CN101343758B - Method for preparing novel energy conservation inert anode material for zinc electrodeposition - Google Patents
Method for preparing novel energy conservation inert anode material for zinc electrodeposition Download PDFInfo
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- CN101343758B CN101343758B CN2008100588234A CN200810058823A CN101343758B CN 101343758 B CN101343758 B CN 101343758B CN 2008100588234 A CN2008100588234 A CN 2008100588234A CN 200810058823 A CN200810058823 A CN 200810058823A CN 101343758 B CN101343758 B CN 101343758B
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Abstract
The invention relates to a novel energy-saving inert anode material preparation method used for zinc galvanic deposition. A multi-pulse galvanic deposition method is adopted to prepare and obtain a lead-lead dioxide-titanium boride-cerium dioxide-polyanion composite plating layer (Pb-PbO2-TiB2-CeO2-PAN) energy-saving inert anode material on an aluminum base body, and when the composite electrode material is used to electrically deposit the metal, a compact film layer is formed on the anode surface to make the anode be in a non-molten state; the adoption of the composite electrode can obviously reduce the voltage of the galvanic deposition cell, and the electric consumption is reduced; meanwhile the electroplating solution cost of the invention is low, the equipment investment is less, theland occupation is less, and the effect is rapid; and the cell voltage can be reduced by 0.2 to 0.5V when zinc galvanic deposition is performed, and the current efficiency is improved by 1 to 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 zinc electrodeposition with inert anode material.
Background technology
Extract in wet method in the metal process such as zinc, copper, nickel, cobalt, manganese, chromium, 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, chromium 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 zinc electrodeposition with inert anode material, lead and lead 2-base alloy anode that this method can replace original technology to use, significantly reduce production costs, reduce the pollution of anode lead dissolving anticathode product, improve the quality of negative electrode product.
The present invention is achieved through the following technical solutions:
A kind of zinc electrodeposition preparation method of inert anode material, the body material of pole plate is an aluminium matter, electrically contacts part and is combined into one with the conduction crossbeam, adopts the method for multipulse galvanic deposit to prepare on aluminum substrate, aluminium matter matrix soaks zinc after oil removal treatment, it is characterized in that having following technical process:
Galvanic deposit alkalescence Lead-tin alloy, galvanic deposit: lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite] Pb-PbO
2-TiB
2-CeO
2-PANI obtains [lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite] Pb-PbO at last on aluminium matter matrix
2-TiB
2-CeO
2-PANI energy-saving inert anode material,
The processing condition of described galvanic deposit alkalescence Lead-tin alloy: plumbous oxide (PbO) 90～150g/L; Sodium hydroxide (NaOH) 10～40g/L; Seignette salt (C
6H
4O
4NaK) 90～150g/L; Sodium stannate (Na
2SnO
3) 2～40g/L; 20～60 ℃ of temperature; Cathode current density 0.5～4A/dm
2
The processing condition of described galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite: plumbic acetate Pb (AC)
2200～300g/L; Fluoroboric acid (HBF
4) 150～250ml/L; Boric acid (HBO
3) 3～20g/L; Plumbic oxide (PbO
2) 50～150g/L; TiB2 (TiB
2) 40～100g/L; Cerium dioxide (CeO
2) 10～50g/L; Polyaniline (PANI) 30～90g/L; 25～40 ℃ of temperature; Cathode current density 1.0～5A/dm
2
Described aluminium matter matrix is pure aluminum plate or fine aluminium rod; The conduction crossbeam adopts copper-clad aluminium sheet or aluminium sheet.
The cross-sectional area size of described conduction crossbeam is 20 * 60mm; Aluminium matter matrix be shaped as fence shape.
Described electrical contacts is divided into the red copper piece of 50 * 50 * 8mm.
The present invention has following advantage: this method is produced anode material, and facility investment is few, takes up an area of and lacks instant effect.The energy-saving inert anode material that utilizes this method to produce can replace the lead and the lead 2-base alloy anode of original technology, significantly reduces production costs, and reduces the pollution of anode lead dissolving anticathode product, improves the quality of negative electrode product; Shortened the Production Flow Chart of producing anode material simultaneously, reduced and produce the waste liquid that produces, reduced and pollute, reduce production costs.Use this combination electrode material when electrowinning, anode surface forms the rete of one deck densification, makes anode be in non-molten state.The use of this combined electrode can significantly reduce Winning cell voltage, reduces power consumption; Plating bath cost of the present invention is low simultaneously, and facility investment is few, takes up an area of to lack instant effect.Bath voltage can reduce by 0.2～0.5V during the zinc electrodeposition, improves current efficiency 1～3%.
