CN102839396B - A kind of film Winning cell for metal chloride refining - Google Patents
A kind of film Winning cell for metal chloride refining Download PDFInfo
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- CN102839396B CN102839396B CN201210366017.XA CN201210366017A CN102839396B CN 102839396 B CN102839396 B CN 102839396B CN 201210366017 A CN201210366017 A CN 201210366017A CN 102839396 B CN102839396 B CN 102839396B
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Abstract
The invention provides a kind of film Winning cell for metal chloride refining, comprise cell body, anode, negative electrode, anode chamber's circulation line, middle compartment circulation line and cathode chamber circulation line, described cell body is by the anode chamber of adjacency from left to right, middle compartment, cathode chamber composition, anode chamber and middle compartment are separated by cation selective barrier film, middle compartment and cathode chamber are separated by anion selectivity barrier film, anode chamber fills anolyte, middle compartment fills hydrochloric acid solution, cathode chamber fills catholyte, described anode chamber's circulation line, middle compartment circulation line, cathode chamber circulation line is connected respectively in anode chamber, middle compartment, the top of cathode chamber and bottom. the present invention solves the problem that in common metal chloride electrolytic deposition process, chlorine produces completely, non-environmental-pollution, and can obtain byproduct hydrochloric acid, and recycling, economic worth is high, and gained metal product quality is good.
Description
Technical field
The invention provides a kind of film Winning cell for metal chloride refining, is a kind of by the device of electrochemistry and membrane separation technique combination, belongs to metal smelt field.
Background technology
At present, the Winning cell major part that in domestic hydrometallurgy field, refining of metal adopts is all to open wide system, and without barrier film setting. Many group anodes and negative electrode are in together in a large metallic compound electrolyte environment, and electrolyte flow is slow, almost static. Open type Winning cell has such shortcoming: if electrolyte volatilizees or have γ-ray emission in electrolytic process, can cause Leakage Gas, enter working environment, if the gas poisonous and harmful producing, can cause severe contamination to environment, can cause very big infringement to staff is healthy simultaneously. Especially the electrodeposition refining process using metal chloride solutions as electrolyte, due to the chlorion that contains high concentration, can be become chlorine by anodic oxidation, the chlorine producing not only can change the character of electrolyte, affect metal electrodeposition quality, and chlorine overflows and causes workshop internal environment severe contamination, even operating personnel's work that Wear respirator. A large amount of chlorine producing is further processed after also must collecting, and to eliminate the impact of chlorine External Environment, the processing of chlorine can cause the further raising of production cost. There is the closed electrodeposition groove of employing in enterprise both at home and abroad, to solve chlorine pollution working environment problem, but has dismounting minus plate operation inconvenience, and dismounting causes the not tight or flimsy problem of sealing surface repeatedly
Summary of the invention
The object of the invention: the open type being adopted for the above-mentioned common metal refinery practice that is raw material with metal chloride or the shortcoming of closed electrolytic tank, provide one can avoid chlorine to produce completely, thoroughly solve the membrane electrolysis cells of chlorine pollution environmental problem.
Concrete technical scheme: a kind of film Winning cell for metal chloride refining, comprise cell body, anode, negative electrode, anode chamber's circulation line, middle compartment circulation line and cathode chamber circulation line, described cell body is by the anode chamber of adjacency from left to right, middle compartment, cathode chamber composition, anode chamber and middle compartment are separated by cation selective barrier film, middle compartment and cathode chamber are separated by anion selectivity barrier film, anode chamber fills anolyte, middle compartment fills hydrochloric acid solution, cathode chamber fills catholyte, described anode chamber's circulation line, middle compartment circulation line, cathode chamber circulation line is connected respectively in anode chamber, middle compartment, the top of cathode chamber and bottom, it is characterized in that:
(1) anode chamber's circulation line is connected in sequence by anolyte import, anolyte circulating box, anolyte force (forcing) pump, and anolyte import is positioned at anolyte circulating box top;
(2) in, compartment circulation line is connected in sequence by extracting mouth, valve 2, valve 1, middle compartment inlet, middle compartment circulating box, middle compartment force (forcing) pump, and middle compartment inlet is arranged in compartment circulating box top;
(3) cathode chamber circulation line is connected in sequence by catholyte import, catholyte circulating box, catholyte force (forcing) pump, and catholyte import is positioned at catholyte circulating box top.
