CN104611609A - Low-silver lead alloy multi-element anode material for non-ferrous metal electrodeposition and preparation method thereof - Google Patents
Low-silver lead alloy multi-element anode material for non-ferrous metal electrodeposition and preparation method thereof Download PDFInfo
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- 229910000978 Pb alloy Inorganic materials 0.000 title claims abstract description 57
- 239000010405 anode material Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 17
- 239000004332 silver Substances 0.000 title claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 102
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 93
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 36
- 229910052738 indium Inorganic materials 0.000 claims abstract description 31
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 31
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 25
- 238000005272 metallurgy Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 8
- -1 silver-lead indium tin zirconium Chemical compound 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002701 Ag-Co Inorganic materials 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 12
- 239000011701 zinc Substances 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052725 zinc Inorganic materials 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 abstract 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005520 cutting process Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 238000010310 metallurgical process Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 238000013019 agitation Methods 0.000 description 6
- 238000009499 grossing Methods 0.000 description 6
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OEZQCMMAFSEXQW-UHFFFAOYSA-N calcium silver Chemical compound [Ca].[Ag] OEZQCMMAFSEXQW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003412 degenerative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
Abstract
The invention relates to a low-silver lead alloy multi-element anode material for non-ferrous metal electrodeposition and a preparation method thereof. The anode material comprises the following components in percentage by weight: 0.1-0.2% of silver, 0.1-1% of indium, 0.1-0.5% of tin, 0.1-0.3% of zirconium, 0.01-0.4% of titanium and the balance of lead. A production process of an anode plate body comprises the following steps: melting a lead block, firstly adding a tin-titanium intermediate alloy, after the tin-titanium intermediate alloy is molten, adding a partial of lead, after lead is molten, adding silver, indium and a lead-zirconium intermediate alloy, after silver, indium and the lead-zirconium intermediate alloy are molten, adding residual lead and melting to obtain molten lead alloy, pouring the molten lead alloy and cooling to obtain a billet plate, rolling to obtain a lead alloy plate, carrying out surface-increasing treatment on the lead alloy plate, flattening, cutting and carrying out activation treatment to obtain the finished product plate. The anode material is excellent in corrosion resistance at a high current density, the voltage of an electrolytic cell is significantly reduced in electric metallurgical processes, such as wet zinc electrodeposition and wet copper and manganese electrodeposition and the energy consumption is decreased.
Description
Technical field
The present invention relates to a kind of novel anode material for electro-deposition of nonferrous metals and preparation method thereof technical field, be specifically related to a kind of electrolysis polynary anode material of low argentalium alloy used for non-ferrous metal and preparation method thereof.
Background technology
In whole industrial production, metallurgical industry remains big power consumer, and production energy consumption is high, and its main unit consumption of energy 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 the energy consumption of whole zinc leaching process 2/3, and the production energy consumption of zinc hydrometallurgy is 3800 ~ 4200kwh/t.Zn, produces 5000000 tons of zinc per year in the whole nation in 2007, power consumption is 20,300,000,000 kilowatt-hours, accounts for 0.64 ~ 0.75% of national industrial total electricity consumption.Especially when current global economy depression, to reduction metallurgical industry energy consumption, improve enterprise independent innovation ability significant with the upgrading industrial structure, one is to alleviate China's energy-intensive situation, two is to exploit in a large number and reserves minimizing, ore grade reduction, price increase, corresponding exploitation tooling cost increase, and can increase the competitive edge of enterprise under the situation of product price degradation in Mineral resources.Both at home and abroad above-mentioned electrolytic deposition process of metal insoluble anode is conducted in-depth research and developed.Research current both at home and abroad and service condition are substantially as follows:
1, Ca system lead based alloy anodes---low Ag multicomponent alloy, being added with of calcium helps the mechanical property improving anode, reduce anode silver content, but anode easily produces local corrosion in electrolytic process, surface anode mud crust is hard, not easily remove and cause bath voltage high, and when anode reclaims, the loss of silver calcium is large.
