CN103572331B - The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode - Google Patents
The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode Download PDFInfo
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Abstract
The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode, anode includes titanium copper-clad busbar (1) and is connected to one group of vertical titanium rod (2) below titanium copper-clad busbar, and every titanium rod is the most successively by Titanium base, pretreatment layer, α PbO2Composite interlayer and β PbO2Multiplicity reactivation top layer is constituted.Manufacture method is first to be connected to by Titanium base below titanium copper-clad busbar, forms fence structure body, then by the Titanium base part of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, then through basic plating α PbO2Composite bed and acid electroplating β PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Positive plate.The Novel anode using the inventive method to prepare has excellent machinery and corrosion resistance, and bath voltage can be greatly reduced during the electrometallurgy such as wet method electrowinning zinc, electro deposited copper, electro deposited nickel, electrodeposition manganese, reduces energy consumption.
Description
Technical field
The present invention relates to the metal electro-deposition anode technology field that the fields such as composite electrodeposition, non-ferrous metal metallurgy and hydrometallurgy use, be specifically related to palisading type titanio PbO2The manufacture method of anode.
Background technology
In whole commercial production, metallurgical industry remains big power consumer, and energy consumption is high, and its main specific energy consumption average specific Foreign Advanced Lerel is high by 40%.In the smelting process of non-ferrous metal, the zinc of about more than 80% is extracted by hydrometallurgical technology.In Zinc Hydrometallurgy Process, electrodeposition operation has consumed whole zinc and has extracted the energy consumption of process 2/3, and the energy consumption of zinc hydrometallurgy is 3800～4200kwh/t.Zn, produces per year in terms of 5,000,000 tons of zinc by the whole nation in 2007, power consumption is 20,300,000,000 kilowatt hours, accounts for the 0.64～0.75% of whole nation industry total electricity consumption.Especially in the case of current global economy depression, to reducing metallurgical industry energy consumption, improve enterprise independent innovation ability and the upgrading industrial structure is significant, one is to alleviate China's energy-intensive situation, and two is to exploit in a large number in mineral resources and can increase the competitive advantage of enterprise under the situation of reserves minimizing, grade of ore reduction, rise in price, corresponding exploitation processing cost increase and product price degradation.
At present, the anode that electrolytic industry uses is platinum (titanium platinum plating, sintering platinum) electrode, titanium-based oxide coated electrode, graphite electrode, lead and lead alloy etc..But, in these electrodes, metal platinum and alloy thereof are expensive, and consume notable when using at higher current densities.Lead oxides electrode manufactures difficulty, and coating easily produces pitting so that corrosion resistance is poor.Titanium-based surface noble metal-coating or its oxide, this anode has the disadvantage that (1) electrode cost is high, (2) life-span is short, its reason is owing in electrolysis production, noble coatings dissolves and the Tunization of matrix titanium, commonly use coating inter coat by improvement people to be prevented, but problem can not be solved at all, (3) in electrodeposition solution, foreign ion (Mn2+) reduce the effect of noble metal-coating after oxidation in the deposition of anode with oxidation state.For above-mentioned reasons so that it is application in the industry is by a definite limitation.Graphite electrode consumption is big, and overpotential is high, therefore, is all widely used.Lead and alloy lead anode have molding easily, in sulfuric acid medium the advantage such as relatively stable, low cost of manufacture, be used widely in production of nonferrous metals at present.But, lead and lead based alloy anodes there is overpotential for oxygen evolution high (close to 1V) and surface passivated membrane is the finest and close, adsorb the shortcomings such as a large amount of non-conductive manganese dioxide in electrolytic process, cause bath voltage high (if Zinc electrolysis is 3.2～3.8V), electrolytic deposition process current efficiency low (75～90%), energy consumption is high (if Zinc electrolysis is 3200～3800 kilowatt hours/ton), anode life short (6～December), the corrosion product of anode lead easily enters cathode product, affects the shortcomings such as cathode product quality.
Along with the continuous exploitation of zinc resource, the zinc concentrate of high-quality is fewer and feweri, and the difficult smelting zinc concentrate rich in impurity gradually increases, and the various material containing zincs in the past not quite trusting use use flow process also into reclaiming.Buying and using of many domestic and international high chlorine zinc concentrates and Zinc Oxide, is the one of the main reasons causing production economy technical specification seriously to glide.It is demonstrated experimentally that electrolyte is chloride more than 1000mg/L, chloride ion will corrode anode, and anode is oxidized to chlorate, and pole plate is thinning, perforation, and the life-span is greatly shortened.Therefore, find a kind of corrosion-resistant, high connductivity, resistance to deformation, long-life novel energy conservation inert anode material is used in the industrialized production of non-ferrous metal electrodeposition has important real value.
