CN101235521A - Energy-saving anode for non-ferrous metal electrodeposition - Google Patents
Energy-saving anode for non-ferrous metal electrodeposition Download PDFInfo
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- CN101235521A CN101235521A CNA2007100343406A CN200710034340A CN101235521A CN 101235521 A CN101235521 A CN 101235521A CN A2007100343406 A CNA2007100343406 A CN A2007100343406A CN 200710034340 A CN200710034340 A CN 200710034340A CN 101235521 A CN101235521 A CN 101235521A
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Abstract
An energy saving anode used in electro-deposition of nonferrous metal is characterized in that the energy saving anode used in electro-deposition of nonferrous metal comprises a metal-conductive base-plate and at least one block of composite structure which is compounded by a metal layer with porous structure, wherein the structure is frame type, sandwich type and slab lattice type. The energy saving anode not only can effectively reduce true current density of the anode in electro-deposition of the nonferrous metal, reduce overpotential for oxygen evolution of the anode and lower energy consumption, but also can reduce the quality of the anode, reduce the creep deformation and the deformation of the anode, form a more dense oxydic film on the surface, reduce the corrosion rate of the anode, extend the service length of the anode and improve the quality of the cathode products. The energy saving anode can make a full use of the existing anode without changing the structure of the groove and have no effect to the process flow, and the energy saving anode has low preparing cost and low investment.
Description
Technical field
The invention belongs to the hydrometallurgy field, particularly the non-ferrous metal electrodeposition anode.
Background technology
In the wet smelting process of metals such as copper, zinc, manganese, nickel, cobalt, chromium, galvanic deposit is the main power consumption operation of whole technology, anode is one of key part of galvanic deposit operation, and the selection of its material not only directly influences power consumption, electrode life, also influences cathode product quality.Essential satisfied following requirement of generalized case lower electrode material: good conductivity, erosion resistance is strong, physical strength and good processability, the counter electrode reaction has good electrocatalysis.At present, the anode of electrolytic industry use has platinum (titanium platinum plating, sintering platinum) electrode, lead dioxide electrode, titanium-based oxide coated electrode, martial ethiops electrode, Graphite Electrodes, lead and lead 2-base alloy electrode etc.But in these electrodes, metal platinum and alloy thereof cost an arm and a leg, and consume significantly when using under high current density; The lead oxides electrode is made difficulty, corrosion-resistant; The titanium-based oxide coated electrode does not fundamentally solve the passivation of titanium matrix, and work-ing life is short; Martial ethiops electrode poor mechanical property is difficult to maximize; Graphite electrode consumption is big, and therefore the overpotential height, all fails to be widely used.Plumbous and with lead be the alloy anode of main component have moulding easily, in sulfuric acid medium advantage such as stable, in production of nonferrous metals, be used widely at present.But, there are shortcomings such as overpotential for oxygen evolution height (near 1V) and surface passivated membrane be not fine and close in lead and lead 2-base alloy anode, (as the zinc electrodeposition is 3.2～3.8V) to cause the bath voltage height, electrolytic deposition process current efficiency low (75～90%), energy consumption height (is 3200～3800 kilowatt-hour/tons as the zinc electrodeposition), anode life short (6～December), the corrosion product of anode lead easily enters the negative electrode product, influences shortcomings such as cathode product quality.
Summary of the invention
The present invention is directed in non-ferrous metal electrodeposition process anode overpotential for oxygen evolution height, energy consumption height and the negative electrode product problems such as Lead contamination is serious, a kind of energy-saving anode for non-ferrous metal electrodeposition of novel texture is provided, and the anode of this class formation has low anode overpotential, corrosion-resistant, life-span length, light weight, manufacturing is easy and have the characteristics of sufficient intensity.
Constitutional features of the present invention is to have the composite structure that the metal level of vesicular structure is formed by conducting metal substrate and at least one, the cellular structure metals layer is connected any one or both sides of conducting metal substrate in the mode of monolithic or polylith by the face contact, also can monolithic or the polylith mode embed the conducting metal substrate.This anode construction can be preferably frame-type, sandwich style or grid formula.Wherein the two-layer equation anode is that porous metallic layers 2 is embedded in the composite structure that forms in the conducting metal substrate 1; The sandwich style anode is to be the middle layer by conducting metal substrate 1, the composite structure that porous metallic layers 2 its both sides of distribution form; Grid formula anode is to be grid by conducting metal substrate 1, and porous metallic layers 2 is embedded in the composite structure that forms in the grid.
The conducting metal substrate can be metallic lead or lead 2-base alloy Pb-Me, and wherein, alloying element Me is at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, the Ba, but alloying element content 0-50wt.%, and thickness is 0.5mm～8mm.Porous metallic layers can be metallic lead or lead 2-base alloy Pb-Me ', wherein, Me ' can be at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, the Fe, its content can be 0.01wt.%～49.9wt.%, thickness is 0.01mm～10mm, porosity is 5%～85%, and the aperture is 0.01～5mm.