Embodiment
Embodiment 1
Pulse electrodeposition inert anode material on fence shape pure aluminum plate, the conduction crossbeam adopts copper-clad aluminium sheet or aluminium sheet, electrical contacts is divided into the red copper piece of 50 * 50 * 8mm, and the red copper piece is combined into one with the conduction crossbeam, and the cross-sectional area size of conduction crossbeam is 20 * 60mm.Aluminium matter matrix soaks zinc after oil removal treatment, technical process is as follows:
Galvanic deposit alkalescence Lead-tin alloy, galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO
2-TiB
2-CeO
2-PANI obtains lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO at last on aluminium matter matrix
2-TiB
2-CeO
2-PANI energy-saving inert anode material.
The processing condition of described galvanic deposit alkalescence Lead-tin alloy: plumbous oxide (PbO) 90～120g/L; Sodium hydroxide (NaOH) 10～20g/L; Seignette salt (C
6H
4O
4NaK) 90～120g/L; Sodium stannate (Na
2SnO
3) 2～10g/L; 20～30 ℃ of temperature; Cathode current density 0.5～4A/dm
2
The processing condition of described galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite: plumbic acetate Pb (AC)
2200～250g/L; Fluoroboric acid (HBF
4) 150～200ml/L; Boric acid (HBO
3) 3～10g/L; Plumbic oxide (PbO
2) 50～100g/L; TiB2 (TiB
2) 40～60g/L; Cerium dioxide (CeO
2) 10～20g/L; Polyaniline (PANI) 30～60g/L; 25～35 ℃ of temperature; Cathode current density 1.0～5A/dm
2
Embodiment 2
Pulse electrodeposition inert anode material on fence shape pure aluminum plate, the conduction crossbeam adopts copper-clad aluminium sheet or aluminium sheet, electrical contacts is divided into the red copper piece of 50 * 50 * 8mm, and the red copper piece is combined into one with the conduction crossbeam, and the cross-sectional area size of conduction crossbeam is 22 * 45mm.Aluminium matter matrix soaks zinc after oil removal treatment, technical process is as follows:
Galvanic deposit alkalescence Lead-tin alloy, galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO
2-TiB
2-CeO
2-PANI obtains lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO at last on aluminium matter matrix
2-TiB
2-CeO
2-PANI energy-saving inert anode material.
The processing condition of described galvanic deposit alkalescence Lead-tin alloy: plumbous oxide (PbO) 100～150g/L; Sodium hydroxide (NaOH) 20～40g/L; Seignette salt (C
6H
4O
4NaK) 100～150g/L; Sodium stannate (Na
2SnO
3) 15～30g/L; 30～60 ℃ of temperature; Cathode current density 0.5～4A/dm
2
The processing condition of described galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite: plumbic acetate Pb (AC)
2250～300g/L; Fluoroboric acid (HBF
4) 250～300ml/L; Boric acid (HBO
3) 10～20g/L; Plumbic oxide (PbO
2) 100～150g/L; TiB2 (TiB
2) 60～100g/L; Cerium dioxide (CeO
2) 30～50g/L; Polyaniline (PANI) 60～90g/L; 30～40 ℃ of temperature; Cathode current density 1.0～5A/dm
2
Embodiment 3
Pulse electrodeposition inert anode material on fence shape pure aluminum plate, the conduction crossbeam adopts copper-clad aluminium sheet or aluminium sheet, electrical contacts is divided into the red copper piece of 50 * 50 * 8mm, and the red copper piece is combined into one with the conduction crossbeam, and the cross-sectional area size of conduction crossbeam is 32 * 56mm.Aluminium matter matrix soaks zinc after oil removal treatment, technical process is as follows:
Galvanic deposit alkalescence Lead-tin alloy, galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO
2-TiB
2-CeO
2-PANI obtains lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite Pb-PbO at last on aluminium matter matrix
2-TiB
2-CeO
2-PANI energy-saving inert anode material.
