CN106086420A - The method extracting valuable metal from germanium-containing alloy - Google Patents
The method extracting valuable metal from germanium-containing alloy Download PDFInfo
- Publication number
- CN106086420A CN106086420A CN201610606563.4A CN201610606563A CN106086420A CN 106086420 A CN106086420 A CN 106086420A CN 201610606563 A CN201610606563 A CN 201610606563A CN 106086420 A CN106086420 A CN 106086420A
- Authority
- CN
- China
- Prior art keywords
- germanium
- containing alloy
- valuable metal
- sulphuric acid
- method extracting
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- 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 a kind of method extracting valuable metal from germanium-containing alloy, comprise the following steps: step S1: use disintegrating apparatus that germanium-containing alloy is crushed, cross 100 mesh sieves；Step S2: siftage step S1 obtained is placed in reaction vessel, by liquid-solid ratio (4 ~ 8): 1 mixes with water, it is uniformly mixed and becomes mixed liquor, the sulphuric acid of stoichiometric proportion it is added beyond in mixed liquor, the speed added by controlling sulphuric acid carrys out controlling potential, after adding sulphuric acid, start reaction vessel is heated and is incubated a period of time；Step S3: in question response container after greenhouse cooling, carries out solid-liquor separation, the filtrate obtained and filtering residue.A kind of method extracting valuable metal from germanium-containing alloy of the present invention, technique is simple, separates thoroughly, it is achieved that in germanic bidery metal, copper, germanium separate with the metal such as ferrum, cobalt, being conducive to the recovery of germanium in bidery metal, the comprehensive reutilization for valuable metal has the biggest economic worth.
Description
Technical field
The present invention relates to the recovery method of valuable metal in a kind of alloy, particularly relating to a kind of extraction from germanium-containing alloy has
The method of valency metal.
Background technology
Bidery metal has many application at the wide spectrum such as communication, medical treatment, can produce during the production and use of bidery metal
Raw substantial amounts of alloyed scrap.Bidery metal waste material often contains the rare metals such as common metal and germanium such as ferrum, cobalt, copper, from vain
Alloyed scrap reclaims wherein valuable metal such as ferrum, cobalt, copper, germanium etc. and for the regeneration of resource, there is the biggest value.
The extract technology of bidery metal mostly is and uses mineral acid oxidizer as leaching agent at ambient pressure at present, makes in alloy
All elements enters in leachate, and this increases difficulty to the separation of follow-up valuable metal.
Thus, it is necessary to design a kind of method of valuable metal of extracting from germanium-containing alloy to solve above-mentioned technical problem.
Summary of the invention
Object of the present invention is to provide a kind of method extracting valuable metal from germanium-containing alloy.
For realizing object defined above, the present invention adopts the following technical scheme that and a kind of extracts valuable metal from germanium-containing alloy
Method, comprises the following steps: step S1: uses disintegrating apparatus to crush germanium-containing alloy, crosses 100 mesh sieves；Step S2: will step
The siftage that rapid S1 obtains is placed in reaction vessel, by liquid-solid ratio (4 ~ 8): 1 mixes with water, is uniformly mixed and becomes mixing
Liquid, is added beyond the sulphuric acid of stoichiometric proportion in mixed liquor, and the speed added by controlling sulphuric acid carrys out controlling potential, adds sulfur
After acid, start reaction vessel is heated and is incubated a period of time；Step S3: after temperature reduces in question response container, carry out
Solid-liquor separation, the filtrate obtained and filtering residue.
As a further improvement on the present invention, in step S2, the mass concentration of added sulphuric acid is 30% ~ 80%.
As a further improvement on the present invention, it is characterised in that: sulphuric acid stoichiometrically 1.2 ~ 1.5 times in step S2
Add.
As a further improvement on the present invention, leaching process controls the flow-control current potential of sulphuric acid, potentiometer reference electricity
Extremely silver/silver chloride electrode, makes mixed liquor current potential be maintained between-500mV ~-200mV.
As a further improvement on the present invention, mixed liquor current potential realizes by controlling the flow of sulphuric acid.
As a further improvement on the present invention, the flow-control of sulphuric acid uses one current potential-flow intelligent control system to realize.
As a further improvement on the present invention, the holding temperature of reaction vessel is 80 ~ 100 DEG C.
As a further improvement on the present invention, the temperature retention time of reaction vessel is 1 ~ 6h.
As a further improvement on the present invention, reaction vessel is three-neck flask.
As a further improvement on the present invention, germanium-containing alloy used is germanic bidery metal.