Described cation selective barrier film and anion selectivity barrier film quantity are all 1, be arranged in parallel, are fixed in cell body by two sheet plastic pressings bonding and with draw-in groove.
Described cell body is made up of lucite, fiberglass or polytetrafluoroethylplastic plastic, is shaped as cuboid.
Catholyte in described cathode chamber is cobalt chloride solution.
Described negative electrode is tabular.
Described anode is tabular or netted.
The feature that the present invention possesses:
This film Winning cell is applicable to the metal electro-deposition refining process taking metal chloride as raw material, produces non-environmental-pollution without chlorine; Can obtain the recycling of hydrochloric acid byproduct at middle compartment, economic worth is high; Gained metal product quality is good,
Brief description of the drawings
A kind of membrane electrolysis cells structural representation for metal chloride refining of Fig. 1
1-cation selective barrier film, 2-anion selectivity barrier film, 3-anode chamber, compartment in 4-, 5-cathode chamber, 6-anode, 7-negative electrode, 8-anode chamber circulation line, 9-anolyte force (forcing) pump,, 10-anolyte circulating box, the import of 11-anolyte, 12-cathode chamber circulation line, 13-catholyte force (forcing) pump, 14-catholyte circulating box, the import of 15-catholyte, compartment circulation line in 16-, compartment force (forcing) pump in 17-, compartment circulating box in 18-, compartment inlet in 19-, 20-valve 1,21-valve 2,22-extracts mouth, 23-cell body.
Detailed description of the invention
Below in conjunction with accompanying drawing 1, the present invention is elaborated.
As shown in Figure 1, a kind of film Winning cell for metal chloride refining, comprise cell body 23, anode 6, negative electrode 7, anode chamber's circulation line 8, middle compartment circulation line 16 and cathode chamber circulation line 12, described cell body 23 is by the anode chamber 3 of adjacency from left to right, middle compartment 4, cathode chamber 5 forms, anode chamber 3 is separated by cation selective barrier film 1 with middle compartment 4, middle compartment 4 is separated by anion selectivity barrier film 2 with cathode chamber 5, anode chamber 3 fills anolyte, middle compartment 4 is contained hydrochloric acid solution, cathode chamber 5 fills catholyte, described anode chamber's circulation line 8, middle compartment circulation line 16, cathode chamber circulation line 12 is connected respectively in anode chamber 3, middle compartment 4, the top of cathode chamber 5 and bottom, it is characterized in that:
(1) anode chamber's circulation line 8 is connected in sequence by anolyte import 11, anolyte circulating box 10, anolyte force (forcing) pump 9; Anolyte import 11 is positioned at anolyte circulating box 10 tops;
(2) in, compartment circulation line 16 is connected in sequence by extraction mouth 22, valve 2 (21), valve 1 (20), middle compartment inlet 19, middle compartment circulating box 18, middle compartment force (forcing) pump 17, and middle compartment inlet 19 is arranged in compartment circulating box 18 tops;
(3) cathode chamber circulation line 12 is connected in sequence by catholyte import 15, catholyte circulating box 14, catholyte force (forcing) pump 13, and catholyte import 15 is positioned at catholyte circulating box 14 tops.
Described cation selective barrier film 1 and anion selectivity barrier film 2 quantity are all 1, be arranged in parallel, with after two sheet plastic pressings bonding, are fixed in cell body 23 with draw-in groove.
Described cell body 23 is made up of lucite, fiberglass or polytetrafluoroethylplastic plastic, is shaped as cuboid.
Catholyte in described cathode chamber 5 is metal chloride electrolyte, as cobalt chloride solution, nickel chloride solution.
Described negative electrode 7 is tabular.
Described anode 6 is tabular or netted.
