CN101538724A - Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning - Google Patents
Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning Download PDFInfo
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- CN101538724A CN101538724A CN200910094405A CN200910094405A CN101538724A CN 101538724 A CN101538724 A CN 101538724A CN 200910094405 A CN200910094405 A CN 200910094405A CN 200910094405 A CN200910094405 A CN 200910094405A CN 101538724 A CN101538724 A CN 101538724A
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Abstract
The invention relates to a method for preparing an energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning, and the method is characterized in that: a serrated pattern is compressed on the surface of a polar plate with a lead-based multinary alloy substrate, and a PbO2 and MnO2 conductive ceramics is prepared on the surface of the serrated pattern. The method adopts the physical and the electro-chemical methods for preparing the metal-based ceramic inert anode material which takes lead-based multinary alloy as the substrate. When the metal-based ceramic inert anode material is used in electrowinning, as the surface of an anode is the conductive ceramic material, the surface of the anode is in the insoluble state, thereby being capable of reducing the pollution of lead dissolution of the anode to a cathode product, improving the quality of the cathode product and ensuring the qualified rate of a cathode zinc No. 0 product to achieve 99 percent. The use of the compound electrode can significantly reduce the bath voltage during the electrowinning process and further reduce the power consumption. When in electrowinning of zinc, copper, nickel, cobalt, manganese and the like, the bath voltage can be reduced by 0.3-0.5V, and the current efficiency can be improved by 2-3 percent.
Description
Technical field
The present invention relates to the matrix material that field of metal surface treatment is used, specifically is the preparation method of a kind of non-ferrous metal electrodeposition with energy-saving metal-based ceramic inert anode material.
Background technology
Extract in wet method in the metal process such as zinc, copper, nickel, cobalt, manganese, anode material still uses lead and lead alloy at present, its shortcoming is: bath voltage height (3.4～3.8V), current efficiency low (75～88%), electrolytic deposition process energy consumption height (3400～4200 degree/ton zinc), anode work-ing life short (0.5～1 year), anode lead easily dissolves and enters in the negative electrode product, causes cathode product quality to descend.For power consumption that reduces electrodeposition such as zinc, copper, nickel, cobalt, manganese and the pollution that prevents anode lead anticathode product, both at home and abroad above-mentioned electrolytic deposition process of metal is furtherd investigate and developed with insoluble anode.Comprehensive present research and service condition both at home and abroad mainly contains following four classes:
1, improved lead-Yin binary, multicomponent alloy anode: mainly comprise lead-Yin (Pb-Ag), lead-arsenic (Pb-As), lead-calcium (Pb-Ca), lead-mercury (Pb-Hg), lead-chromium (Pb-Cd), lead-titanium (Pb-Ti), lead-calcium-barium (Pb-Ca-Ba), lead-Yin-calcium (Pb-Ag-Ca), lead-Yin-strontium (Pb-Ag-Sr), lead-calcium-Xi (Pb-Ca-Sn) and lead-Yin-calcium-Xi (Pb-Ag-Ca-Sn) etc., but still exist work-ing life short, shortcomings such as the high and easy pollution cathode product of energy consumption.
2, titanium-based surface is coated with/plates dimensionally stable anode: this type of anode is to be base with titanium Ti, surface-coated precious metal or its oxide compound, but this anode has the following disadvantages: (1) adopts titanium matrix, electrode cost height; (2), cause the life-span of electrode short owing to the passivation of noble coatings dissolving and matrix titanium in the electrolysis production; (3) in electrodeposition solution, foreign ion as manganese, has reduced the effect of noble metal-coating layer in the anodic deposition with the oxidation states of matter after the oxidation.
3, titanium base oxide anode: this type of anode is a matrix with metal titanium (Ti), adopts the method for galvanic deposit at first to deposit plumbic oxide (PbO at titanium (Ti) primary surface
2), again at the thick Manganse Dioxide (MnO of 10 microns of plumbic oxide surface depositions (μ m)
2), form titanium-plumbic oxide-Manganse Dioxide (Ti/PbO
2/ MnO
2) electrode.This electrode is compared with lead-silver anode, the overpotential of oxygen has reduced by 0.344 volt, has certain application prospect, but this electrode have only 170-200 days the work-ing life in zinc electrodeposition solution (500 peaces/square metre current density under), await further raising, and this type of anode is body material with the titanium, and the cost height has limited application.