A kind of method extracting valuable metal from germanium-containing alloy of the present invention, technique is simple, separates thoroughly, only with sulphuric acid
For leaching agent, it is not added with other oxidants, it is achieved that in germanic bidery metal, copper, germanium separate with the metal such as ferrum, cobalt, is conducive to white
The recovery of germanium in alloy, the comprehensive reutilization for valuable metal has the biggest economic worth.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
A kind of method extracting valuable metal from germanium-containing alloy, comprises the following steps.
Step S1: use disintegrating apparatus that germanium-containing alloy is crushed, cross 100 mesh sieves.
Step S2: siftage step S1 obtained is placed in reaction vessel, by liquid-solid ratio (4 ~ 8): 1 mixes with water, stirs
Mix mix homogeneously and become mixed liquor, in mixed liquor, be added beyond the sulphuric acid of stoichiometric proportion, by controlling the speed that sulphuric acid adds
Degree carrys out controlling potential, after adding sulphuric acid, starts heat reaction vessel and be incubated a period of time.
Step S3: after temperature reduces in question response container, carry out solid-liquor separation, the filtrate obtained is molten rich in ferrum and cobalt
Liquid；Filtering residue is rich in copper, the solid content of germanium.
The present invention achieves germanium in leaching stage and separates with the metal such as ferrum, cobalt, and germanium has obtained well in leached mud
Enrichment, it is to avoid germanium together enters solution and produces and separate in difficulty, the loss problem, beneficially bidery metal such as greatly with ferrum, cobalt etc.
The synthetical recovery of valuable metal.
Used by the present invention, the typical composition of germanic bidery metal is shown in Table 1.
Table 1 germanic bidery metal typical composition.
| Composition | Fe/% | Co/% | Cu/% | Ge/% | Other/% |
| Content | 65.8 | 19.2 | 11.6 | 0.44 | 2.96 |
Embodiment 1.
Inject 2L deionized water in 5L three-neck flask, then put into the germanic bidery metal after 500g crushed 100 mesh sieves
Raw material, opens stirring paddle, sets mixing speed as 300r/min, to be mixed be formed uniformly mixed liquor after, originally with 0.75L/h's
Flow adds the sulphuric acid 2.1L of mass concentration 30%, and the flow-control of sulphuric acid uses one current potential-flow intelligent control system to realize,
Add between sulfuric acid process keeping solution system current potential for-500 ~-320mV, be incubated after adding sulphuric acid and react 4h at 85 ~ 95 DEG C.
After reaction terminates, after temperature in three-neck flask is down to 70 DEG C, using vacuum filtration machine to carry out solid-liquor separation, the filtrate obtained is
Rich in ferrum and the solution of cobalt, ICP-MS detection gained filtrate component analysis result is Fe:112.8g/L, Co:34.4g/L, Cu:
23mg/L, Ge:3mg/L, filtering residue is rich in copper, the solid content of germanium.
Embodiment 2.
Inject 2.3L deionized water in 5L three-neck flask, then put into the germanic white conjunction after 350g crushed 100 mesh sieves
Gold raw material, opens stirring paddle, sets mixing speed as 200r/min, to be mixed be formed uniformly mixed liquor after, with the stream of 0.5L/h
Amount adds the sulphuric acid 0.56L of mass concentration 80%, and the flow-control of sulphuric acid uses one current potential-flow intelligent control system to realize, and adds
Keeping solution system current potential in sulfuric acid process is between-280 ~-250mV, is incubated and reacts 1h at 80 ~ 90 DEG C after adding sulphuric acid；Instead
After should terminating, after temperature in three-neck flask is down to 65 DEG C, using vacuum filtration machine to carry out solid-liquor separation, the filtrate obtained is richness
Iron content and the solution of cobalt, ICP-MS detection filtrate component result is Fe:74.3g/L, Co:21.7g/L, Cu:34 mg/L, Ge:8
Mg/L, filtering residue is rich in copper, the solid content of germanium.
Embodiment 3.
Inject 0.8L deionized water in 2L three-neck flask, then put into the germanic white conjunction after 100g crushed 100 mesh sieves
Gold raw material, opens stirring paddle, sets mixing speed as 200r/min, to be mixed be formed uniformly mixed liquor after, with the stream of 0.25L/h
Amount adds the sulphuric acid 0.25L of 50%, and the flow-control of sulphuric acid uses one current potential-flow intelligent control system to realize, and adds sulfuric acid process
Middle holding solution system current potential is between-320 ~-200mV, is incubated and reacts 6h at 85 ~ 100 DEG C after adding sulphuric acid；Reaction terminates
After, after temperature in three-neck flask is down to 60 DEG C, use vacuum filtration machine to carry out solid-liquor separation, the filtrate obtained for rich in ferrum and
The solution of cobalt, ICP-MS detection filtrate component result is Fe:73.1g/L, Co:21.3g/L, Cu:33 mg/L, Ge:6 mg/L,
Filtering residue is rich in copper, the solid content of germanium.
