CN102828205A - Novel metal electro-deposition refining technology - Google Patents
Novel metal electro-deposition refining technology Download PDFInfo
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- CN102828205A CN102828205A CN2011102591854A CN201110259185A CN102828205A CN 102828205 A CN102828205 A CN 102828205A CN 2011102591854 A CN2011102591854 A CN 2011102591854A CN 201110259185 A CN201110259185 A CN 201110259185A CN 102828205 A CN102828205 A CN 102828205A
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Abstract
The invention provides a novel metal electro-deposition refining technology, and especially relates to a metal electro-deposition technology with a metal sulfate as a raw material, wherein the technology is a new technique organically combining membrane separation with the electrochemistry. An electro-deposition tank is separated into an anode chamber and a cathode chamber by an anionic selective diaphragm, a metal sulfate solution is injected into the cathode chamber through a cathode cycle system, metal ions are reduced into metals at the cathode, dilute sulfuric acid (H2SO4) is injected into the anode chamber through an anode cycle system during initial operation, high-density H2SO4 can be obtained in the anode chamber along the performing of the electrode process, and equal pure water is simultaneously added when the H2SO4 is extracted through the anode cycle system. The metal products obtained through the technology have the advantages of good quality and no environmental pollution. The H2SO4 byproduct can be recycled, and has an excellent economic performance.
Description
Technical field
The present invention provides a kind of novel metal electrodeposition refinery practice, and relating in particular to a kind of is the metal electrodeposition process of raw material with the metal sulfate, is a kind of novel technique with membrane sepn and electrochemistry combination.
Background technology
Current domestic metal electrodeposition refinery practice, general employing all is the electrowinning with insoluble anode method, no ion-exchange membrane is participated in; Anode adopts noble electrode; Negative electrode adopts the pure metal material, injects pure metal electric hydrops in the electrode vessel, and the yin, yang ion is respectively in electrode generation redox reaction in the solution.As being electric effusion with the sulfuric acid metal salt solution, be necessary for acidity, pH＜3, this will ask reactor drum must be acid corrosion-resistant, gained anodic product SO
2Though exist with water-soluble form, but when reaching capacity state, can escape in the air, cause environmental pollution.As being electric effusion with the chlorination metal salt solution, Cl
-In anodic oxidation is Cl
2, Cl
2Have toxicity,, can influence the healthy and destruction ecotope of staff, will increase production cost like this, and cause complex manufacturing if further do not handle.
The electrolysis with ion-exchange film technology is the technology with comprehensive function characteristic that electrodialysis and electrolysis combine; Successfully be applied to chlorine industry; This technology demonstrates efficiently, high-quality, characteristic that pollution is few have caused people's great attention, and is very active at the hydrometallurgy area research.Abroad, electrolysis with ion-exchange film technology successfully has been used for the preparation of pure metal.For example, people such as U.S. Redden have developed a kind of pair of membrane electrolyser, and two anion-exchange membranes are divided into anolyte compartment and cathode compartment with electrolyzer; Impure metal anode; Electrodissolution in the anolyte compartment, the anolyte that obtains is recycled to cathode compartment after purifying, on negative electrode, can deposit high pure metal.But use cavity block blocking anode liquid impurity to transfer in the catholyte, thereby realize the electrorefining of high impurity raw material.U.S. mineral bureau combines two membrane electrolyser technology with suitable solution purification, from the superalloy waste material of severe contamination, reclaim high-purity cobalt and nickel, and low-quality cobalt is purified to the A level.The laboratory scale electrolyzer successfully expands demonstration scale device to, and the result shows that operation and investment are all comparatively economical, and operational efficiency has surpassed 97%, and power consumption is 4.0～5.1kWh/kg cobalt.
Utilize the electrolysis with ion-exchange film technology to enhance productivity, simplify the metallurgical technology flow process greatly, both recyclable useful matter; Can not produce secondary pollution again, can also reach more effectively utilizing of the energy, can be used as unit operation; Utilization flexibly, and is easy to operate, is convenient to realize robotization control.
Summary of the invention
The present invention relates to a kind of novel metal electrodeposition refinery practice; Provide technical scheme following: to be reduced to refining of metal technology to the metal sulfate electric effusion, to utilize the anion-selective barrier film that Winning cell is divided into anolyte compartment and cathode compartment, solution of metal sulfates is injected cathode compartment through the cathode compartment recycle system; Metals ion is in cathodic reduction; Initial launch is injected the anolyte compartment through the anode recycle system with dilute sulphuric acid, along with electrode process carries out, can obtain high density H in the anolyte compartment
2SO
4, extract H through the anode recycle system
2SO
4, and add the pure water of equivalent simultaneously.
Specifically, under the traction of direct current field force, the metallic cation in the cathode chamber solution receives negative electrode and attracts, and does directional migration to negative electrode, and on negative electrode the generating electrodes reduction reaction; And SO
4 2-The cathode compartment of moving out passes cavity block and gets into the anolyte compartment, and the anolyte compartment is a pure water, H
2The reducing power of O on negative electrode is greater than SO
4 2-Reducing power on negative electrode, thereby water is oxidized, the generating electrodes oxidizing reaction generates H
+And O
2H
+Because the barrier effect of cavity block can not pass cavity block and get into cathode compartment.Electrochemical reaction formula is like (1), (2).