4, the aluminium base or stainless steel-based combination electrode material of producing: this type of combination electrode material is a matrix with aluminium or stainless steel, adopts: oil removing → soak zinc (Zn) → lead plating (Pb) → electrochemical oxidation → pulse electrodeposition Manganse Dioxide (MnO
2) technology produce.Use this combination electrode material when electrowinning, anode surface forms the rete of one deck densification, makes anode be in non-molten state, can improve the quality of negative electrode product, reduces bath voltage.But there is deficiency in process of production in this anode material: Production Flow Chart is long, the production energy consumption height.Soak technologies such as zinc, lead plating, rinsing, can produce a large amount of waste liquids, environmental pollution is comparatively serious.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of non-ferrous metal electrodeposition with energy-saving metal-based ceramic inert anode material, this method can significantly reduce production costs, and reduces the pollution of anode lead dissolving anticathode product, overcomes the deficiency that above-mentioned prior art exists.
The present invention is achieved through the following technical solutions:
A kind of non-ferrous metal electrodeposition preparation method of energy-saving metal-based ceramic inert anode material is characterized in that: at base material is the polar board surface compacting prionodont decorative pattern of lead-based multi-component alloy, again at prionodont decorative pattern surface preparation PbO
2And MnO
2Conductivity ceramics, technical process is as follows:
Pure lead and multicomponent alloy element batching → melting → ingot casting → rolling → lead-based multi-component alloy pole plate → compacting prionodont decorative pattern → preparation PbO
2And MnO
2Conductivity ceramics → energy-saving metal-based ceramic inert anode material.
Described lead-based multi-component alloy interalloy constituent content: silver (Ag) 0.1～0.3%; Aluminium (Al) 0.01～0.50%; Titanium (Ti) 0.01～0.10%; Manganese (Mn) 0.1～0.8%; Calcium (Ca) 0.02～0.10%; Strontium (Sr) 0.02～0.25%; Rare earth (RE) 0.005～0.02%, all the other are plumbous.
Described preparation PbO
2And MnO
2Processing condition: lead nitrate Pb (NO
3)
2180～200g/L; Nitric acid (HNO
3) 1～3g/L; Manganous nitrate Mn (NO
3)
240～50g/L; 70～80 ℃ of temperature; 4～5 hours time, anodic current density 5～6A/dm
2
Described polar board surface compacting prionodont decorative pattern, the width 1～1.5mm of prionodont decorative pattern, the degree of depth 0.5～1.0mm of prionodont decorative pattern.
The material of matrix lead is selected pure stereotype or pure lead rod for use in the described lead-based multi-component alloy.
It is the metal-based ceramic inert anode material of matrix with the lead-based multi-component alloy that the present invention adopts physics and the preparation of electrochemical method, use metal-based ceramic inert anode material when electrowinning, because anode surface is a conducting ceramic material, anode surface is in non-molten state, can reduce the pollution of anode lead dissolving anticathode product, improve the quality of negative electrode product, can guarantee that the qualification rate of No. 0 product of cathode zinc reaches 99%; The use of this kind combined electrode can significantly reduce the bath voltage of electrolytic deposition process, thereby reduces power consumption.Bath voltage can reduce by 0.3～0.5V during electrodeposition such as zinc, copper, nickel, cobalt, manganese, improves current efficiency 2～3%.Compare with traditional lead 2-base alloy anode, owing to, can increase the anodic specific surface area more than one times, thereby can improve anodic work-ing life more than one times at lead-based multi-component alloy plate surface compacting prionodont decorative pattern.
Embodiment
Embodiment
Prepare burden at first as following weight percent: silver (Ag) 0.1～0.3%; Aluminium (Al) 0.01～0.50%; Titanium (Ti) 0.01～0.10%; Manganese (Mn) 0.1～0.8%; Calcium (Ca) 0.02～0.10%; Strontium (Sr) 0.02～0.25%; Rare earth (RE) 0.005～0.02%, all the other are plumbous, the component summation is 100%.Molten refining, ingot casting and rolling technology routinely makes the lead-based multi-component alloy pole plate of thickness 2～5mm then, suppresses prionodont decorative pattern, the width 1～1.5mm of prionodont decorative pattern, the degree of depth 0.5～1.0mm of prionodont decorative pattern again on the lead-based multi-component alloy polar board surface; Last surface preparation PbO at the prionodont decorative pattern
2And MnO
2Conductivity ceramics obtains energy-saving metal-based ceramic inert anode material.
