed in claim 2, it is characterized in that: the processing condition that indium is extracted in chlorinated distillation gained vinasse extraction are: vinasse is with the kerosene of secondary octanol+30% of 60% TBP+10%, O/A=1: 1 extraction, with the back extraction of 0.8N hydrochloric acid, O/A=1: 2, the extraction of one-level and back extraction be all more than 79%, 4 grades of extractions and 4 grades of back extractions, and the rate of recovery of indium is more than 99% in the vinasse.
4. sulfuration and the reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material as claimed in claim 3, it is characterized in that: strip liquor obtains the sponge indium after replacing with aluminium sheet, 300～400 ℃ of meltings under alkali covers obtain 99.5% thick indium through the group of pressure, be mixed with again and contain In80～100g/l, the electrolytic solution of NaCl80～100g/l adopts current density 50～100A/M
2, electrolysis obtains 99.99% indium under the condition of groove pressure 0.20～0.35V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100388232A CN101525693B (en) | 2009-04-17 | 2009-04-17 | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100388232A CN101525693B (en) | 2009-04-17 | 2009-04-17 | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101525693A CN101525693A (en) | 2009-09-09 |
| CN101525693B true CN101525693B (en) | 2011-02-09 |
Family
ID=41093762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100388232A Active CN101525693B (en) | 2009-04-17 | 2009-04-17 | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101525693B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282610A (en) * | 2016-10-17 | 2017-01-04 | 扬州宁达贵金属有限公司 | From containing the method for recovery indium liquid crystal indium concentrate |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831563B (en) * | 2010-05-12 | 2012-06-06 | 云南天浩稀贵金属股份有限公司 | Method for gathering and recovering indium and germanium from indium and germanium containing material by using one-step method |
| CN102628103A (en) * | 2012-02-23 | 2012-08-08 | 永兴县华鑫铅锡有限责任公司 | Method for enriching valuable metal from mine tailing and smelting slag by fire method |
| CN102618730B (en) * | 2012-02-23 | 2013-11-06 | 永兴县华鑫铅锡有限责任公司 | Process for separating materials containing indium, lead, silver, copper and bismuth |
| CN103290212A (en) * | 2012-02-24 | 2013-09-11 | 于军 | Clean smelting method of indium |
| CN102787242B (en) * | 2012-08-27 | 2013-12-11 | 中南大学 | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process |
| CN107058728A (en) * | 2017-05-25 | 2017-08-18 | 江苏省冶金设计院有限公司 | A kind of system and method for comprehensively utilizing ferrous material and germanic lignite |
| CN109402409A (en) * | 2018-11-29 | 2019-03-01 | 广东省稀有金属研究所 | A method of the enriched germanium from germanic lignite cigarette ash |
| CN109439909B (en) * | 2018-12-15 | 2023-09-05 | 六盘水中联工贸实业有限公司 | Method for recycling germanium from high-silicon-content optical fiber production waste |
| CN113584307B (en) * | 2021-08-02 | 2022-04-01 | 云南大学 | Device and method for enriching germanium in low-grade germanium concentrate through two-stage reduction and volatilization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420184A (en) * | 2002-11-07 | 2003-05-28 | 长沙矿冶研究院 | Method for extracting refined indium from indium tin oxide waste material |
| EP1408127A1 (en) * | 2001-06-07 | 2004-04-14 | Elcogas, S.A. | Method for recovering metals from the flying ashes generated in an integrated gasification combined cycle-type (igcc) thermal station |
-
2009
- 2009-04-17 CN CN2009100388232A patent/CN101525693B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1408127A1 (en) * | 2001-06-07 | 2004-04-14 | Elcogas, S.A. | Method for recovering metals from the flying ashes generated in an integrated gasification combined cycle-type (igcc) thermal station |
| CN1420184A (en) * | 2002-11-07 | 2003-05-28 | 长沙矿冶研究院 | Method for extracting refined indium from indium tin oxide waste material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282610A (en) * | 2016-10-17 | 2017-01-04 | 扬州宁达贵金属有限公司 | From containing the method for recovery indium liquid crystal indium concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101525693A (en) | 2009-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525693B (en) | Method for vulcanization, reducing oxidation and enrichment of low-grade material containing arsenic, indium and germanium | |
| CN103667720B (en) | Method for recovering zinc, indium, iron, and lead from high-iron zinc oxide mixture smelted with zinc | |
| CN102191391B (en) | Method for extracting germanium from high-impurity low-grade complex zinc oxide powder | |
| CN100591783C (en) | Method for recovering zinc and lead from waste electrolytic anode mud | |
| CN102776376B (en) | Method for recovering valuable metal from waste residue containing lead and zinc through wet-fire combination process | |
| CN103643044B (en) | The direct extracting copper of a kind of Bellamya aeruginosa wet method, zinc technology | |
| CN106544511B (en) | A kind of synthetical recovery manganese from Manganese anode slime, lead, the method for silver and selenium | |
| CN102925706B (en) | Method for treating cobalt-nickel-copper hydrometallurgy wastewater residue | |
| CN102094119A (en) | Method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching | |
| CN102766765B (en) | Zinc oxide powder recycling method | |
| CN105039713A (en) | Method for leaching solid arsenic out of arsenic sulfide slag through one step and enriching valuable metal | |
| CN105293564A (en) | Method for recycling zinc-containing dust ash in steel plant | |
| CN102787240A (en) | Method for comprehensive recovery of valuable metals from tin anode mud | |
| CN103555962B (en) | Method for comprehensively recovering selenium, vanadium and silver from vanadium-silver-selenium polymetallic ore by wet method | |
| CN105648214B (en) | It is a kind of to control the method that current potential vulcanization separates valuable metal in solution | |
| CN102642953B (en) | Treatment method for high-salinity heavy-metal-containing production sewage | |
| CN104480325A (en) | Method for extracting cobalt from cobalt-containing raw material | |
| CN101760654B (en) | Method for recovering indium from indium-containing waste | |
| CN103160688A (en) | Method for preparing germanium concentrate from germanium-containing leachate through utilizing zinc powder replacement method | |
| CN102560123A (en) | Method for utilization and harmless treatment of multi-metal material containing arsenic and indium | |
| CN111088433A (en) | Method for enriching and recovering thallium from lead smelting system | |
| CN114318417A (en) | Method for producing electrolytic manganese by using low-grade manganese oxide three-ore method | |
| CN110157924B (en) | Method for secondary zinc enrichment of low-grade high-oxidation-rate oxygen-sulfur mixed zinc ore | |
| CN102002584A (en) | Method of recovering manganese, lead and silver from zinc electrolyzed anode mud by utilizing acid-making tail gas | |
| CN103484694A (en) | Method for extracting bismuth from copper-bismuth concentrate |
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 |