Have a kind of novel inertia anode of lead dioxide, the preparation of this electrode at present, generally select titanium, graphite, plastics and pottery etc. for matrix material, by matrix surface roughening treatment, coating bottom, α-PbO2Intermediate layer and plating β-PbO2Etc. basic process, it is coated with and obtains PbO2Electrode.Its advantage can operate at higher current densities for (1)；(2) generation of mud can be suppressed；(3) oxidation efficiency can be improved；(4) good corrosion resistance and long-life；(5) in Zinc electrolysis, chemical conversion treatment need not be carried out, and the amount that lead is mixed in zinc reduces, good to the corrosion resistance of chlorine, and chlorine can be removed, manganese slag will not be produced, the current efficiency extracting zinc is high.But the PbO that so plating prepares2Electrode, as insoluble anode, in use occur the problem that (1) PbO2Sedimentary is combined not tight with electrode surface or sedimentary is uneven；(2)PbO2Sedimentary porous and coarse, internal stress is big；(3)α-PbO2Intermediate layer poorly conductive, easily produces big voltage drop；(4)PbO2Sedimentary is easily peeled off or corrodes, and the life-span is the longest.And doped fluor-containing resin and (or) inactive granule PbO2The tank voltage that electrode is used in non-ferrous metal electrodeposition is high；(4) current efficiency is low, although PbO2The electro catalytic activity of electrode is higher, but the current efficiency in non-ferrous metal electrodeposition is applied is not the highest.This is to cause owing to one part of current is used for the electrolysis of water.
Additionally, want to obtain high performance electrode material in electrolytic non-ferrous metal field, not only improve the performance of coating and it is necessary to electrode matrix self structure is improved.For electrode material, electro-chemical activity depends on active center quantity and distribution thereof.The active center of high dispersive not only have be electrode activity improve effect, and make be on active service homogeneous current distribution, electric current density decline, improve coating corrosion resistance.
Summary of the invention
The invention aims to the shortcoming overcoming the existence of above-mentioned prior art, it is provided that a kind of electro catalytic activity is good, electrode conductivity is strong, the non-ferrous metal electrodeposition palisading type titanio PbO that tank voltage is low, length in service life, energy consumption are low in electrodeposition2The manufacture method of anode.
The purpose of the present invention is achieved through the following technical solutions:
Non-ferrous metal electrodeposition palisading type titanio PbO2The manufacture method of anode, described non-ferrous metal electrodeposition palisading type titanio PbO2Anode includes titanium copper-clad busbar and is connected to one group of vertical titanium rod below titanium copper-clad busbar, and every titanium rod is the most successively by Titanium base, pretreatment layer, α-PbO2Composite interlayer and β-PbO2Multiplicity reactivation top layer is constituted；Manufacture method is first to be connected to by Titanium base below titanium copper-clad busbar, form fence structure body, then by the Titanium base part of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, after through basic plating α-PbO2Composite bed and acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Positive plate, specifically comprises the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into ebuillition of heated oil removing 30min～2h in weight percent concentration 20%～50%NaOH solution, again after mechanical spray coarsening processes, remove oxide-film via pickling 20～90min in the boiling solution of weight percent concentration 10%～20% oxalic acid again, finally Titanium base is cleaned up in placement dehydrated alcohol stand-by with deionized water；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the activation Titanium base of pretreatment layer；Activating solution formula is 10-60ml/L titanous chloride., 0.1-0.5g/L pyrovinic acid nickel or pyrovinic acid cobalt, 0.05-5g/L rare earth chloride or cobaltous chloride, 300-800ml/L hydrochloric acid；Poling processing technique condition is temperature 30～60 DEG C, soak time 0.5～1.5 hours；
(3) being immediately placed in alkalescence composite plating solution after step (2) processing the activation Titanium base deionized water cleaning prepared, using rustless steel as negative electrode, temperature is 20～80 DEG C, and electric current density is 0.5～6A/dm2, plating 1～12 hour under mechanical stirring, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution245～80g/L, sodium hydroxide NaOH 100～160g/L, trisodium citrate or sodium potassium tartrate tetrahydrate 60～80g/L, the silver-plated silica dioxide granule of electrical-conductive nanometer 5～20g/L；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, and using Titanium board as negative electrode, temperature is 30～70 DEG C, and electric current density is 2～5A/dm2, plating 4-16 hour under mechanical stirring, form β-PbO2Multiplicity reactivation top layer, i.e. obtains non-ferrous metal electrodeposition palisading type titanio PbO2Anode；Containing plumbi nitras Pb (NO in described acid composite plating solution3) 2100～200g/L, nitric acid HNO320～30g/L, sodium tungstate Na2WO4Or sodium molybdate Na2MoO4160～200g/L, nanometer tungsten carbide 5～20g/L.
