CN102839396A - Membrane electrodeposition cell for metal chloride refinement - Google Patents
Membrane electrodeposition cell for metal chloride refinement Download PDFInfo
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- CN102839396A CN102839396A CN201210366017XA CN201210366017A CN102839396A CN 102839396 A CN102839396 A CN 102839396A CN 201210366017X A CN201210366017X A CN 201210366017XA CN 201210366017 A CN201210366017 A CN 201210366017A CN 102839396 A CN102839396 A CN 102839396A
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Abstract
The invention provides a membrane electrodeposition cell for metal chloride refinement, which comprises a cell body, an anode, a cathode, an anode chamber, a circulation pipeline, a septal chamber circulation pipeline and a cathode chamber circulation pipeline, wherein the cell body is composed of the anode chamber, the septal chamber and the cathode chamber which are connected adjacently from left to right; the anode chamber and the septal chamber are separated by a cationic selective membrane; the septal chamber and the cathode chamber are separated by an anionic selective diaphragm; the anode chamber contains an anolyte; the septal chamber contains a hydrochloric acid solution; the cathode chamber contains a catholyte; and the anode chamber circulation pipeline, the septal chamber circulation pipeline and the cathode chamber circulation pipeline are respectively correspondingly connected to the tops and bottoms of the anode chamber, the septal chamber and the cathode chamber. The invention completely solves the problem of chlorine gas generation in the conventional metal chloride electrodeposition process, does not generate environmental pollution, can obtain the byproduct hydrochloric acid to be recycled, and has the advantages of high economic value and high metal product quality.
Description
Technical field
The present invention provides a kind of metal chloride purified film Winning cell that is used for, and is a kind of device with electrochemistry and membrane separation technique combination, belongs to the Metal smelting field.
Background technology
At present, the Winning cell major part that refining of metal adopted in the domestic hydrometallurgy field all is to open wide system, and does not have the barrier film setting.Many group anodes and negative electrode are in together in the big metallic compound electrolytic solution environment, and electrolyte flow is slow, and is almost static.The open type Winning cell has such shortcoming: electrolytic solution is if volatilization perhaps has gas to produce in electrolytic process; Can cause gas leakage, get into Working environment, if the gas poisonous and harmful that produces; Can cause severe contamination to environment, can cause very big infringement to the staff is healthy simultaneously.Especially with the electrodeposition refining process of metal chloride solutions as electrolytic solution; Owing to contain the cl ions of high density; Can be become chlorine by anodic oxidation, the chlorine of generation not only can change the character of electrolytic solution, influences the metal electrodeposition quality; And chlorine overflows and causes production plant internal medium severe contamination, even operator's work that Wear respirator.A large amount of chlorine that produce also must be collected the back and further handle, and to eliminate the influence of chlorine to 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, pollutes the Working environment problem to solve chlorine, but has dismounting negative plate operation inconvenience, and dismounting causes the not tight or flimsy problem of trim repeatedly
Summary of the invention
The object of the invention: to above-mentioned be the open type that adopted of the common metal refinery practice of raw material or the shortcoming of closed electrolysis groove with the metal chloride, provide a kind of chlorine of avoiding fully to produce, thoroughly solve the membrane electrolyser of chlorine environmental pollution problem.
Concrete technical scheme: a kind of metal chloride purified film Winning cell that is used for; Comprise cell body, anode, negative electrode, anolyte compartment's circulation line, middle compartment circulation line and cathode compartment circulation line; Described cell body is by anolyte compartment, middle compartment, the cathode compartment of adjacency are formed from left to right; Anolyte compartment and middle compartment are separated by the cation selective barrier film, and middle compartment and cathode compartment are separated by the anion-selective barrier film, and the anolyte compartment fills anolyte; Middle compartment fills hydrochloric acid soln; Cathode compartment fills catholyte, and corresponding respectively top and the bottom that is connected in anolyte compartment, middle compartment, cathode compartment of described anolyte compartment circulation line, middle compartment circulation line, cathode compartment circulation line is characterized in that:
(1) anolyte compartment's circulation line is connected in sequence by anolyte import, anolyte circulating box, anolyte force (forcing) pump, and the anolyte import is positioned at anolyte circulating box top;
(2) the compartment circulation line is connected in sequence by extraction mouth, valve 2, valve 1, middle compartment fluid inlet, middle compartment circulating box, middle compartment force (forcing) pump in, and middle compartment fluid inlet is arranged in compartment circulating box top;
(3) the cathode compartment circulation line is connected in sequence by catholyte import, catholyte circulating box, catholyte force (forcing) pump, and the catholyte import is positioned at catholyte circulating box top.
Described cation selective barrier film and anion-selective barrier film quantity are 1 all, laterally arrange, and are fixed in the cell body with two sheet plastic pressing bondings and with draw-in groove.
