CN106400052A - Method for purification tin removing for copper electrolyte - Google Patents
Method for purification tin removing for copper electrolyte Download PDFInfo
- Publication number
- CN106400052A CN106400052A CN201611152712.0A CN201611152712A CN106400052A CN 106400052 A CN106400052 A CN 106400052A CN 201611152712 A CN201611152712 A CN 201611152712A CN 106400052 A CN106400052 A CN 106400052A
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- China
- Prior art keywords
- tin
- copper electrolyte
- electrolyte
- removes
- phosphoric acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for purification tin removing for a copper electrolyte. Limestone powder and phosphoric acid serve as a combined precipitating agent, tin ions in the copper electrolyte can be effectively removed, and tin can be recycled from tin removing slag obtained after precipitation through a pyrogenic process. The method is easy and convenient to operate and easy to achieve, the limestone powder and the phosphoric acid serve as the combined precipitating agent, the tin the electrolyte can be precipitated more thoroughly, the slag type of precipitate is changed, filtering is easy, and the purpose of tin removing is achieved. The method is a new technology which is simple, effective and capable of facilitating tin metal recycling.
Description
Technical field
The present invention relates to the method that in non-ferrous metal hydrometallurgy, cleaning copper electrolyte removes tin.
Background technology
During blister copper electrorefining, because the oxidation-reduction potential of Sn is defeated by Cu, in blister copper positive plate, Sn is entered with divalent ion
Enter electrolyte, continue and be oxidized to tetravalent tin.Easily it is hydrolyzed into water insoluble, sulfuric acid, salt after tin ion reaches finite concentration
Acid, β-(the SnO2 H2O) 5 of nitric acid.β-(SnO2 H2O) 5 has colloidal nature, is suspended in solution, makes electrolyte muddy.
In copper electrolyte, Sn concentration is higher, and formation β-(SnO2 H2O) 5 colloids are more, on the one hand pollute electrolyte, also reduces cloudy
The quality of pole copper, on the other hand causes earth of positive pole filtration difficulty, hinders the normal production of electrorefining.Therefore, purification removes
Tin, is allowed in control range, is to ensure that the normal important measures producing with Cathode Copper Quality of blister copper electrorefining.
At present, in copper electrolyte, detinning method is few, β-(SnO2 H2O) 5 that in electrolyte, the hydrolysis of a Sn part produces
Precipitation enters copper anode mud, and another part tin separates out in condensing crystallizing nickel sulfate process, and this had both caused nickel sulfate quality and has reduced,
Also huge economic losses are caused because tin is not recycled.
Tin electrorefining is general, prevents solution feculence, is usually added into phenol sulfonic acid or cresol sulfonic acid.In tin electrolyte tin with
Based on Bivalent Tin, using the chemical substance adding reproducibility, complexing, suppression Bivalent Tin is oxidized to tetravalent tin, has both prevented Xi Shui
Solution makes solution feculence, in turn ensure that electrolyte divalence tin concentration, and industrial at present application must compare many stannous sulphate electrolytes one-tenth
Divide and be mainly made up of sulfuric acid, stannous sulfate, cresol sulfonic acid or phenyl methylcarbamate sulfonic acid etc..
Above method is for copper electrolyte except tin has little significance.Add reproducibility, the chemical substance of complexing, suppression
Bivalent Tin is oxidized to tetravalent tin, and one side tin is enriched with the electrolytic solution, increases bath resistance, reduces current efficiency；The opposing party
Face tin had both reduced the loss that nickel sulfate grade also result in tin in nickel sulfate.Using polyacrylamide and polyethyleneimine amine
Although organic synthesis macromolecule is combined and is made sedimentation agent and can precipitate tin, usage amount and sedimentation agent excessive concentration, cost is larger.
Content of the invention
Purpose of the present invention tin ion in removing copper electrolyte, improves copper electrolyte situation, provides with process is simple,
Easy to operate it is easy to separate, the method that a kind of cleaning copper electrolyte the advantages of effect is significant removes tin.
To achieve these goals, the technical solution used in the present invention is：
A kind of method that cleaning copper electrolyte removes tin, processing solution is stanniferous copper electrolyte, and this processing step includes：Oxidation neutralization
Operation and purifying detinning operation；
Oxidation neutralization step：Pending stanniferous copper electrolyte is warming up to 70-80 DEG C, is passed through compressed air oxidation tin to tetravalence
Partly sour, with phosphoric acid precipitates tetravalence tin ion with copper electrolyte in tin ice agstone；
Purifying detinning operation：Above liquid is filtered, and the filtrate after filtration is liquid after purifying, and filter residue removes scruff, can
As stanniferous material, tin is reclaimed by pyrogenic process.