The processing condition of described galvanic deposit alkalescence Lead-tin alloy: plumbous oxide (PbO) 90～150g/L; Sodium hydroxide (NaOH) 10～40g/L; Seignette salt (C
6H
4O
4NaK) 90～150g/L; Sodium stannate (Na
2SnO
3) 2～40g/L; 20～60 ℃ of temperature; Cathode current density 0.5～4A/dm
2
The processing condition of described galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite: plumbic acetate Pb (AC)
2200～300g/L; Fluoroboric acid (HBF
4) 150～250ml/L; Boric acid (HBO
3) 3～20g/L; Plumbic oxide (PbO
2) 50～150g/L; TiB2 (TiB
2) 40～100g/L; Cerium dioxide (CeO
2) 10～50g/L; Polyaniline (PANI) 30～90g/L; 25～40 ℃ of temperature; Cathode current density 1.0～5A/dm
2
Claims (6)
1. a zinc electrodeposition is with the preparation method of inert anode material, the body material of pole plate is an aluminium matter, electrically contacts part and is combined into one with the conduction crossbeam, adopts the method for multipulse galvanic deposit to prepare on aluminum substrate, aluminium matter matrix soaks zinc after oil removal treatment, it is characterized in that having following technical process:
Galvanic deposit alkalescence Lead-tin alloy, galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite obtain lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite inert anode material at last on aluminium matter matrix,
The processing condition of described galvanic deposit alkalescence Lead-tin alloy: plumbous oxide (PbO) 90～150g/L; Sodium hydroxide (NaOH) 10～40g/L; Seignette salt (C
6H
4O
4NaK) 90～150g/L; Sodium stannate (Na
2SnO
3) 2～40g/L; 20～60 ℃ of temperature; Cathode current density 0.5～4A/dm
2
The processing condition of described galvanic deposit lead-plumbic oxide-TiB2-cerium dioxide-polyaniline composite deposite: plumbic acetate Pb (AC)
2200～300g/L; Fluoroboric acid (HBF
4) 150～250ml/L; Boric acid (HBO
3) 3～20g/L; Plumbic oxide (PbO
2) 50～150g/L; TiB2 (TiB
2) 40～100g/L; Cerium dioxide (CeO
2) 10～50g/L; Polyaniline (PANI) 30～90g/L; 25～40 ℃ of temperature; Cathode current density 1.0～5A/dm
2
2. preparation method according to claim 1 is characterized in that: aluminium matter matrix is pure aluminum plate or fine aluminium rod.
3. preparation method according to claim 1 is characterized in that: the conduction crossbeam adopts copper-clad aluminium sheet or aluminium sheet.
4. preparation method according to claim 1 is characterized in that: the cross-sectional area size of conduction crossbeam is 20 * 60mm.
5. preparation method according to claim 1 is characterized in that: aluminium matter matrix be shaped as fence shape.
6. preparation method according to claim 1 is characterized in that: electrical contacts is divided into the red copper piece of 50 * 50 * 8mm.
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| CN101608323B (en) * | 2009-07-02 | 2011-12-07 | 昆明理工大学 | Method for preparing zero-anode-potential hydrogen-diffusion anodes |
| 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 |
| CN101962788B (en) * | 2010-09-03 | 2012-05-30 | 昆明理工大学 | Preparation method of Al-based Pb-WC-CeO2 inert composite anode material |
| 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 |
| CN102051640B (en) * | 2010-11-17 | 2012-10-31 | 昆明理工大学 | Preparation method of Al-based Pb-ZrO2-CeO2 composite anode material for zinc electrodepositing |
| CN102296330B (en) * | 2011-08-10 | 2014-01-22 | 昆明理工恒达科技有限公司 | Method for preparing titanium-based lead-tungsten carbide-cerium oxide-polyaniline composite anode plate |
| CN102433573B (en) * | 2011-11-17 | 2014-11-12 | 常州大学 | Titanium-lead composite anode and preparation method thereof |
| CN102443822B (en) * | 2011-12-05 | 2015-04-22 | 昆明理工大学 | Gradient functional inert anode material used for zinc electrodeposition and its preparation method |
| CN102409366B (en) * | 2011-12-05 | 2015-05-20 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| 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 |
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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 |
| CN103741167A (en) * | 2013-12-25 | 2014-04-23 | 中国矿业大学 | Method for improving oxidization resistance of carbon anode for electrolyzing aluminum |
| CN111534837B (en) * | 2020-05-07 | 2021-07-09 | 北京科技大学 | Preparation method of inert anode suitable for high-temperature molten salt system |
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