2, Co system lead based alloy anodes---low Ag or without Ag alloy, Co has good electrocatalysis effect, Pb-Co
3o
4with Pb-Ag (0.2%)-Sn (0.12%)-Co (0.06%) alloy anode, there is the overpotential for oxygen evolution lower than Pb-Ag (1.0%) anode and stronger corrosion resistance nature, but the solubleness of Co in plumbous melt is atomic, preparation method is complicated.
3, DSA---with Fe, Pt, pottery etc. for substrate, wherein Ti base DSA is study hotspot, and physical dimension is stablized, without the short circuit problem that bending causes; Zinc percentage of product is high; Pole plate is lightweight, and convenient carrying and process are changed; Can be used for multiple electric effusion system; Be applicable to high current density (4.5 ~ 6.0kA/m
2) and the electrodeposition condition of narrow interpole gap (about 5mm).But work-ing life is short, the metal adopted in the easy passivation of Titanium base and anode coating easily causes and burns plate phenomenon etc.
4, lead base composite anode---at Pb matrix surface composite noble metal oxide catalyst, IrOx, RuO
2analyse oxygen electro catalytic activity and electrochemical stability with good, but the preparation cost of anode and anode make a breakthrough not yet, limit applying of such anode work-ing life.
In order to overcome the weakness of lead-based multi-component alloy, people study the strong degenerative element of solidity to corrosion further, its object is to improve plumbous recrystallization temperature, the crystal grain of refinement lead, improve plumbous physical strength and bending resistance, tensile strength, and keep good conductivity and resistance to corrosion.Such as, Ivanov is at " Ivanov I, Stefanov Y, Noncheva Z, Petrova M, Dobrev Ts, Mirkova L, Vermeersch R, Demaerel J.-P. Insoluble anodes used in hydrometallurgy Part I. Anodic behaviour of lead and lead-alloy anodes [J]. Hydrometallurgy, 2000,57:109-124 " review the anti-corrosion of different lead based alloy anodes and electrocatalysis characteristic in a literary composition.Find that Ti adds in pb-ag alloy the anode forming ternary alloy and has good erosion resistance, along with the increase of Ti content, the dissolving of Pb lead alloy in sulphuric acid soln reduces, and the proportioning of best erosion resistance is Pb-0.75%Ag-0.5%Ti.W. Zhang is at " Zhang W, Houlachi G. Electrochemical studies of the performance of different Pb-Ag anodes during and after zinc electrowinning [J]. Hydrometallurgy, 2010,104 (2): 129-35 " think in a literary composition alterant element Zr can be formed in sulfuric acid erosion resistance strong Cubic ZrO
2.But their preparation method has no report.R. H. NEWNHAM is at " Newnham R H. Corrosion rates of lead based anodes for zinc electrowinning at high current densities. Journal of Applied Electrochemistry, 1992,22 (2): 116-124 " one the article pointed out, at 5000A/m
2high current density polarization find Pb-(0.37%) Ag-(0.99%) Tl-0.12%Ca anode, be considered to a kind of perfectly alloy anode, erosion resistance increases by four times, and the solubleness of Pb reduces by five times.But Tl has very high toxicity, is unfavorable for industrial applicability.And along with the increase of labor cost, improve current density and can reduce labor force, be easy to change electrolyzer, servicing time is short, and electrolytic solution is not easy to reveal, and more can energy-saving consumption-reducing.But traditional lead-silver anode is perishable at higher current densities, the Lead contamination negative electrode of generation, can not satisfy social needs.
summary of the invention:the object of the invention is the shortcoming of the existence in order to overcome above-mentioned prior art, polynary anode material of the low argentalium alloy of a kind of non-ferrous metal electrodeposition and preparation method thereof is provided, the anode obtained is used at higher current densities there is the advantage that electro catalytic activity is good and electrode life is long.
Object of the present invention is achieved through the following technical solutions:
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, described anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, the composition of this plate body alloy material is silver 0.1 ~ 0.2% by weight percentage, indium 0.1 ~ 1%, tin 0.1 ~ 0.5%, zirconium 0.1 ~ 0.3%, titanium 0.01 ~ 0.4%, surplus is plumbous.