The inventive method is by Titanium base oil removing, sandblasting, removing oxide-film, activation processing, basic plating α-PbO2Composite bed and acid electroplating β-PbO2In the whole process technique of composite bed, wrap the gum cover (4) of acid and alkali-resistance at lead-sheathing copper busbar (1) and Titanium base junction, prevent liquid from connecing position corrosion；During process, Titanium base is placed on horizontal support (3).Support of the present invention (3) is plastic stent, and described gum cover (4) is silica gel sheath.
α-the PbO that above-mentioned steps of the present invention (3) obtains2Composite interlayer thickness is 200 μm～600 μm.The silver-plated silica dioxide granule of described electrical-conductive nanometer is to obtain being placed in alkalescence silver plating liquid by the nano silicon after stannous chloride sensitization, the formula of alkalescence silver plating liquid is 3～10g/L silver nitrate, 5g/L sodium hydroxide, 3～10g/L glucoses, treatment process condition is temperature 0～10 DEG C, electroless plating time 2～6h.
Above-mentioned steps of the present invention (4) processes the β-PbO obtained2Multiplicity reactivation skin depth is 0.3mm～2mm.The particle diameter of described nanometer tungsten carbide is 5nm～30nm.
The inventive method can separately add 0.05g/L PVP in the formula of alkalescence silver plating liquid.
Titanium copper-clad busbar of the present invention is at titanium copper-clad busbar bear with the connected mode of titanium rod, is then inserted in the hole by titanium rod, then is welded to connect with titanium copper-clad busbar by titanium rod.Described titanium rod is titanium bar or titanium pipe.Described titanium bar is cylindrical or elliptical cylinder-shape, and described titanium pipe is round tube or oval pipe.The surface of described titanium bar or titanium pipe draws vertical corrugated type or sawtooth pattern decorative pattern.Described cylindrical titanium shank diameter is 3mm～12mm, and circular titanium pipe external diameter is 6mm～12mm.The space width of described corrugated type or sawtooth pattern decorative pattern is 0.1～0.9mm, tooth depth is 0.1～0.5mm.
The present invention has the advantage that compared to existing technology
1, the non-ferrous metal electrodeposition of present invention palisading type titanio PbO2Anode, can avoid that titanium net or titanium plate Lead oxide brown occurred owing to catching a packet, the applied force such as collision time, coating easily produces the phenomenon come off, and extends electrode life；
2, palisading type positive plate is used to substitute traditional planar anode plate, compared with classic flat-plate type positive plate, the mobility of electrolyte can be improved, reduce the concentration polarization on cathode chamber metal ion (copper, zinc, nickel), improve the deposition of cathodic metal, thus improve cathode efficiency；
3, palisading type positive plate will not occur bending and deformation, and can avoid the phenomenon of cathode-anode plate short circuit；
4, titanium rod surface is drawn into corrugated type or sawtooth pattern decorative pattern, the adhesion of Lead oxide brown and matrix can be greatly enhanced, it is to avoid the internal stress intrinsic because of coating Lead oxide brown and the obscission that produces, extend electrode life；
5, α-PbO2 coating introduces the silver-plated silica dioxide granule of electrical-conductive nanometer, not only can be greatly enhanced the electric conductivity of α-PbO2, also make α-PbO2 coating be combined more firm with β-PbO2 composite deposite so that it is and not Presence of an interface resistance between each coating；
6, introducing has the nanometer WC particle of catalysis activity, can significantly improve the catalysis activity of electrode so that the tank voltage that electrode is used in non-ferrous metal electrodeposition significantly reduces.
7, the manufacture method of non-ferrous metal electrodeposition palisading type titanio PbO2 anode of the present invention is simple, and the electrode prepared is cheap, can substitute the alloy lead anode of original technique.
Accompanying drawing explanation
Fig. 1 is the structural representation of palisading type titanium substrate anode of the present invention；
Fig. 2 is the Section A-A figure of Fig. 1；
Fig. 3 is the section B-B figure of Fig. 1；
Fig. 4 is the C partial enlarged drawing of Fig. 1；
Fig. 5 is the schematic top plan view that Fig. 1 medium-height trestle supports titanium rod；
Fig. 6 is that surface draws the cylindrical titanium bar cross-sectional view having zigzag decorative pattern；
Fig. 7 is that surface draws the ellipse shape titanium bar cross-sectional view having zigzag decorative pattern.