Cathodic reduction reaction: M
N++ ne → M ↓ (1)
Anodic oxidation reactions:
Final under the acting in conjunction of electrode reaction and membrane sepn, the solution of two utmost point chambers changes respectively as follows: the metals ion in the cathode compartment solution of metal sulfates is reduced to pure metal simple substance, SO on negative electrode
4 2-Move out of cathode compartment and get into the anolyte compartment, metal sulfate concentration constantly reduces, and the anolyte compartment constantly accepts the H that the anode water oxidation produces
+The SO that migration is come with cathode compartment
4 2-, form the sulfuric acid sub product, recyclable utilization again.
This kind film electrodeposition process not only can prevent that the anodic oxidation product from getting into cathode compartment, and not influence also proper mass of cathodic metal, can also guarantee stable working condition simultaneously comprehensively.Also have the anolyte compartment to produce vitriolic sub product income in addition.
The present invention relates to a kind of novel metal electrodeposition refinery practice cathode compartment electric effusion is single pure metal sulfate, can not allow any other material to get into electric effusion, can be NiSO
4, CuSO
4, CoSO
4, ZnSO
4
The dilute sulphuric acid concentration of injecting when the present invention relates to a kind of novel metal electrodeposition refinery practice initial launch is 0.5%～1%.
The present invention relates to a kind of novel metal electrodeposition refinery practice gained H of anolyte compartment
2SO
4Concentration is 5%～10%.
The present invention relates to a kind of novel metal electrodeposition refinery practice anion-selective barrier film and select Nafion series membranes, ACIPLEX-F series membranes, Flemion film for use.
The present invention relates to a kind of novel metal electrodeposition refinery practice negative electrode and adopt the pure metal material, select nickel plate, copper coin, cobalt plate, zine plate for use, anode employing titanium is coated with ruthenium iridium, titanium is coated with ruthenium, graphite electrode plate.
The advantage that has:
This technology is applicable to the metal sulfate to be the metal electrodeposition refining process of raw material, and gained metal product quality is good, and energy consumption is low, non-environmental-pollution.Gained H
2SO
4Sub product, recyclable utilization again, economic worth is high.This novel metal electrodeposition refinery practice is a novel process that meets following green chemical industry environmental protection developing direction.
Embodiment
A kind of novel metal electrodeposition refinery practice; Utilize the anion-selective barrier film that Winning cell is divided into anolyte compartment and cathode compartment; Through the negative electrode recycle system metal sulfate liquid is injected cathode compartment, metals ion is in cathodic reduction, and initial launch is injected the anolyte compartment through the anode recycle system with dilute sulphuric acid; Along with the carrying out of electrolytic deposition process, can obtain high density H in the anolyte compartment
2SO
4, extract H through the anode recycle system
2SO
4, technology is dissolved in the acidleach that can be back to hydrometallurgy, and adds the pure water of equivalent simultaneously.
Embodiment 1
As the electrodeposition liquid stock, is to obtain high density NiSO through the molten leaching of acid, IX enrichment with nickel-contained waste slag
4, NiSO
4Concentration is 2.6g/L～2.8g/L, and pH=4.5, electric current are 20mA/cm
2～30mA/cm
2Anode selects for use inert electrode-titanium to be coated with ruthenium plate or net, and negative electrode is selected the pure metallic nickel plate for use, and the anion selectivity barrier film is selected the ACIPLEX-F series membranes for use; By the negative electrode circulatory system with NiSO
4Solution injects cathode chamber, metal ion Ni
2+In cathodic reduction is metal Ni; By the anode circulatory system 0.5% dilute sulfuric acid is injected the anode chamber during initial launch, as the H of anode chamber
2SO
4Concentration is 10% o'clock, utilizes the anode circulatory system to extract H
2SO
4, and add the pure water of equivalent simultaneously.The metal Ni purity of cathodic reduction can reach more than 99.6% through measuring.
Embodiment 2
To contain the cobalt waste residue, be to obtain high density CoSO through the molten leaching of acid, IX enrichment as the electrodeposition liquid stock
4, CoSO
4Concentration is 5.7g/L, and pH=5.0, electric current are 50mA/cm
2Anode adopts titanium to be coated with the ruthenium mesh electrode, and negative electrode adopts rectangle simple metal Co plate, and the anion selectivity barrier film is selected the Flemion film for use; By the cathode chamber circulatory system with CoSO
4Inject cathode chamber, metal ion Co
2+In the cathodic reduction metal Co; By the anode circulatory system 0.5% dilute sulfuric acid is injected the anode chamber during initial launch, as the H of anode chamber
2SO
4Concentration is 8%, utilizes the anode circulatory system to extract H
2SO
4, and add the pure water of equivalent simultaneously.The metal Co purity of cathodic reduction can reach more than 99.5% through measuring.