Described preparation PbO
2And MnO
2Processing condition: lead nitrate Pb (NO
3)
2180～200g/L; Nitric acid (HNO
3) 1～3g/L; Manganous nitrate Mn (NO
3)
240～50g/L; 70～80 ℃ of temperature; 4～5 hours time, anodic current density 5～6A/dm
2
The material of matrix lead is selected pure stereotype or pure lead rod for use in the described lead-based multi-component alloy.
Claims (5)
1. a non-ferrous metal electrodeposition is with the preparation method of energy-saving metal-based ceramic inert anode material, it is characterized in that: be the polar board surface compacting prionodont decorative pattern of lead-based multi-component alloy at base material, at lead-based multi-component alloy surface compacting prionodont decorative pattern, at prionodont decorative pattern surface preparation PbO
2MnO
2Conductivity ceramics, technical process is as follows:
Pure lead and multicomponent alloy element batching → melting → ingot casting → rolling → lead-based multi-component alloy plate → compacting prionodont decorative pattern → preparation PbO
2And MnO
2Conductivity ceramics → energy-saving metal-based ceramic inert anode material.
2. preparation method according to claim 1 is characterized in that: described lead-based multi-component alloy interalloy constituent content is by weight percentage: silver (Ag) 0.1～0.3%; Aluminium (Al) 0.01～0.50%; Titanium (Ti) 0.01～0.10%; Manganese (Mn) 0.1～0.8%; Calcium (Ca) 0.02～0.10%; Strontium (Sr) 0.02～0.25%; Rare earth (RE) 0.005～0.02%, all the other are plumbous.
3. preparation method according to claim 1 is characterized in that: described preparation PbO
2And MnO
2Processing condition: lead nitrate Pb (NO
3)
2180～200g/L; Nitric acid (HNO
3) 1～3g/L; Manganous nitrate Mn (NO
3)
240～50g/L; 70～80 ℃ of temperature; 4～5 hours time; Anodic current density 5～6A/dm
2
4. preparation method according to claim 1 is characterized in that: the width 1～1.5mm of described compacting prionodont decorative pattern, the degree of depth 0.5～1.0mm of prionodont decorative pattern.
5. preparation method according to claim 1 is characterized in that: the material of base aluminum is pure aluminum plate or fine aluminium rod.
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| CN101736369B (en) * | 2009-12-29 | 2011-08-17 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102206838A (en) * | 2011-04-22 | 2011-10-05 | 昆明理工恒达科技有限公司 | Method for preparing novel anode material for non-ferrous metal electrodeposition |
| CN102433581A (en) * | 2011-12-05 | 2012-05-02 | 昆明理工恒达科技有限公司 | Method for preparing novel anode material for electro-deposition of nonferrous metals |
| CN102465313A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Method for pretreating lead base inert anode for electro-deposit copper |
| CN102465314A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Preprocessing method of lead/lead-alloy inert anode for zinc electrowinning |
| CN102627002A (en) * | 2012-03-27 | 2012-08-08 | 昆明理工恒达科技有限公司 | Preparation method of aluminum-base lead and lead alloy composite material |
| CN102626776A (en) * | 2012-03-27 | 2012-08-08 | 昆明理工恒达科技有限公司 | Preparing method of aluminum-based lead and lead alloy composite anode |
| CN102888625A (en) * | 2012-10-10 | 2013-01-23 | 昆明理工恒达科技有限公司 | Fence type anode plate for electrodeposition of nonferrous metals |
| CN106435652A (en) * | 2016-11-11 | 2017-02-22 | 中南大学 | Rolled porous lead alloy anode and preparation process thereof |
| CN108728872A (en) * | 2018-06-13 | 2018-11-02 | 昆明理工大学 | Copper electrodeposition aluminium bar Pb-Sn-Sb/ α-PbO2-Co3O4Combination electrode material and preparation method |
| CN109537000A (en) * | 2018-11-27 | 2019-03-29 | 昆明理工大学 | A kind of stainless base steel β-PbO2-MnO2-CeO2-ZrO2The preparation method of inertia composite anode materials |