The method that a kind of above-mentioned cleaning copper electrolyte removes tin, stanniferous below the 10g/L of copper electrolyte.
The method that a kind of above-mentioned cleaning copper electrolyte removes tin, with copper electrolyte acid in agstone, its concentration is 15-
20g/L.
The method that a kind of above-mentioned cleaning copper electrolyte removes tin, phosphoric acid consumption：When in electrolyte, Sn concentration is less than 5g/L, phosphorus
0.5 ‰ that volume is electrolyte volume are added in acid；When in electrolyte, Sn concentration is 5-10 g/L, it is electrolyte that phosphoric acid adds volume
The 1 ‰ of volume.
The method that a kind of above-mentioned cleaning copper electrolyte removes tin, the oxidation neutralization time is 60min, and the purifying detinning time is
60min.
Separation of solid and liquid process are realized by flame filter press, and filtration temperature, at 70-80 DEG C, filters initial stage filtrate muddiness and need to return
Return and again filter, clear filtrate can carry out storage tank.
Beneficial effects of the present invention are：（1）Method is easy and simple to handle, it is easy to accomplish, with agstone and phosphoric acid as joint
Precipitating reagent, tin can precipitate more thoroughly in electrolyte, and change sediment slag type it is easy to filter, thus reaching the purpose except tin.
（2）Tin is opened a way, except scruff other tenor is less than 0.5, tin can reclaim further.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
As shown in figure 1, a kind of method that cleaning copper electrolyte removes tin, processing solution is stanniferous copper electrolyte, and this technique walks
Rapid inclusion：Oxidation neutralization step and purifying detinning operation；
Oxidation neutralization step：Pending stanniferous copper electrolyte is warming up to 70-80 DEG C, is passed through compressed air oxidation tin to tetravalence
Partly sour, with phosphoric acid precipitates tetravalence tin ion with copper electrolyte in tin ice agstone；
Purifying detinning operation：Above liquid is filtered, and the filtrate after filtration is liquid after purifying, and filter residue removes scruff, can
As stanniferous material, tin is reclaimed by pyrogenic process.
Wherein, stanniferous below the 10g/L of copper electrolyte, in agstone and when copper electrolyte is sour, its concentration is 15-20g/L.
Phosphoric acid consumption：When in electrolyte, Sn concentration is less than 5g/L, phosphoric acid adds 0.5 ‰ that volume is electrolyte volume；Electricity
When in solution liquid, Sn concentration is 5-10 g/L, phosphoric acid adds 1 ‰ that volume is electrolyte volume, and further, the oxidation neutralization time is excellent
Elect 60min as, the purifying detinning time is preferably 60min.
By flame filter press filtration, purification electrolyte, at 70-80 DEG C, filter initial stage filtrate muddiness needs to return filtration temperature
Again filter, clear filtrate can carry out storage tank.
It is specifically described with reference to two specific embodiments：
Embodiment 1
Copper electrolyte chemical composition is shown in Table 1
Table 1 copper electrolyte chemical composition（%）
| H2SO4 | Cu | Ni | Sn | As | Sb | Cl | Fe |
| 142.82 | 37.77 | 38.61 | 7.96 | 0.47 | 0.74 | 0.13 | 6.16 |
According to table 1 cupric electrolysis chemical composition, with 15g/L agstone, 1 ‰ phosphoric acid volumes, oxidized in, purifying detinning, mistake
After three steps of filter, in electrolyte, Sn concentration is only 0.2g/L.Except in scruff, Cu, Ni content is less than 0.5%, Sn content 18.75%,
CaO18.57%.
Embodiment 2
Copper electrolyte chemical composition is shown in Table 2
Table 2 copper electrolyte chemical composition（%）
| H2SO4 | Cu | Ni | Sn | As | Sb | Cl | Fe |
| 144.25 | 36.18 | 36.25 | 3.42 | 0.19 | 0.22 | 0.12 | 5.72 |
According to table 2 cupric electrolysis chemical composition, with 10g/L agstone, 0.5 ‰ phosphoric acid volumes, oxidized in, purifying detinning,
After filtering three steps, in electrolyte, Sn concentration is only 0.12g/L.Except in scruff, Cu, Ni content is less than 0.5%, Sn content
15.23%, CaO22.04%.
The method is easy and simple to handle, it is easy to accomplish, with agstone and phosphoric acid as co-precipitation agent, can be by tin in electrolyte
Precipitation is more thorough, and changes sediment slag type it is easy to filter, thus reaching the purpose except tin, tin is opened a way, except scruff its
Its tenor is less than 0.5, and tin can reclaim further.