In figure, 1 titanium copper-clad conducting beam；2 titanium rods；3 supports；4 gum covers.
Detailed description of the invention
Embodiment 1
The cylindrical titanium bar of a diameter of 3～5mm is drawn into surface there is the Titanium base of sawtooth pattern decorative pattern as shown in Figure 6, the tooth depth 0.3mm of zigzag decorative pattern, space width 0.4mm.Bottom titanium copper-clad busbar 1, make a call to one group of circular hole side by side, then one group of Titanium base is inserted in the hole, and be welded to connect with titanium copper-clad busbar, be combined into the fence structure body of 976mm × 620mm size.By the Titanium base part of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, then through basic plating α-PbO2Composite bed and acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Anode.Specifically comprise the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into ebuillition of heated oil removing 1h in concentration 30%NaOH solution, again after mechanical spray coarsening processes, remove oxide-film via pickling 40min in the boiling solution of concentration 15% oxalic acid again, finally Titanium base is cleaned up in placement dehydrated alcohol stand-by with deionized water；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the activation Titanium base of pretreatment layer；Activating solution formula is 40ml/L titanous chloride., 0.3g/L pyrovinic acid nickel, 0.5g/L rare earth chloride, 400ml/L hydrochloric acid；Poling processing technique condition is temperature 40 DEG C, soak time 1 hour；
(3) being immediately placed in alkalescence composite plating solution after step (2) processing the activation Titanium base deionized water cleaning prepared, using rustless steel as negative electrode, temperature is 60 DEG C, and electric current density is 2A/dm2, plating 6 hours under mechanical stirring, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution260g/L, sodium hydroxide NaOH 140g/L, trisodium citrate 60g/L, electrical-conductive nanometer silver-plated silica dioxide granule 10g/L；Wherein, the preparation of the silver-plated silica dioxide granule of electrical-conductive nanometer is to obtain being placed in alkalescence silver plating liquid by the nano silicon after stannous chloride sensitization, the formula of alkalescence silver plating liquid is 5g/L silver nitrate, 5g/L sodium hydroxide, 8g/L glucose, treatment process condition is temperature 0 DEG C, electroless plating time 4h；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, and using Titanium board as negative electrode, temperature is 50 DEG C, and electric current density is 3A/dm2, plating 8 hours under mechanical stirring, form β-PbO2Multiplicity reactivation top layer, i.e. obtains non-ferrous metal electrodeposition palisading type titanio PbO as Figure 1-Figure 42Anode；Containing plumbi nitras Pb (NO in described acid composite plating solution3)2150g/L, nitric acid HNO325g/L, sodium tungstate Na2WO4180g/L, particle diameter are 10nm nanometer tungsten carbide 10g/L；
α-PbO on the Titanium base that above-mentioned process finally gives2Composite interlayer thickness is 300 μm, β-PbO2Multiplicity reactivation skin depth is 1mm.
The non-ferrous metal electrodeposition palisading type titanio PbO that the present embodiment is finally given2Positive plate is at electrowinning zinc bath system (Zn2+50g/L, H2SO4150g/L, Mn2+12g/L, C1-1000mg/L, 1000A/m2, temperature is 35 DEG C) and application, compared with traditional metal Pb-0.8%Ag positive plate, the tank voltage of this anode reduces by 11%, and current efficiency improves 5%, and the life-span improves 50%.