A kind of non-ferrous metal electrodeposition preparation method of the polynary anode material of low argentalium alloy, the fabrication processing of anode plate body is: first add tin titanium master alloy after being melted by the lead of total lead weight 2/3, part lead is added again after to be melted, silver-colored indium and plumbous zirconium master alloy is added again after to be melted, the lead adding surplus after to be melted obtains lead alloy liquid to fusing, then lead alloy liquid is poured into a mould, blank flat is obtained after cooling, rolling afterwards obtains lead alloy plate, again increasing list processing is carried out to lead alloy plate, then smooth, shear, production board is obtained after activated process.
Silver-colored indium master alloy employing high vacuum arc melting method of the present invention is molten into the AI alloy containing indium mass percent 40 ~ 60%.Described plumbous zirconium master alloy employing vacuum metallurgy method is molten into the plumbous zirconium alloy containing zirconium mass percent 20%.Described tin titanium master alloy adopts vacuum metallurgy method to be molten into the tin titanium alloy of titaniferous mass percent 9%.The pouring type of lead alloy liquid aluminium alloy is poured into quick water-cooled to erect in mould, is cooled to room temperature.The pattern depth that lead alloy plate increases after list processing is 0.1 ~ 0.25 millimeter, and decorative pattern width is 2.5 ~ 4.0 millimeters.Described activation treatment is placed on containing in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES liquid fused salt by increasing the lead alloy plate after list processing, under temperature 90 ~ 160 DEG C of conditions, soak 0.5 ~ 3h.Lead alloy plate after increasing list processing is also placed in the nitrate solution of Ag and Co or Ag-Co alloy by described activation treatment soaks 0.5 ~ 3h, then to be placed in heat treatment tank type stove thermal treatment 1 ~ 28h under 100 ~ 300 DEG C of temperature condition, nitrate solution concentration is 0.01g/L ~ 10g/L.Can acetum be adopted to clean lead alloy plate before activation treatment.
The present invention compared to existing technology tool has the following advantages:
1) because alterant silver and indium can improve the solidity to corrosion of lead alloy and the bath voltage reduced in electrolytic process, Ag doped and In play collaborative effect, and lead based alloy anodes can be made to have minimum overpotential for oxygen evolution and best solidity to corrosion;
2) silver-colored indium master alloy adopts the fusing of high vacuum arc melting method can reduce the scaling loss of precious metal and make alloying constituent even;
3) plumbous zirconium and tin titanium master alloy adopt vacuum smelting method can reduce the scaling loss of zirconium and titanium metal;
4) introducing has alterant element titanium and zirconium, greatly can strengthen the erosion resistance of anode;
5) adopt quick water-cooled to erect die casting and prepare lead-based multi-component alloy, quick cooling makes the normal desolvation process of the not free generation of alloy material, can be dissolved in when liquid state in another material, generally insoluble when solid-state, so just obtain the uniform mixture of all elements, the solidity to corrosion of alloy is improved greatly, and performance is homogeneous;
6) adopt activation treatment can improve the catalytic activity of anode surface, make anode more easily release oxygen at higher current densities, reduce bath voltage;
Anode material of the present invention uses under being particluarly suitable for high current density, can improve production capacity, reduces the labor force of cleaning trough, is easy to safeguard.Also can reduce the quantity of additive, and improve the overvoltage of liberation of hydrogen, favourable to current efficiency, and the careful cathode product of crystallization can be obtained.
Embodiment
embodiment 1
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.18% by weight percentage, indium 0.6%, tin 0.3%, zirconium 0.21%, titanium 0.09%, surplus is plumbous.Plate body is manufactured 240mm(high) × 160mm(is wide) × 6mm(is thick) sample, manufacture method comprises the steps:
A, by purity be 99.9% electrolysis lead melt under 340 DEG C of conditions in intermediate frequency furnace, be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy, to be melted and after stirring, add that surplus is plumbous obtains lead alloy liquid to fusing.Plumbous point adds for three times, first time add-on be 2/3 of total lead weight, after twice leading play the effect reducing temperature, it is determined according to temperature and raising the efficiency.Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 40% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, by after the lead alloy liquid of gained respectively magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, adopt the acetum cleaning of weight percent concentration 10% after shearing, then is immersed after washing 150 DEG C containing soaking 2h in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES liquid fused salt, hot water obtains production board after cleaning.