| CN112962119A (en) * | 2021-01-19 | 2021-06-15 | 昆明理工大学 | Composite electrode plate for non-ferrous metal electrodeposition and preparation method thereof |
| CN113604841A (en) * | 2021-07-22 | 2021-11-05 | 田成 | Method for extracting and recovering valuable metal from waste liquid by non-inert anode plate |
| CN115110122A (en) * | 2022-04-11 | 2022-09-27 | 贵州大学 | Columnar Pb-based pseudomorphic anode for hydrometallurgy and preparation method thereof |
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| CN101736369B (en) * | 2009-12-29 | 2011-08-17 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102465313A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Method for pretreating lead base inert anode for electro-deposit copper |
| CN102465314A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Preprocessing method of lead/lead-alloy inert anode for zinc electrowinning |
| CN102206838A (en) * | 2011-04-22 | 2011-10-05 | 昆明理工恒达科技有限公司 | Method for preparing novel anode material for non-ferrous metal electrodeposition |
| CN102206838B (en) * | 2011-04-22 | 2013-03-13 | 昆明理工恒达科技有限公司 | Method for preparing novel anode material for non-ferrous metal electrodeposition |
| CN102433581B (en) * | 2011-12-05 | 2014-06-18 | 昆明理工恒达科技股份有限公司 | Method for preparing novel anode material for electro-deposition of nonferrous metals |
| CN102433581A (en) * | 2011-12-05 | 2012-05-02 | 昆明理工恒达科技有限公司 | Method for preparing novel anode material for electro-deposition of nonferrous metals |
| CN102627002A (en) * | 2012-03-27 | 2012-08-08 | 昆明理工恒达科技有限公司 | Preparation method of aluminum-base lead and lead alloy composite material |
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| CN102888625B (en) * | 2012-10-10 | 2015-08-05 | 昆明理工恒达科技股份有限公司 | Non-ferrous metal electrodeposition palisading type positive plate |
| CN102888625A (en) * | 2012-10-10 | 2013-01-23 | 昆明理工恒达科技有限公司 | Fence type anode plate for electrodeposition of nonferrous metals |
| CN106435652A (en) * | 2016-11-11 | 2017-02-22 | 中南大学 | Rolled porous lead alloy anode and preparation process thereof |
| CN108728872A (en) * | 2018-06-13 | 2018-11-02 | 昆明理工大学 | Copper electrodeposition aluminium bar Pb-Sn-Sb/ α-PbO2-Co3O4Combination electrode material and preparation method |
| CN108728872B (en) * | 2018-06-13 | 2020-03-27 | 昆明理工大学 | Aluminum bar Pb-Sn-Sb/α -PbO for copper electrodeposition2-Co3O4Composite electrode material and preparation method thereof |
| CN109537000A (en) * | 2018-11-27 | 2019-03-29 | 昆明理工大学 | A kind of stainless base steel β-PbO2-MnO2-CeO2-ZrO2The preparation method of inertia composite anode materials |
| CN109537000B (en) * | 2018-11-27 | 2020-12-08 | 昆明理工大学 | Stainless steel based beta-PbO2-MnO2-CeO2-ZrO2Preparation method of inert composite anode material |
| CN112962119A (en) * | 2021-01-19 | 2021-06-15 | 昆明理工大学 | Composite electrode plate for non-ferrous metal electrodeposition and preparation method thereof |
| CN113604841A (en) * | 2021-07-22 | 2021-11-05 | 田成 | Method for extracting and recovering valuable metal from waste liquid by non-inert anode plate |
| CN115110122A (en) * | 2022-04-11 | 2022-09-27 | 贵州大学 | Columnar Pb-based pseudomorphic anode for hydrometallurgy and preparation method thereof |
| CN115110122B (en) * | 2022-04-11 | 2024-01-26 | 贵州大学 | Columnar Pb-based pseudoshape stable anode for hydrometallurgy and preparation method thereof |
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Effective date of registration: 20151223 Address after: 650000 two street base, Jinning Industrial Park, Kunming, Yunnan Patentee after: Jinning science and technology Hengda Technology Co., Ltd. Address before: 650101, No. 1299 Chang Yuan North Road, Kunming hi tech Development Zone, Yunnan Patentee before: KUNMING HENDERA SCIENCE AND TECHNOLOGY CO., LTD. |