Anolyte, hydrochloric acid solution and catholyte flow into anode chamber 3, middle compartment 4 and cathode chamber 5 by anode chamber's circulation line 8, middle compartment circulation line 16 and cathode chamber circulation line 12 correspondences respectively, maintain separately constant density. When Winning cell initial launch, the concentration that middle compartment 4 injects hydrochloric acid solution is 0.5%～1%, and now the valve 1 on middle compartment circulation line 16 is opened, and valve 2 is closed; Along with the carrying out of electrolytic deposition process, central compartment 4 concentration of hydrochloric acid solution reach 5%～10%, and the valve 1 on middle compartment circulation line 16 is closed, and valve 2 is opened, and hydrochloric acid solution, by extracting mouthful 22 discharges, injects the pure water of equivalent simultaneously to middle compartment 4.
Embodiment 1
With solid cobalt chloride preparation electrolyte, concentration is 45g/L. Cell body 23 is made up of lucite, is shaped as cuboid. Anode 6 is selected inert electrode Tai Tu iridium net, and negative electrode 7 is selected simple metal cobalt plate; Cation selective barrier film 1 is selected perfluor cationic membrane, and anion selectivity barrier film 2 is selected Flemion film, and they are respectively with after two sheet plastic pressings bonding, is fixed in cell body 23 with draw-in groove, and be arranged in parallel, and spacing is 50mm. 1% sulfuric acid solution, 0.5% hydrochloric acid solution and 45g/L cobalt chloride electrolyte are flow into anode chamber 3, middle compartment 4 and cathode chamber 5 by anode chamber's circulation line 8, middle compartment circulation line 16 and cathode chamber circulation line 12 correspondences respectively, maintain constant density at electrolytic deposition process Anodic liquid and catholyte, pass into direct current electrodeposition after 3 hours, after testing, chlorine ion concentration approaches zero to sulfuric acid solution in anode chamber 3; Obtain electrode reducing metal cobalt at negative electrode 7, its purity is 99.7% after testing; The concentration of hydrochloric acid solution of middle compartment 4 gained is 7%, by extracting mouthful 22 discharges, injects the pure water of equivalent to middle compartment simultaneously.
Embodiment 2
Cell body 23 is made up of fiberglass, is shaped as cuboid. Anode 6 is selected inert electrode Tai Tu the Liao Dynasty net, and negative electrode 7 is selected pure metallic nickel plate; Cation selective barrier film 1 is selected perfluor cationic membrane, and anion selectivity barrier film 2 is selected Flemion film, and they are respectively with after two sheet plastic pressings bonding, is fixed in cell body 23 with draw-in groove, and be arranged in parallel, and spacing is 60mm. 0.8% sulfuric acid solution, 1% hydrochloric acid solution and 20g/L nickel chloride electrolyte are flow into anode chamber 3, middle compartment 4 and cathode chamber 5 by anode chamber's circulation line 8, middle compartment circulation line 16 and cathode chamber circulation line 12 correspondences respectively, maintain constant density at electrolytic deposition process Anodic liquid and catholyte, pass into direct current electrodeposition after 4 hours, after testing, chlorine ion concentration approaches zero to sulfuric acid solution in anode chamber 3; Obtain electrode reducing metal nickel at negative electrode 7, its purity is 98.9% after testing; The concentration of hydrochloric acid solution of middle compartment 4 gained is 10%, by extracting mouthful 22 discharges, injects the pure water of equivalent to middle compartment 4 simultaneously.