By the polynary positive plate of above-mentioned low argentalium alloy at electrowinning zinc bath system (Zn
2+50g/L, H
2sO
4150 g/L, Mn
2+5g/L, temperature is 35 DEG C) in application, with 5000A/m
2current density carry out electrolysis, compared with traditional alloy lead anode plate, the bath voltage of the polynary anode of this low argentalium alloy reduces by 14%, and corrosion rate reduces 60%.To energy saving, the consumption reducing lead anode has significant effect.
embodiment 2
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.2% by weight percentage, indium 0.1%, tin 0.5%, zirconium 0.21%, titanium 0.2%, surplus is plumbous.Plate body is manufactured 240mm(high) × 160mm(is wide) × 8mm(is thick) sample, manufacture method comprises the steps:
A, by purity be 99.9% electrolysis lead in intermediate frequency furnace, under 340 DEG C of conditions, melt (electrolysis lead weight is total lead 2/3), be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy respectively, add the plumbous extremely fusing of surplus after stirring after to be melted and obtain lead alloy liquid; Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 50% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, after the lead alloy liquid of gained difference magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, the acetum cleaning of 10% is adopted after shearing, immersed in the silver nitrate solution of volumetric concentration 0.2g/L after washing again and soaked 3h, then being placed in heat treatment tank type stove with temperature is obtain production board after 200 DEG C of thermal treatment 20h cool.
By the polynary positive plate of above-mentioned low argentalium alloy at electro deposited copper bath system (Cu
2+40g/L, H
2sO
4180 g/L, temperature is 60 DEG C) in application, with 2000A/m
2current density carry out electrolysis, compared with traditional alloy lead anode plate, the bath voltage of the polynary anode of this low argentalium alloy reduces by 20%, and corrosion rate reduces 80%.
embodiment 3
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.1% by weight percentage, indium 1 %, tin 0.3%, zirconium 0.3%, titanium 0.01%, surplus is plumbous.
Plate body manufacture method is as follows:
A, by purity be 99.9% electrolysis lead melt under 340 DEG C of conditions in intermediate frequency furnace, be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy, to be melted and after stirring, add that surplus is plumbous obtains lead alloy liquid to fusing; ; Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 45% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, by after the lead alloy liquid of gained respectively magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, adopt the acetum cleaning of weight percent concentration 10% after shearing, then is immersed after washing 160 DEG C containing soaking 0.5h in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES liquid fused salt, hot water obtains production board after cleaning.
embodiment 4
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.18% by weight percentage, indium 0.8 %, tin 0.3%, zirconium 0.2%, titanium 0.3%, surplus is plumbous.
Plate body manufacture method is as follows:
A, by purity be 99.9% electrolysis lead melt under 340 DEG C of conditions in intermediate frequency furnace, be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy respectively, add the plumbous extremely fusing of surplus after stirring after to be melted and obtain lead alloy liquid; Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 55% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, after the lead alloy liquid of gained difference magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, the acetum cleaning of 10% is adopted after shearing, what after washing, immersed volumetric concentration 0.01g/L again soaks 2h containing in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES dissolved salt liquid, then being placed in heat treatment tank type stove with temperature is obtain production board after 300 DEG C of thermal treatment 1h cool.
embodiment 5
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.15% by weight percentage, indium 0.5 %, tin 0.1%, zirconium 0.1%, titanium 0.4%, surplus is plumbous.