Embodiment 2
By major axis be 5mm, short axle be that the ellipse titanium bar of 3mm is drawn into surface and has the Titanium base of sawtooth pattern decorative pattern as shown in Figure 7, the tooth depth 0.1mm of zigzag decorative pattern, space width 0.1mm.Bottom titanium copper-clad busbar 1, make a call to the elliptical aperture of a group leader axle 5mm side by side, then one group of Titanium base is inserted in the hole, and be welded to connect with titanium copper-clad busbar, be combined into the fence structure body of 960mm × 630mm size.By the Titanium base part of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, then through basic plating α-PbO2Composite bed and acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Anode.Specifically comprise the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into ebuillition of heated oil removing 2h in concentration 20%NaOH solution, again after mechanical spray coarsening processes, remove oxide-film via pickling 90min in the boiling solution of concentration 10% oxalic acid again, finally Titanium base is cleaned up in placement dehydrated alcohol stand-by with deionized water；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the activation Titanium base of pretreatment layer；Activating solution formula is 10ml/L titanous chloride., 0.5g/L pyrovinic acid nickel, 5g/L cobaltous chloride, 300ml/L hydrochloric acid；Poling processing technique condition is temperature 60 C, soak time 0.5 hour；
(3) being immediately placed in alkalescence composite plating solution after step (2) processing the activation Titanium base deionized water cleaning prepared, using rustless steel as negative electrode, temperature is 80 DEG C, and electric current density is 0.5A/dm2, plating 1 hour under mechanical stirring, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution245g/L, sodium hydroxide NaOH 160g/L, trisodium citrate 80g/L, electrical-conductive nanometer silver-plated silica dioxide granule 5g/L；Wherein, the preparation of the silver-plated silica dioxide granule of electrical-conductive nanometer is to obtain being placed in alkalescence silver plating liquid by the nano silicon after stannous chloride sensitization, the formula of alkalescence silver plating liquid is g/L silver nitrate, 5g/L sodium hydroxide, 10g/L glucose, treatment process condition is temperature 5 DEG C, 0.05g/L PVP, electroless plating time 2h；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, using Titanium board as negative electrode, temperature is 70 DEG C, electric current density is 2A/dm2, plating 16 hours under mechanical stirring, form β-PbO2 multiplicity reactivation top layer, i.e. obtain non-ferrous metal electrodeposition palisading type titanio PbO2 anode；Described acid composite plating solution is 30nm nanometer tungsten carbide 20g/L containing plumbi nitras Pb (NO3) 2 100g/L, nitric acid HNO3 20g/L, sodium molybdate Na2MoO4 160g/L, particle diameter；
α-PbO on the Titanium base that above-mentioned process finally gives2Composite interlayer thickness is 200 μm, β-PbO2Multiplicity reactivation skin depth is 2mm.
The non-ferrous metal electrodeposition palisading type titanio PbO that the present embodiment is finally given2Positive plate is at electrowinning zinc bath system (Zn2+50g/L, H2SO4150g/L, Mn2+12g/L, C1-1000mg/L, 1000A/m2, temperature is 35 DEG C) and application, compared with traditional metal Pb-0.8%Ag positive plate, the tank voltage of this anode reduces by 9%, and current efficiency improves 4%, and the life-span improves 150%.
Embodiment 3
The titanium bar of a diameter of 12mm is drawn into surface there is the Titanium base of corrugated type decorative pattern, the Concha Arcae tooth depth 0.9mm of corrugated decorative pattern, space width 0.5mm.Bottom titanium copper-clad busbar 1, make a call to the circular hole of one group of Ф 12mm side by side, then one group of Titanium base is inserted in the hole, and be welded to connect with titanium copper-clad busbar, be combined into the fence structure body of 1080mm × 640mm size.By the Titanium base part of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, then through basic plating α-PbO2Composite bed and acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Anode.Specifically comprise the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into ebuillition of heated oil removing 0.5h in concentration 50%NaOH solution, again after mechanical spray coarsening processes, remove oxide-film via pickling 20min in the boiling solution of concentration 20% oxalic acid again, finally Titanium base is cleaned up in placement dehydrated alcohol stand-by with deionized water；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the activation Titanium base of pretreatment layer；Activating solution formula is 60ml/L titanous chloride., 0.1g/L pyrovinic acid cobalt, 0.05g/L rare earth chloride, 800ml/L hydrochloric acid；Poling processing technique condition is temperature 30 DEG C, soak time 1.5 hours；
(3) being immediately placed in alkalescence composite plating solution after step (2) processing the activation Titanium base deionized water cleaning prepared, using rustless steel as negative electrode, temperature is 20 DEG C, and electric current density is 6A/dm2, plating 12 hours under mechanical stirring, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution280g/L, sodium hydroxide NaOH 100g/L, sodium potassium tartrate tetrahydrate 70g/L, electrical-conductive nanometer silver-plated silica dioxide granule 20g/L；Wherein, the preparation of the silver-plated silica dioxide granule of electrical-conductive nanometer is to obtain being placed in alkalescence silver plating liquid by the nano silicon after stannous chloride sensitization, the formula of alkalescence silver plating liquid is 10g/L silver nitrate, 5g/L sodium hydroxide, 3g/L glucose, treatment process condition is temperature 10 DEG C, electroless plating time 6h；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, and using Titanium board as negative electrode, temperature is 30 DEG C, and electric current density is 5A/dm2, plating 4 hours under mechanical stirring, form β-PbO2Multiplicity reactivation top layer, i.e. obtains non-ferrous metal electrodeposition palisading type titanio PbO2Anode；Containing plumbi nitras Pb (NO in described acid composite plating solution3)2200g/L, nitric acid HNO330g/L, sodium tungstate Na2WO4200g/L, particle diameter are 5nm nanometer tungsten carbide 5g/L；
α-PbO on the Titanium base that above-mentioned process finally gives2Composite interlayer thickness is 600 μm, β-PbO2Multiplicity reactivation skin depth is 0.3mm.