The present invention can reduce anode real current density, reduces electrochemical polarization, reduces overpotential for oxygen evolution, and energy efficient improves current efficiency.When being used for the electrodeposition of copper, zinc, manganese, nickel, cobalt, chromium etc., the anode overpotential for oxygen evolution can reduce by 50～180mV, and current efficiency improves 1～10%.Can reduce anodic creep and distortion, the oxide film that the surface is formed is more fine and close, reduces anodic corrosion speed, improves the quality of electrodeposition product.The meniscus liquid film that forms at the three phase boundary place is thinner, increases limiting diffusion current density, reduces concentration polarization, improves the diffusion mass transfer of electrolytic solution.Can make full use of existing anode, need not to change the groove structure, not influence technical process, preparation cost is low, less investment.
Description of drawings
Fig. 1: frame-type anode construction synoptic diagram;
Fig. 2: sandwich style anode construction synoptic diagram;
Fig. 3: grid formula anode construction synoptic diagram.
Number in the figure: 1. conducting metal substrate; 2. porous metallic layers
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Embodiment 1:
As shown in Figure 1, during as copper electrodeposition anode, wherein the conducting metal substrate is pure Pb with tower structure, and thickness is 1mm; Porous metallic layers is the Pb-Ca-Sn alloy, and thickness is 0.5mm, and porosity is 10%, and the aperture is 0.1～0.2mm, and Ca content is 0.12wt.%, and Sn content is 1wt.%.The conducting metal substrate combines with metallurgical state with porous metallic layers, to eliminate contact resistance.This structure anode combines with stainless steel cathode, is 120g/L H at bath composition
2SO
4, 45g/L Cu
2+, temperature is 25 ± 0.5 ℃, current density is 250A/m
2Under the condition during electrolysis, anode is analysed oxygen and is crossed electricity and be 600mv, with the overpotential for oxygen evolution of the Pb base alloy anode of existing industrial application relatively, reduce about 60mV.
Embodiment 2:
As shown in Figure 2, during as zinc electrodeposition anode, wherein the conducting metal substrate is the Pb-Ag alloy with sandwiched type structure, and thickness is 3mm, and Ag content is 0.3wt.%; The both sides porous metallic layers is the Pb-Ag-Ca-Sr quad alloy, and thickness is 2mm, and porosity is 50%, and the aperture is 0.7～0.9mm, and Ag, Ca, Sr content are respectively 0.3wt.%, 0.03wt.%, 0.03wt.%.The conducting metal substrate combines with metallurgical state with the both sides porous metallic layers, to eliminate contact resistance.This structure anode combines with the aluminium negative electrode, is 160g/L H at bath composition
2SO
4, 60g/L Zn
2+, temperature is 35 ± 0.5 ℃, current density is 500A/m
2During electrolysis, the anode overpotential for oxygen evolution is 860mv under the condition, with the overpotential for oxygen evolution of the Pb base alloy anode of existing industrial application relatively, reduce about 90mV.
Embodiment 3:
As shown in Figure 3, during as manganese electrodeposition anode, wherein the metallic conduction plate is the Pb-Sn alloy with grid formula structure, and thickness is 6mm, and Sn content is 40wt.%; Porous metallic layers is the Pb-Sb-Sn-Ag quad alloy, and thickness is 8mm, and porosity is 80%, and the aperture is 4.1～4.2mm, and Sb, Sn, Ag content are respectively 1wt.%, 38wt.%, 0.8wt.%.The conducting metal substrate combines with metallurgical state with porous metallic layers, to eliminate contact resistance.This structure anode combines with the titanium negative electrode, is 120g/L (NH at bath composition
4)
2SO
4, 17g/L Mn
2+, pH value is 7, and temperature is 40 ℃, and current density is 800A/m
2During electrolysis, the anode overpotential for oxygen evolution is 980mv under the condition, with the overpotential for oxygen evolution of the Pb base alloy anode of existing industrial application relatively, reduce about 100mV.
Claims (7)
1. energy-saving anode for non-ferrous metal electrodeposition, it is characterized in that: have the composite structure that the metal level of vesicular structure is formed by conducting metal substrate and at least one, the cellular structure metals layer is connected any one or both sides of conducting metal substrate in the mode of monolithic or polylith by the face contact, or embeds the conducting metal substrate.
2. energy-saving anode for non-ferrous metal electrodeposition according to claim 1 is characterized in that: the composite structure that described cellular structure metals layer is formed is a frame-type, and promptly porous metallic layers is embedded in the composite structure that forms in the conducting metal substrate.