Plate body manufacture method is as follows:
A, by purity be 99.9% electrolysis lead melt under 340 DEG C of conditions in intermediate frequency furnace, be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy respectively, add the plumbous extremely fusing of surplus after stirring after to be melted and obtain lead alloy liquid; Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 40 ~ 60% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, after the lead alloy liquid of gained difference magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, the acetum cleaning of 10% is adopted after shearing, immersed in the cobalt nitrate solution of volumetric concentration 10g/L after washing again and soaked 0.5h, then being placed in heat treatment tank type stove with temperature is obtain production board after 100 DEG C of thermal treatment 28h cool.
embodiment 6
A kind of non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, this anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, and the composition of this plate body alloy material is silver 0.1% by weight percentage, indium 0.5 %, tin 0.4%, zirconium 0.3%, titanium 0.2%, surplus is plumbous.
Plate body manufacture method is as follows:
A, by purity be 99.9% electrolysis lead melt under 340 DEG C of conditions in intermediate frequency furnace, be rapidly heated after fusing 860 ~ 980 DEG C and add tin titanium master alloy, stir after to be melted, add part lead again, after temperature 700 DEG C, add silver-colored indium, plumbous zirconium master alloy, to be melted and after stirring, add that surplus is plumbous obtains lead alloy liquid to fusing; ; Tin titanium master alloy is the tin titanium alloy of the titaniferous mass percent 9% adopting the fusing of vacuum metallurgy method, silver indium master alloy is the AI alloy containing indium mass percent 45% adopting the fusing of high vacuum arc melting method, and plumbous zirconium master alloy is the plumbous zirconium alloy containing zirconium mass percent 20% adopting the fusing of vacuum metallurgy method;
B, by after the lead alloy liquid of gained respectively magnetic agitation and mechanical stirring 20min, drag for slag, proceeding to quick water-cooled erects in die device, obtain blank flat, lead alloy plate is obtained through rolling, then lead alloy plate is carried out increasing list processing, the pattern depth 0.1 ~ 0.25 millimeter of lead alloy plate after increasing list processing, decorative pattern width 2.5 ~ 4.0 millimeters, finally by smoothing, adopt the acetum cleaning of weight percent concentration 10% after shearing, then is immersed after washing 90 DEG C containing soaking 2h in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES liquid fused salt, hot water obtains production board after cleaning.
Claims (10)
1. the non-ferrous metal electrodeposition polynary anode material of low argentalium alloy, it is characterized in that, described anode material is the Ti alloyed anode plate body of low silver-lead indium tin zirconium, the composition of this plate body alloy material is silver 0.1 ~ 0.2% by weight percentage, indium 0.1 ~ 1%, tin 0.1 ~ 0.5%, zirconium 0.1 ~ 0.3%, titanium 0.01 ~ 0.4%, surplus is plumbous.
2. a kind of non-ferrous metal electrodeposition as claimed in claim 1 preparation method of the polynary anode material of low argentalium alloy, it is characterized in that, the fabrication processing of anode plate body is: first add tin titanium master alloy after being melted by the lead of total lead weight 2/3, part lead is added again after to be melted, silver-colored indium and plumbous zirconium master alloy is added again after to be melted, the lead adding surplus after to be melted obtains lead alloy liquid to fusing, then lead alloy liquid is poured into a mould, blank flat is obtained after cooling, rolling afterwards obtains lead alloy plate, again increasing list processing is carried out to lead alloy plate, then smooth, shear, production board is obtained after activated process.
3. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, it is characterized in that, described silver-colored indium master alloy employing high vacuum arc melting method is molten into the AI alloy containing indium mass percent 40 ~ 60%.
4. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, is characterized in that, described plumbous zirconium master alloy employing vacuum metallurgy method is molten into the plumbous zirconium alloy containing zirconium mass percent 20%.
5. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, is characterized in that, described tin titanium master alloy adopts vacuum metallurgy method to be molten into the tin titanium alloy of titaniferous mass percent 9%.
6. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, is characterized in that, the pouring type of lead alloy liquid aluminium alloy is poured into quick water-cooled to erect in mould, is cooled to room temperature.
7. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, is characterized in that, the pattern depth that lead alloy plate increases after list processing is 0.1 ~ 0.25 millimeter, and decorative pattern width is 2.5 ~ 4.0 millimeters.