The non-ferrous metal electrodeposition palisading type titanio PbO that the present embodiment is finally given2Positive plate is at electrowinning zinc bath system (Zn2+50g/L, H2SO4150g/L, Mn2+12g/L, C1-1000mg/L, 1000A/m2, temperature is 35 DEG C) and application, compared with traditional metal Pb-0.8%Ag positive plate, the tank voltage of this anode reduces by 10%, and current efficiency improves 4%, and the life-span improves 150%.
Embodiment 4
The titanium pipe selecting external diameter to be 6mm～12mm, is drawn into surface and has the Titanium base of corrugated type decorative pattern, the Concha Arcae tooth depth 0.6mm of corrugated decorative pattern, space width 0.4mm.Bottom titanium copper-clad busbar 1, make a call to the circular hole of a group side by side, then one group of Titanium base is inserted in the hole, and be welded to connect with titanium copper-clad busbar, be combined into fence structure body.By the Titanium base of fence structure body through oil removing, sandblasting, removing oxide-film, activation processing, then through basic plating α-PbO2Composite bed and acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Anode.Specifically comprise the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into ebuillition of heated oil removing 1.5h in concentration 45%NaOH solution, again after mechanical spray coarsening processes, remove oxide-film via pickling 20min in the boiling solution of concentration 18% oxalic acid again, finally Titanium base is cleaned up in placement dehydrated alcohol stand-by with deionized water；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the activation Titanium base of pretreatment layer；Activating solution formula is 50ml/L titanous chloride., 0.3g/L pyrovinic acid nickel, 2g/L rare earth chloride, 700ml/L hydrochloric acid；Poling processing technique condition is temperature 50 C, soak time 1 hour；
(3) being immediately placed in alkalescence composite plating solution after step (2) processing the activation Titanium base deionized water cleaning prepared, using rustless steel as negative electrode, temperature is 40 DEG C, and electric current density is 4A/dm2, plating 8 hours under mechanical stirring, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution27g/L, sodium hydroxide NaOH 120g/L, trisodium citrate 65g/L, electrical-conductive nanometer silver-plated silica dioxide granule 15g/L；Wherein, the preparation of the silver-plated silica dioxide granule of electrical-conductive nanometer is to obtain being placed in alkalescence silver plating liquid by the nano silicon after stannous chloride sensitization, the formula of alkalescence silver plating liquid is 7g/L silver nitrate, 5g/L sodium hydroxide, 6g/L glucose, treatment process condition is temperature 8 DEG C, electroless plating time 3h；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, and using Titanium board as negative electrode, temperature is 50 DEG C, and electric current density is 4A/dm2, plating 7 hours under mechanical stirring, form β-PbO2Multiplicity reactivation top layer, i.e. obtains non-ferrous metal electrodeposition palisading type titanio PbO2Anode；Containing plumbi nitras Pb (NO in described acid composite plating solution3)2150g/L, nitric acid HNO325g/L, sodium tungstate Na2WO4180g/L, particle diameter are 15nm nanometer tungsten carbide 15g/L；
α-PbO on the Titanium base that above-mentioned process finally gives2Composite interlayer thickness is 450 μm, β-PbO2Multiplicity reactivation skin depth is 1.5mm.
The non-ferrous metal electrodeposition palisading type titanio PbO that the present embodiment is finally given2Positive plate is at electrowinning zinc bath system (Zn2+50g/L, H2SO4150g/L, Mn2+12g/L, C1-1000mg/L, 1000A/m2, temperature is 35 DEG C) and application, compared with traditional metal Pb-0.8%Ag positive plate, the tank voltage of this anode reduces by 8%, and current efficiency improves 5%, and the life-span improves 200%.
In various embodiments above, by Titanium base pretreatment, activation, basic plating α-PbO2Composite bed and acid electroplating β-PbO2In the whole process technique of composite bed, wrap the gum cover 4 of acid and alkali-resistance at lead-sheathing copper busbar 1 and Titanium base junction, to prevent liquid from connecing position corrosion.During process, support 3 is set, Titanium base is placed on support as shown in Figure 1, shown in Figure 5.Support 3 typically uses the plastic stent of insulation, and Titanium base both sides use insulating blanked clamper edge strip to fix, and block by insulated rivet.Gum cover 4 typically uses silica gel sheath.