General principle, principal character and the advantages of the present invention of the present invention have been shown and described above.The technology of the industry
The simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and specification for the personnel
Principle, without departing from the spirit and scope of the present invention the present invention also have various changes and modifications, these change and
Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and its
Equivalent defines.
Claims (6)
1. a kind of method that cleaning copper electrolyte removes tin, processing solution is stanniferous copper electrolyte, and this processing step includes：In oxidation
With operation and purifying detinning operation；
It is characterized in that, aoxidize neutralization step：Pending stanniferous copper electrolyte is warming up to 70-80 DEG C, is passed through compressed air
Tin oxide to tetravalent tin and with agstone and copper electrolyte partly sour, with phosphoric acid precipitates tetravalence tin ion；
Purifying detinning operation：Above liquid is filtered, and the filtrate after filtration is liquid after purifying, and filter residue removes scruff, can
As stanniferous material, tin is reclaimed by pyrogenic process.
2. a kind of cleaning copper electrolyte according to claim 1 removes the method for tin it is characterised in that copper electrolyte is stanniferous
Below 10g/L.
3. a kind of cleaning copper electrolyte according to claim 1 removes the method for tin it is characterised in that in agstone and copper
Electrolyte acid, its concentration is 15-20g/L.
4. a kind of cleaning copper electrolyte according to claim 1 removes the method for tin it is characterised in that phosphoric acid consumption：Electrolysis
When in liquid, Sn concentration is less than 5g/L, phosphoric acid adds 0.5 ‰ that volume is electrolyte volume；In electrolyte, Sn concentration is 5-10 g/L
When, phosphoric acid adds 1 ‰ that volume is electrolyte volume.
5. a kind of cleaning copper electrolyte according to claim 1 remove tin method it is characterised in that oxidation the neutralization time be
60min, the purifying detinning time is 60min.
6. a kind of cleaning copper electrolyte according to claim 1 removes the method for tin it is characterised in that filtration temperature is in 70-
80 DEG C, filtration initial stage filtrate muddiness need to return and again filter, and clear filtrate can carry out storage tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611152712.0A CN106400052A (en) | 2016-12-14 | 2016-12-14 | Method for purification tin removing for copper electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611152712.0A CN106400052A (en) | 2016-12-14 | 2016-12-14 | Method for purification tin removing for copper electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN106400052A true CN106400052A (en) | 2017-02-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611152712.0A Pending CN106400052A (en) | 2016-12-14 | 2016-12-14 | Method for purification tin removing for copper electrolyte |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110499521A (en) * | 2019-09-29 | 2019-11-26 | 湖南仁发材料科技有限公司 | A kind of method of copper electrolyte and copper removal scruff synergistic purification and processing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108534A (en) * | 1985-11-18 | 1986-09-03 | 鞍山市冶炼厂 | Extraction process of tin from copper-smelting sludge |
| CN102925920A (en) * | 2012-10-31 | 2013-02-13 | 崖巨钊 | Copper electrolyte extracting and purifying process technology |
| CN103243223A (en) * | 2013-05-23 | 2013-08-14 | 广州有色金属研究院 | Method for removing tin from crude copper |
| CN104630826A (en) * | 2015-01-29 | 2015-05-20 | 中南大学 | Technique for recovering tin from tin anode sludge |
-
2016
- 2016-12-14 CN CN201611152712.0A patent/CN106400052A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108534A (en) * | 1985-11-18 | 1986-09-03 | 鞍山市冶炼厂 | Extraction process of tin from copper-smelting sludge |
| CN102925920A (en) * | 2012-10-31 | 2013-02-13 | 崖巨钊 | Copper electrolyte extracting and purifying process technology |
| CN103243223A (en) * | 2013-05-23 | 2013-08-14 | 广州有色金属研究院 | Method for removing tin from crude copper |
| CN104630826A (en) * | 2015-01-29 | 2015-05-20 | 中南大学 | Technique for recovering tin from tin anode sludge |
Non-Patent Citations (1)
| Title |
|---|
| 傅作健: "关于废杂铜料处理方法的讨论", 《有色金属(冶炼部分)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110499521A (en) * | 2019-09-29 | 2019-11-26 | 湖南仁发材料科技有限公司 | A kind of method of copper electrolyte and copper removal scruff synergistic purification and processing |
| CN110499521B (en) * | 2019-09-29 | 2021-07-16 | 湖南仁发材料科技有限公司 | Method for cooperatively purifying and treating copper electrolyte and copper and tin slag |
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