Using a kind of method extracting valuable metal from germanium-containing alloy of the present invention, the leaching rate of ferrum and cobalt all reaches 95%
Above, the leaching rate of copper and germanium is all below 1%.
Compared with prior art, the present invention has the advantages that.
1, the invention belongs to normal pressure acidleach, operating condition requires low, and technique is simple, and ferrum cobalt leaching rate is high, separates thoroughly.
2, the present invention is only with sulphuric acid as leaching agent, is not added with other oxidants, by control sulphuric acid add inbound traffics control
The current potential of leachate processed, it is achieved that in germanic bidery metal, copper, germanium separate with the metal such as ferrum, cobalt, it is to avoid have valency gold in raw material
Belong to the difficulty together entering the separation and recovery that leachate produces.
3, valuable metal germanium has obtained good enrichment in filtering residue, reduces germanium loss in separation and recovery, is conducive to
The recovery of germanium in bidery metal, the comprehensive reutilization for valuable metal has the biggest economic worth.
Although being example purpose, have been disclosed for the preferred embodiment of the present invention, but the ordinary skill people of this area
Member it will be appreciated that in the case of without departing from by scope and spirit of the present invention disclosed in appending claims, various changes
It is possible for entering, increasing and replacing.
Claims (10)
1. the method extracting valuable metal from germanium-containing alloy, it is characterised in that: comprise the following steps:
Step S1: use disintegrating apparatus that germanium-containing alloy is crushed, cross 100 mesh sieves；
Step S2: siftage step S1 obtained is placed in reaction vessel, by liquid-solid ratio (4 ~ 8): 1 mixes with water, stirring is mixed
Closing and uniformly become mixed liquor, be added beyond the sulphuric acid of stoichiometric proportion in mixed liquor, the speed added by controlling sulphuric acid is come
Controlling potential, after adding sulphuric acid, starts heat reaction vessel and be incubated a period of time；
Step S3: after temperature reduces in question response container, carry out solid-liquor separation, the filtrate obtained and filtering residue.
2. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: in step S2
The mass concentration of added sulphuric acid is 30% ~ 80%.
3. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: in step S2
1.2 ~ 1.5 times of additions of the stoichiometric proportion that sulphuric acid is reacted completely by ferrum and cobalt.
4. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: leaching process
The current potential of middle control mixed liquor, potential measurement use silver/silver chloride reference electrode, make mixed liquor current potential be maintained at-500mV ~-
Between 200mV.
5. according to the method extracting valuable metal from germanium-containing alloy described in claim 4, it is characterised in that: mixed liquor electricity
Position realizes by controlling the flow of sulphuric acid.
6. according to the method extracting valuable metal from germanium-containing alloy described in claim 5, it is characterised in that: the stream of sulphuric acid
Amount controls to use one current potential-flow intelligent control system to realize.
7. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: reaction vessel
Holding temperature be 80 ~ 100 DEG C.
8. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: reaction vessel
Temperature retention time be 1 ~ 6h.
9. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: reaction vessel
For three-neck flask.