Described cell body is processed by synthetic glass, glass reinforced plastic or polytetrafluoroethylplastic plastic, is shaped as rectangular parallelepiped.
Catholyte in the described cathode compartment is a metal chloride electrolytic solution, like cobalt chloride solution, nickel chloride solution.
Described negative electrode is tabular.
Described anode is tabular or netted.
The characteristics that the present invention possesses:
This film Winning cell is applicable to the metal chloride to be the metal electrodeposition refining process of raw material, and no chlorine produces, non-environmental-pollution; Can obtain the recycling of hydrochloric acid sub product at middle compartment, economic worth is high; Gained metal product quality is good,
Description of drawings
A kind of metal chloride purified membrane electrolyser structural representation that is used for of Fig. 1
1-cation selective barrier film, 2-anion-selective barrier film, 3-anolyte compartment, compartment among the 4-, 5-cathode compartment; The 6-anode, 7-negative electrode, 8-anolyte compartment circulation line, 9-anolyte force (forcing) pump; 10-anolyte circulating box, the import of 11-anolyte, 12-cathode compartment circulation line, 13-catholyte force (forcing) pump, 14-catholyte circulating box; The import of 15-catholyte, compartment circulation line among the 16-, compartment force (forcing) pump among the 17-, compartment circulating box among the 18-, compartment fluid inlet among the 19-; 20-valve 1,21-valve 2,22-extract mouth, 23-cell body.
Embodiment
1 couple of the present invention elaborates below in conjunction with accompanying drawing.
As shown in Figure 1; A kind of metal chloride purified film Winning cell that is used for; Comprise cell body 23, anode 6, negative electrode 7, anolyte compartment's circulation line 8, middle compartment circulation line 16 and cathode compartment circulation line 12, described cell body 23 is made up of anolyte compartment 3, middle compartment 4, the cathode compartment 5 of adjacency from left to right, and anolyte compartment 3 is separated by cation selective barrier film 1 with middle compartment 4; Middle compartment 4 is separated by anion-selective barrier film 2 with cathode compartment 5; Anolyte compartment 3 fills anolyte, and middle compartment 4 is contained hydrochloric acid soln, and cathode compartment 5 fills catholyte; Corresponding respectively top and the bottom that is connected in anolyte compartment 3, middle compartment 4, cathode compartment 5 of described anolyte compartment circulation line 8, middle compartment circulation line 16, cathode compartment circulation line 12 is characterized in that:
(1) anolyte compartment'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) compartment circulation line 16 is connected in sequence by extraction mouth 22, valve 2 (21), valve 1 (20), middle compartment fluid inlet 19, middle compartment circulating box 18, middle compartment force (forcing) pump 17 in, and middle compartment fluid inlet 19 is arranged in compartment circulating box 18 tops;
(3) cathode compartment 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 is 1 all with anion-selective barrier film 2 quantity, laterally arranges, and after two sheet plastic pressing bondings, is fixed in the cell body 23 with draw-in groove.
Described cell body 23 is processed by synthetic glass, glass reinforced plastic or polytetrafluoroethylplastic plastic, is shaped as rectangular parallelepiped.
Catholyte in the described cathode compartment 5 is a metal chloride electrolytic solution, like cobalt chloride solution, nickel chloride solution.
Described negative electrode 7 is tabular.
Described anode 6 is tabular or netted.
Anolyte, hydrochloric acid soln and catholyte flow into anolyte compartment 3, middle compartment 4 and cathode compartment 5 by anolyte compartment's circulation line 8, middle compartment circulation line 16 and cathode compartment circulation line 12 correspondences respectively, keep constant density separately.During the Winning cell initial launch, the concentration that middle compartment 4 injects hydrochloric acid soln is 0.5%～1%, and the valve 1 in this moment on the 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 the middle compartment circulation line 16 is closed, and valve 2 is opened, and hydrochloric acid soln injects the pure water of equivalent simultaneously by extracting mouthful 22 discharges to middle compartment 4.
Embodiment 1
With solid NSC 51149 preparing electrolyte, concentration is 45g/L.Cell body 23 is processed by synthetic glass, is shaped as rectangular parallelepiped.Anode 6 selects for use the inert electrode titanium to be coated with the iridium net, and negative electrode 7 is selected simple metal cobalt plate for use; Cation selective barrier film 1 is selected the perfluor cationic membrane for use, and anion selectivity barrier film 2 is selected the Flemion film for use, and they with after two sheet plastic pressing bondings, are fixed in the cell body 23 with draw-in groove, and laterally arrange respectively, and spacing is 50mm.1% sulphuric acid soln, 0.5% hydrochloric acid soln and 45g/L NSC 51149 electrolytic solution are flow into anolyte compartment 3, middle compartment 4 and cathode compartment 5 by anolyte compartment's circulation line 8, middle compartment circulation line 16 and cathode compartment circulation line 12 correspondences respectively; Anolyte and catholyte are kept constant density in electrolytic deposition process; Feed the direct current electrodeposition after 3 hours; Sulphuric acid soln in the anolyte compartment 3 is through detecting, and chlorine ion concentration is near zero; Obtaining electrode reducing metal cobalt at negative electrode 7, is 99.7% through detecting its purity; The concentration of hydrochloric acid solution of middle compartment 4 gained is 7%, by extracting mouthful 22 discharges, injects the pure water of equivalent simultaneously to middle compartment.