3. energy-saving anode for non-ferrous metal electrodeposition according to claim 1, it is characterized in that: the composite structure that described cellular structure metals layer is formed is a sandwich style, be that the conducting metal substrate is the middle layer, porous metallic layers is distributed in the composite structure that its two sides form.
4. according to the described energy-saving anode for non-ferrous metal electrodeposition of claim 1, it is characterized in that: the composite structure that described cellular structure metals layer is formed is the grid formula, and promptly porous metallic layers is embedded in the composite structure that forms in the grid formula conducting metal substrate.
5. according to claim 1,2,3 or 4 described energy-saving anode for non-ferrous metal electrodeposition, it is characterized in that: the conducting metal substrate is metallic lead or lead 2-base alloy Pb-Me, and wherein alloying element Me is at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, the Ba; Porous metallic layers is metallic lead or lead 2-base alloy Pb-Me ', and wherein Me ' is at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, the Fe.
6. energy-saving anode for non-ferrous metal electrodeposition according to claim 5 is characterized in that: the alloy constituent element Me content of conducting metal substrate is 0～50wt.%, and thickness is 0.5mm～8mm.
7. energy-saving anode for non-ferrous metal electrodeposition according to claim 5, it is characterized in that: the alloy constituent element Me ' content of porous metallic layers is 0.01wt.%～49.9wt.%, thickness is 0.01mm～10mm, and porosity is 5%～85%, and the aperture is 0.01mm～5mm.
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| CN2007100343406A CN101235521B (en) | 2007-01-29 | 2007-01-29 | Energy-saving anode for non-ferrous metal electrodeposition |
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| CN2007100343406A CN101235521B (en) | 2007-01-29 | 2007-01-29 | Energy-saving anode for non-ferrous metal electrodeposition |
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| CN101235521B CN101235521B (en) | 2010-07-14 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022649A1 (en) * | 2008-08-27 | 2010-03-04 | 东莞市松山科技集团有限公司 | Combined negative plate for electrolyzing |
| CN101949031A (en) * | 2010-10-18 | 2011-01-19 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
| CN102274935A (en) * | 2011-07-15 | 2011-12-14 | 云南大泽电极科技有限公司 | Horizontal continuous casting manufacturing method of lead alloy plates |
| CN106835193A (en) * | 2017-03-15 | 2017-06-13 | 江西理工大学 | A kind of Pb bases/3D PbO2/MeOx composite anodes and preparation method thereof |
| CN106854767A (en) * | 2015-12-08 | 2017-06-16 | 胡桂生 | A kind of application in zinc electrolysis of composite anode plate |
| CN108360018A (en) * | 2018-03-20 | 2018-08-03 | 中南大学 | Electrolytic manganese composite anode and preparation method thereof |
| CN112159987A (en) * | 2020-09-03 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Sandwich structure composite lead electrode and preparation method thereof |
| CN114411201A (en) * | 2022-02-15 | 2022-04-29 | 江西理工大学 | Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3973991A (en) * | 1973-02-13 | 1976-08-10 | Nl Industries, Inc. | Light-weight lead-acid battery with laminated electrodes |
| CN1037620C (en) * | 1995-03-17 | 1998-03-04 | 贵州省新材料研究开发基地 | Compound alloy anode for electrolytic production of metal manganes and its preparation method |
| CN2400907Y (en) * | 1999-12-08 | 2000-10-11 | 张宝义 | Lead-high molecular multicomponent polymer composite battery plate electrode |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022649A1 (en) * | 2008-08-27 | 2010-03-04 | 东莞市松山科技集团有限公司 | Combined negative plate for electrolyzing |
| CN101949031A (en) * | 2010-10-18 | 2011-01-19 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
| CN102383145A (en) * | 2010-10-18 | 2012-03-21 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
| WO2012051797A1 (en) * | 2010-10-18 | 2012-04-26 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
| CN102383145B (en) * | 2010-10-18 | 2013-11-06 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
| CN102274935A (en) * | 2011-07-15 | 2011-12-14 | 云南大泽电极科技有限公司 | Horizontal continuous casting manufacturing method of lead alloy plates |
| CN106854767A (en) * | 2015-12-08 | 2017-06-16 | 胡桂生 | A kind of application in zinc electrolysis of composite anode plate |
| CN106835193A (en) * | 2017-03-15 | 2017-06-13 | 江西理工大学 | A kind of Pb bases/3D PbO2/MeOx composite anodes and preparation method thereof |
| CN108360018A (en) * | 2018-03-20 | 2018-08-03 | 中南大学 | Electrolytic manganese composite anode and preparation method thereof |
| CN112159987A (en) * | 2020-09-03 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Sandwich structure composite lead electrode and preparation method thereof |
| CN114411201A (en) * | 2022-02-15 | 2022-04-29 | 江西理工大学 | Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof |
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| CN101235521B (en) | 2010-07-14 |
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