Except as otherwise noted, heretofore described percent concentration is weight percent concentration.
The Novel anode using the inventive method to prepare has excellent machinery and corrosion resistance, and bath voltage can be greatly reduced during the electrometallurgy such as wet method electrowinning zinc, electro deposited copper, electro deposited nickel, electrodeposition manganese, reduces energy consumption.
Claims (14)
1. non-ferrous metal electrodeposition palisading type titanio PbO2The manufacture method of anode, it is characterised in that described non-ferrous metal electrodeposition
With palisading type titanio PbO2Anode includes titanium copper-clad busbar (1) and is connected to one group of vertical titanium below titanium copper-clad busbar
Rod (2), every titanium rod is the most successively by Titanium base, pretreatment layer, α-PbO2Composite interlayer and β-PbO2Multiplicity reactivation table
Layer is constituted；Manufacture method is first to be connected to by Titanium base below titanium copper-clad busbar, forms fence structure body, then by fence
The Titanium base part of structure through oil removing, sandblasting, removing oxide-film, activation processing, after through basic plating α-PbO2Composite bed
With acid electroplating β-PbO2Composite bed, it is thus achieved that non-ferrous metal electrodeposition palisading type titanio PbO2Positive plate, specifically comprises the following steps that
(1) the whole group of Titanium base being connected to below titanium copper-clad busbar is put into weight percent concentration 20%～50%NaOH molten
Ebuillition of heated oil removing 30min～2h in liquid, then after mechanical spray coarsening processes, then via weight percent concentration 10%～20%
In the boiling solution of oxalic acid, pickling 20～90min removes oxide-film, finally with deionized water, Titanium base cleans up placement anhydrous
In ethanol stand-by；
(2) Titanium base that step (1) processes is placed in activating solution process, obtains being formed on Titanium base surface the work of pretreatment layer
Change Titanium base；Activating solution formula is 10-60ml/L titanous chloride., 0.1-0.5g/L pyrovinic acid nickel or pyrovinic acid cobalt, 0.05-5g/L
Rare earth chloride or cobaltous chloride, 300-800ml/L hydrochloric acid；Poling processing technique condition is temperature 30～60 DEG C, soak time 0.5～
1.5 hour；
(3) it is immediately placed in alkalescence composite plating solution after step (2) being processed the activation Titanium base deionized water cleaning prepared,
Using rustless steel as negative electrode, temperature is 20～80 DEG C, and electric current density is 0.5～6A/dm2, plating 1～12 under mechanical stirring
Hour, form α-PbO2Composite interlayer；Containing lead acetate Pb (AC) in described alkaline composite plating solution245～80g/L,
Sodium hydroxide NaOH 100～160g/L, trisodium citrate or sodium potassium tartrate tetrahydrate 60～80g/L, the silver-plated silicon dioxide of electrical-conductive nanometer
Granule 5～20g/L；
(4) Titanium base after step (3) being processed is placed in acid composite plating solution, using Titanium board as negative electrode, temperature is
30～70 DEG C, electric current density is 2～5A/dm2, plating 4-16 hour under mechanical stirring, form β-PbO2Multiplicity reactivation top layer,
I.e. obtain non-ferrous metal electrodeposition palisading type titanio PbO2Anode；Containing plumbi nitras Pb (NO in described acid composite plating solution3)2100～200g/L, nitric acid HNO320～30g/L, sodium tungstate Na2WO4Or sodium molybdate Na2MoO4160～200g/L, receive
Rice tungsten carbide 5～20g/L.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, by Titanium base oil removing, sandblasting, removing oxide-film, activation processing, basic plating α-PbO2Composite bed and acid electroplating β-PbO2
In the whole process technique of composite bed, wrap the gum cover (4) of acid and alkali-resistance at lead-sheathing copper busbar (1) and Titanium base junction, anti-
Only liquid connects position corrosion；During process, Titanium base is placed on horizontal support (3).