Claims (4)
1. for a film Winning cell for metal chloride refining, comprise cell body, anode, negative electrode, anode chamber's circulation line, inCompartment circulation line and cathode chamber circulation line, described cell body is by anode chamber, middle compartment, the cathode chamber group of adjacency from left to rightBecome, anode chamber and middle compartment are separated by perfluor cationic membrane, and middle compartment and cathode chamber are separated by Flemion film, and anode chamber fillsAnolyte, middle compartment fills hydrochloric acid solution, and cathode chamber fills catholyte, described anode chamber's circulation line, middle compartment circulation pipeRoad, cathode chamber circulation line are connected respectively in anode chamber, top and the bottom of middle compartment, cathode chamber, it is characterized in that:
(1) anode chamber's circulation line is connected in sequence by anolyte import, anolyte circulating box, anolyte force (forcing) pump, anodeLiquid import is positioned at anolyte circulating box top;
(2) in compartment circulation line by extract mouth, valve 2, valve 1, middle compartment inlet, middle compartment circulating box, in everyChamber force (forcing) pump is connected in sequence, and middle compartment inlet is arranged in compartment circulating box top;
(3) cathode chamber circulation line is connected in sequence by catholyte import, catholyte circulating box, catholyte force (forcing) pump, negative electrodeLiquid import is positioned at catholyte circulating box top.
2. a kind of film Winning cell for metal chloride refining according to claim 1, is characterized in that: described perfluorCationic membrane and Flemion film quantity are all 1, be arranged in parallel, are fixed on by two sheet plastic pressings bonding and with draw-in grooveIn cell body.
3. a kind of film Winning cell for metal chloride refining according to claim 1, is characterized in that: described cell bodyMade by lucite, fiberglass or polytetrafluoroethylplastic plastic, be shaped as cuboid.
4. a kind of film Winning cell for metal chloride refining according to claim 1, is characterized in that: described negative electrodeCatholyte in chamber is cobalt chloride solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210366017.XA CN102839396B (en) | 2012-09-27 | 2012-09-27 | A kind of film Winning cell for metal chloride refining |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210366017.XA CN102839396B (en) | 2012-09-27 | 2012-09-27 | A kind of film Winning cell for metal chloride refining |
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| Publication Number | Publication Date |
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| CN102839396A CN102839396A (en) | 2012-12-26 |
| CN102839396B true CN102839396B (en) | 2016-05-25 |
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| CN201210366017.XA Expired - Fee Related CN102839396B (en) | 2012-09-27 | 2012-09-27 | A kind of film Winning cell for metal chloride refining |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN107354487A (en) * | 2017-07-21 | 2017-11-17 | 耿琮 | A kind of apparatus and method for lifting electrolysis speed |
| CN109112569B (en) * | 2018-09-19 | 2023-07-25 | 兰州交通大学 | Production method for simultaneously preparing manganese metal and manganese dioxide by ion exchange membrane electrolysis method |
| CN110205646B (en) * | 2019-06-25 | 2024-02-02 | 江苏安凯特科技股份有限公司 | Small-size pilot scale experimental apparatus of electrolysis trough |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389789A (en) * | 2004-01-16 | 2009-03-18 | 巴特尔纪念研究所 | Methods and apparatus for producing ferrate (vi) |
| CN202246926U (en) * | 2011-08-30 | 2012-05-30 | 湖南海纳新材料有限公司 | Novel electrolysis bath |
| CN202925116U (en) * | 2012-09-27 | 2013-05-08 | 兰州交通大学 | Membrane electrodeposition tank for refining metal chlorides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0911653B1 (en) * | 2008-04-11 | 2019-07-30 | François Cardarelli | ELECTROCHEMICAL PROCESS FOR RECOVERY OF METAL IRON AND SULFURIC ACID VALUES FROM IRON-RICH SULPHATE RESIDUES, MINING WASTE AND STRAPPING LIQUIDS |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389789A (en) * | 2004-01-16 | 2009-03-18 | 巴特尔纪念研究所 | Methods and apparatus for producing ferrate (vi) |
| CN202246926U (en) * | 2011-08-30 | 2012-05-30 | 湖南海纳新材料有限公司 | Novel electrolysis bath |
| CN202925116U (en) * | 2012-09-27 | 2013-05-08 | 兰州交通大学 | Membrane electrodeposition tank for refining metal chlorides |
Non-Patent Citations (1)
| Title |
|---|
| 膜电解法在处理酸性含镍废水中的研究;唐玉霖 等;《工业用水与废水》;20040630;第35卷(第3期);38-41 * |
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