10. according to the method extracting valuable metal from germanium-containing alloy described in claim 1, it is characterised in that: used germanic
Alloy is germanic bidery metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610606563.4A CN106086420A (en) | 2016-07-29 | 2016-07-29 | The method extracting valuable metal from germanium-containing alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610606563.4A CN106086420A (en) | 2016-07-29 | 2016-07-29 | The method extracting valuable metal from germanium-containing alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106086420A true CN106086420A (en) | 2016-11-09 |
Family
ID=57479269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610606563.4A Pending CN106086420A (en) | 2016-07-29 | 2016-07-29 | The method extracting valuable metal from germanium-containing alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106086420A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756002A (en) * | 2017-01-12 | 2017-05-31 | 江苏凯力克钴业股份有限公司 | Germanic bidery metal synthetical recovery germanium, cobalt, copper, iron process |
| CN112442606A (en) * | 2020-11-24 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for recovering germanium from germanium-containing copper-cobalt alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109043A (en) * | 2006-07-21 | 2008-01-23 | 刘伟锋 | Method for processing cunico |
| CN101157982A (en) * | 2006-10-08 | 2008-04-09 | 中国恩菲工程技术有限公司 | Method for leaching bidery metal by sulfuric acid and inflation agitation leaching trough |
| CN101812585A (en) * | 2009-08-27 | 2010-08-25 | 浙江华友钴业股份有限公司 | Microbubble oxidization and acid dissolution method for copper-cobalt alloy |
| CN104087758A (en) * | 2014-07-15 | 2014-10-08 | 长沙矿冶研究院有限责任公司 | Method for extracting valuable metals in cobalt-copper alloy by virtue of full hydrometallurgy |
-
2016
- 2016-07-29 CN CN201610606563.4A patent/CN106086420A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109043A (en) * | 2006-07-21 | 2008-01-23 | 刘伟锋 | Method for processing cunico |
| CN101157982A (en) * | 2006-10-08 | 2008-04-09 | 中国恩菲工程技术有限公司 | Method for leaching bidery metal by sulfuric acid and inflation agitation leaching trough |
| CN101812585A (en) * | 2009-08-27 | 2010-08-25 | 浙江华友钴业股份有限公司 | Microbubble oxidization and acid dissolution method for copper-cobalt alloy |
| CN104087758A (en) * | 2014-07-15 | 2014-10-08 | 长沙矿冶研究院有限责任公司 | Method for extracting valuable metals in cobalt-copper alloy by virtue of full hydrometallurgy |
Non-Patent Citations (4)
| Title |
|---|
| LIU W 等: "Selective leaching of cobalt and iron from cobalt white alloy in sulfuric acid solution with catalyst", 《INTERNATIONAL JOURNAL OFMINERAL PROCESSING》 * |
| SHEIN ET AL: "Electrochemical bahaviour of eutectic metal-germanium alloys in sulphuric acid", 《ELECTROCHIMICAACTA》 * |
| 张琴: "钴白合金电化学溶解的试验研究", 《江西有色金属》 * |
| 曹洪杨: "氧压酸浸在锗铜钴白合金有价组分分离中的应用", 《氧压酸浸在含锗铜钴白合金有价组分分离中的应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756002A (en) * | 2017-01-12 | 2017-05-31 | 江苏凯力克钴业股份有限公司 | Germanic bidery metal synthetical recovery germanium, cobalt, copper, iron process |
| CN112442606A (en) * | 2020-11-24 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for recovering germanium from germanium-containing copper-cobalt alloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110093506B (en) | Method for efficiently extracting valuable metals from germanium-containing zinc leaching residues and reducing valuable metals | |
| CN107385215B (en) | A kind of method that cupric electrolysis black copper mud resource utilizes | |
| CN106868306B (en) | A kind of method of zinc leaching residue valuable metal high efficiente callback | |
| CN106916945B (en) | A kind of method of the integrated treatment recycling valuable metal of the low germanium zinc-oxide calcine of high-speed rail and zinc sulfite | |
| EP3269832B1 (en) | Method of recycling and processing waste battery | |
| CN110117723B (en) | Germanium-rich zinc oxide smoke leaching method | |
| CN106868307A (en) | A kind of pyrite cinder arsenic removal is enriched with the comprehensive utilization process of gold and silver | |
| CN107236872B (en) | A method of recycling rhenium from the difficult poor rhenium slag of high-sulfur high-arsenic | |
| CN102051478A (en) | Wet process for treating lead copper matte | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN110184482A (en) | A kind of germanic Second-rate zinc oxide powder extract technology | |
| CN106435176A (en) | Two-stage selective heterogenite leaching method | |
| CN103343242B (en) | Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate | |
| CN108249480A (en) | A kind of comprehensive recovering process of Copper making arsenic sulfide slag, flue dust leachate arsenic | |
| CN107557570A (en) | Method for comprehensively recovering valuable metals from cyanidation tailings | |
| CN104388711A (en) | Method for recovering rare earth by leaching rare earth oxide molten slag | |
| CN105039724A (en) | Smelting furnace soot treatment method | |
| CN106086420A (en) | The method extracting valuable metal from germanium-containing alloy | |
| CN108315553A (en) | A kind of leaching method of copper cobalt sulfide ore | |
| CN104032131A (en) | Method for processing high-tin anode slurry | |
| CN111057847A (en) | Green method for preparing battery-grade nickel sulfate from nickel salt | |
| CN104386737B (en) | A kind of zinc abstraction prepares the method for Cadmium oxide containing cadmium fumes | |
| CN106148688A (en) | A kind of zinc hydrometallurgy leaches heavy iron process | |
| CN105734303A (en) | Method for controlling concentration of cyanide ions to weaken copper dissolution in gold leaching process | |
| CN110643811B (en) | Clean smelting process for nickel-molybdenum ore by full-wet method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161109 |