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 22The manufacture method of anode, its feature exists
In, described support (3) is plastic stent, and described gum cover (4) is silica gel sheath.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, the α-PbO that above-mentioned steps (3) obtains2Composite interlayer thickness is 200 μm～600 μm.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, the silver-plated silica dioxide granule of above-mentioned steps (3) described electrical-conductive nanometer is by by the nano silicon after stannous chloride sensitization
Being placed in acquisition in alkalescence silver plating liquid, the formula of alkalescence silver plating liquid is 3～10g/L silver nitrate, 5g/L sodium hydroxide, 3～10g/L Portugals
Grape sugar, treatment process condition is temperature 0～10 DEG C, electroless plating time 2～6h.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, above-mentioned steps (4) processes the β-PbO obtained2Multiplicity reactivation skin depth is 0.3mm～2mm.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, the particle diameter of the nanometer tungsten carbide described in above-mentioned steps (4) is 5nm～30nm.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, can separately add 0.05g/L PVP in the formula of alkalescence silver plating liquid.
Non-ferrous metal electrodeposition palisading type titanio PbO the most according to claim 12The manufacture method of anode, its feature exists
In, described titanium copper-clad busbar (1) is at titanium copper-clad busbar bear with the connected mode of titanium rod (2), then by titanium
Rod inserts in the hole, then is welded to connect with titanium copper-clad busbar by titanium rod.
10. according to the palisading type titanio PbO of the non-ferrous metal electrodeposition described in claim 1 or 92The manufacture method of anode, it is special
Levying and be, described titanium rod (2) is titanium bar or titanium pipe.
11. non-ferrous metal electrodeposition palisading type titanio PbO according to claim 102The manufacture method of anode, its feature
Being, described titanium bar is cylindrical or elliptical cylinder-shape, and described titanium pipe is round tube or oval pipe.
12. non-ferrous metal electrodeposition palisading type titanio PbO according to claim 102The manufacture method of anode, its feature
Being, the surface of described titanium bar or titanium pipe draws vertical corrugated type or sawtooth pattern decorative pattern.
13. non-ferrous metal electrodeposition palisading type titanio PbO according to claim 112The manufacture method of anode, its feature
Being, described cylindrical titanium shank diameter is 3mm～12mm, and circular titanium pipe external diameter is 6mm～12mm.
14. non-ferrous metal electrodeposition palisading type titanio PbO according to claim 122The manufacture method of anode, its feature
Being, the space width of described corrugated type or sawtooth pattern decorative pattern is 0.1～0.9mm, tooth depth is 0.1～0.5mm.
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| 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 |
| CN113394408A (en) * | 2021-06-17 | 2021-09-14 | 昆明高聚科技有限公司 | Long-life light composite positive grid and preparation method thereof, and positive electrode plate and preparation method thereof |
| CN114808067B (en) * | 2022-04-29 | 2024-04-09 | 中宁县宁华再生资源循环利用科技有限公司 | Titanium-based nano composite anode for zinc electrodeposition and processing technology thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5754291A (en) * | 1980-09-18 | 1982-03-31 | Agency Of Ind Science & Technol | Electrolytic extraction of nickel by lead dioxide electrode |
| CN87106028A (en) * | 1986-08-29 | 1988-03-30 | 通商产业省工业技术院 | The lead oxide-coated electrode of use in electrolysis and manufacture method thereof |
| US5431798A (en) * | 1992-07-17 | 1995-07-11 | Permelec Electrode Ltd. | Electrolytic electrode and method of production thereof |
| CN101054684A (en) * | 2007-02-07 | 2007-10-17 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
| 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 |
| CN102899683A (en) * | 2012-09-17 | 2013-01-30 | 淮南师范学院 | Preparation method of Ti-based nano-CeO2/PbO2 modified electrode |
| CN103205780A (en) * | 2013-04-15 | 2013-07-17 | 昆明理工恒达科技有限公司 | Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode |
-
2013
- 2013-11-14 CN CN201310565008.8A patent/CN103572331B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5754291A (en) * | 1980-09-18 | 1982-03-31 | Agency Of Ind Science & Technol | Electrolytic extraction of nickel by lead dioxide electrode |
| CN87106028A (en) * | 1986-08-29 | 1988-03-30 | 通商产业省工业技术院 | The lead oxide-coated electrode of use in electrolysis and manufacture method thereof |
| US5431798A (en) * | 1992-07-17 | 1995-07-11 | Permelec Electrode Ltd. | Electrolytic electrode and method of production thereof |
| CN101054684A (en) * | 2007-02-07 | 2007-10-17 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
| CN102899683A (en) * | 2012-09-17 | 2013-01-30 | 淮南师范学院 | Preparation method of Ti-based nano-CeO2/PbO2 modified electrode |
| 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 |
| CN103205780A (en) * | 2013-04-15 | 2013-07-17 | 昆明理工恒达科技有限公司 | Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode |
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