Embodiment 2
Claims (6)
1. one kind is used for metal chloride purified film Winning cell; Comprise cell body, anode, negative electrode, anolyte compartment's circulation line, middle compartment circulation line and cathode compartment circulation line, described cell body is made up of anolyte compartment, middle compartment, the cathode compartment of adjacency from left to right, and anolyte compartment and middle compartment are separated by the cation selective barrier film; Middle compartment and cathode compartment are separated by the anion-selective barrier film; The anolyte compartment fills anolyte, and middle compartment fills hydrochloric acid soln, and cathode compartment fills catholyte; Corresponding respectively top and the bottom that is connected in anolyte compartment, middle compartment, cathode compartment of described anolyte compartment circulation line, middle compartment circulation line, cathode compartment circulation line is characterized in that:
(1) anolyte compartment's circulation line is connected in sequence by anolyte import, anolyte circulating box, anolyte force (forcing) pump, and the anolyte import is positioned at anolyte circulating box top;
(2) the compartment circulation line is connected in sequence by extraction mouth, valve 2, valve 1, middle compartment fluid inlet, middle compartment circulating box, middle compartment force (forcing) pump in, and middle compartment fluid inlet is arranged in compartment circulating box top;
(3) the cathode compartment circulation line is connected in sequence by catholyte import, catholyte circulating box, catholyte force (forcing) pump, and the catholyte import is positioned at catholyte circulating box top.
2. a kind of metal chloride purified film Winning cell that is used for according to claim 1; It is characterized in that: described cation selective barrier film and anion-selective barrier film quantity all are 1; Laterally arrange, be fixed in the cell body with two sheet plastic pressing bondings and with draw-in groove.
3. a kind of metal chloride purified film Winning cell that is used for according to claim 1, it is characterized in that: described cell body is processed by synthetic glass, glass reinforced plastic or polytetrafluoroethylplastic plastic, is shaped as rectangular parallelepiped.
4. a kind of metal chloride purified film Winning cell that is used for according to claim 1, it is characterized in that: the catholyte in the described cathode compartment is a metal chloride electrolytic solution, like cobalt chloride solution, nickel chloride solution.
5. a kind of metal chloride purified film Winning cell that is used for according to claim 1, it is characterized in that: described negative electrode is tabular.
6. a kind of metal chloride purified film Winning cell that is used for according to claim 1, it is characterized in that: described anode is tabular or netted.
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 true CN102839396A (en) | 2012-12-26 |
| CN102839396B CN102839396B (en) | 2016-05-25 |
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Cited By (4)
| 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 |
| CN107354487A (en) * | 2017-07-21 | 2017-11-17 | 耿琮 | A kind of apparatus and method for lifting electrolysis speed |
| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
| CN110205646A (en) * | 2019-06-25 | 2019-09-06 | 江苏安凯特科技股份有限公司 | A kind of electrolytic cell small scale pilot experimental provision |
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| US20110089045A1 (en) * | 2008-04-11 | 2011-04-21 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| 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 |
-
2012
- 2012-09-27 CN CN201210366017.XA patent/CN102839396B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389789A (en) * | 2004-01-16 | 2009-03-18 | ***纪念研究所 | Methods and apparatus for producing ferrate (vi) |
| US20110089045A1 (en) * | 2008-04-11 | 2011-04-21 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| CN202246926U (en) * | 2011-08-30 | 2012-05-30 | 湖南海纳新材料有限公司 | Novel electrolysis bath |
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Non-Patent Citations (1)
| Title |
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| 唐玉霖 等: "膜电解法在处理酸性含镍废水中的研究", 《工业用水与废水》, vol. 35, no. 3, 30 June 2004 (2004-06-30) * |
Cited By (7)
| 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 |
| CN107354487A (en) * | 2017-07-21 | 2017-11-17 | 耿琮 | A kind of apparatus and method for lifting electrolysis speed |
| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
| 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 |
| CN110205646A (en) * | 2019-06-25 | 2019-09-06 | 江苏安凯特科技股份有限公司 | A kind of electrolytic cell small scale pilot experimental provision |
| 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 |
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| CN102839396B (en) | 2016-05-25 |
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