Claims (6)
1. novel metal electrodeposition refinery practice: utilize the anion-selective barrier film that Winning cell is divided into anolyte compartment and cathode compartment; Through the negative electrode recycle system solution of metal sulfates is injected cathode compartment; Metals ion is a metal in cathodic reduction; Through the anode recycle system dilute sulphuric acid is injected the anolyte compartment during initial launch,, can obtain high density H in the anolyte compartment along with electrode process carries out
2SO
4, extract H through the anode recycle system
2SO
4, and add the pure water of equivalent simultaneously.
2. a kind of novel metal electrodeposition refinery practice according to claim 1, it is characterized in that: the cathode compartment electric effusion is single pure metal sulfate, can not allow any other material to get into electric effusion, can be NiSO
4, CuSO
4, CoSO
4, ZnSO
4
3. a kind of novel metal electrodeposition refinery practice according to claim 1, it is characterized in that: the dilute sulphuric acid concentration of injecting during initial launch is 0.5%～1%.
4. a kind of novel metal electrodeposition refinery practice according to claim 1 is characterized in that: the gained sub product H of anolyte compartment
2SO
4Concentration is 5%～10%.
5. a kind of novel metal electrodeposition refinery practice according to claim 1, it is characterized in that: the anion-selective barrier film is selected Nafion series membranes, ACIPLEX-F series membranes, Flemion film for use.
6. a kind of novel metal electrodeposition refinery practice according to claim 1; It is characterized in that: different according to cathode compartment electric effusion type; Negative electrode adopts the pure metal material, selects nickel plate, copper coin, cobalt plate, zine plate for use, and anode employing titanium is coated with ruthenium iridium, titanium is coated with ruthenium, graphite electrode plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102591854A CN102828205A (en) | 2011-08-26 | 2011-08-26 | Novel metal electro-deposition refining technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102591854A CN102828205A (en) | 2011-08-26 | 2011-08-26 | Novel metal electro-deposition refining technology |
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| Publication Number | Publication Date |
|---|---|
| CN102828205A true CN102828205A (en) | 2012-12-19 |
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ID=47331501
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|---|---|---|---|
| CN2011102591854A Pending CN102828205A (en) | 2011-08-26 | 2011-08-26 | Novel metal electro-deposition refining technology |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103388161A (en) * | 2013-08-20 | 2013-11-13 | 兰州交通大学 | Membrane electrode device for refining metal sulfate solution |
| CN104532293A (en) * | 2014-12-22 | 2015-04-22 | 无锡市瑞思科环保科技有限公司 | Method of purifying nickel from chemical nickel-plating waste liquid and nickel purification device |
| CN110724964A (en) * | 2019-11-20 | 2020-01-24 | 深圳市臻鼎环保科技有限公司 | Preparation method of nickel sulfamate solution |
| CN111621810A (en) * | 2020-07-19 | 2020-09-04 | 河南科技大学 | Method for reducing cobalt dendrite growth in high-purity cobalt electrolytic refining process |
| CN114318418A (en) * | 2021-12-30 | 2022-04-12 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670258A (en) * | 2005-02-06 | 2005-09-21 | 金川集团有限公司 | Method for producing copper powder by electrodeposition |
-
2011
- 2011-08-26 CN CN2011102591854A patent/CN102828205A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670258A (en) * | 2005-02-06 | 2005-09-21 | 金川集团有限公司 | Method for producing copper powder by electrodeposition |
Non-Patent Citations (1)
| Title |
|---|
| 熊志臣等: "应用阴离子交换膜从氯化亚铜中电解沉积铜的试验研究", 《水处理技术》, no. 4, 31 December 1981 (1981-12-31), pages 5 - 7 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103388161A (en) * | 2013-08-20 | 2013-11-13 | 兰州交通大学 | Membrane electrode device for refining metal sulfate solution |
| CN103388161B (en) * | 2013-08-20 | 2016-05-11 | 兰州交通大学 | A kind of film electrowinning plant for solution of metal sulfates refining |
| CN104532293A (en) * | 2014-12-22 | 2015-04-22 | 无锡市瑞思科环保科技有限公司 | Method of purifying nickel from chemical nickel-plating waste liquid and nickel purification device |
| CN104532293B (en) * | 2014-12-22 | 2017-06-09 | 无锡市瑞思科环保科技有限公司 | The method of purifying nickel and nickel purifying plant in chemical nickel plating waste solution |
| CN110724964A (en) * | 2019-11-20 | 2020-01-24 | 深圳市臻鼎环保科技有限公司 | Preparation method of nickel sulfamate solution |
| CN111621810A (en) * | 2020-07-19 | 2020-09-04 | 河南科技大学 | Method for reducing cobalt dendrite growth in high-purity cobalt electrolytic refining process |
| CN114318418A (en) * | 2021-12-30 | 2022-04-12 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
| CN114318418B (en) * | 2021-12-30 | 2024-01-26 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
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Application publication date: 20121219 |
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