8. a kind of non-ferrous metal electrodeposition according to claim 2 preparation method of the polynary anode material of low argentalium alloy, it is characterized in that, described activation treatment is placed on containing in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES liquid fused salt by increasing the lead alloy plate after list processing, under temperature 90 ~ 160 DEG C of conditions, soak 0.5 ~ 3h.
9. a kind of non-ferrous metal electrodeposition according to claim 8 preparation method of the polynary anode material of low argentalium alloy, it is characterized in that, described activation treatment is placed in the nitrate solution of Ag and Co or Ag-Co alloy soaks 0.5 ~ 3h by increasing the lead alloy plate after list processing, then to be placed in heat treatment tank type stove thermal treatment 1 ~ 28h under 100 ~ 300 DEG C of temperature condition, nitrate solution concentration is 0.01g/L ~ 10g/L.
10. the preparation method of the polynary anode material of low argentalium alloy of a kind of non-ferrous metal electrodeposition according to any one of claim 2-9, is characterized in that, before activation treatment, adopt acetum to clean lead alloy plate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191930A (en) * | 2016-07-04 | 2016-12-07 | 北京有色金属研究总院 | A kind of electrification is metallurgical with alloy lead anode plate and preparation method thereof |
| CN106435652A (en) * | 2016-11-11 | 2017-02-22 | 中南大学 | Rolled porous lead alloy anode and preparation process thereof |
| CN106756228A (en) * | 2016-12-02 | 2017-05-31 | 北京有色金属研究总院 | A kind of method for extending the calendering alloy lead anode material military service life-span |
| 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 |
| CN114232035A (en) * | 2021-12-21 | 2022-03-25 | 贵州省新材料研究开发基地 | Modified anode for hydrometallurgy and preparation method thereof |
| CN115354190A (en) * | 2022-07-07 | 2022-11-18 | 水口山有色金属有限责任公司 | Ternary lead-based alloy and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63243300A (en) * | 1987-03-31 | 1988-10-11 | Kawasaki Steel Corp | Insoluble anode for electroplating |
| CN1936091A (en) * | 2006-07-20 | 2007-03-28 | 陈文鹏 | Low silver-lead multielement alloy anode material for zinc electrolysis |
| US20070193879A1 (en) * | 2006-02-23 | 2007-08-23 | Prengaman David R | Alloy and anode for use in the electrowinning of metals |
| 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 |
| CN103898354A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Lead alloy anode material for zinc electrodeposition and rolling method thereof |
-
2015
- 2015-02-13 CN CN201510077638.XA patent/CN104611609B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63243300A (en) * | 1987-03-31 | 1988-10-11 | Kawasaki Steel Corp | Insoluble anode for electroplating |
| US20070193879A1 (en) * | 2006-02-23 | 2007-08-23 | Prengaman David R | Alloy and anode for use in the electrowinning of metals |
| CN1936091A (en) * | 2006-07-20 | 2007-03-28 | 陈文鹏 | Low silver-lead multielement alloy anode material for zinc electrolysis |
| 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 |
| CN103898354A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Lead alloy anode material for zinc electrodeposition and rolling method thereof |
Non-Patent Citations (1)
| Title |
|---|
| W. ZHANG ET AL.: "Electrochemical studies of the performance of different Pb–Ag anodes during and after zinc electrowinning", 《HYDROMETALLURGY》, vol. 104, no. 129135, 31 December 2010 (2010-12-31) * |
Cited By (8)
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| CN106191930A (en) * | 2016-07-04 | 2016-12-07 | 北京有色金属研究总院 | A kind of electrification is metallurgical with alloy lead anode plate and preparation method thereof |
| CN106191930B (en) * | 2016-07-04 | 2018-06-15 | 北京有色金属研究总院 | A kind of metallurgical alloy lead anode plate and preparation method thereof of electrification |
| CN106435652A (en) * | 2016-11-11 | 2017-02-22 | 中南大学 | Rolled porous lead alloy anode and preparation process thereof |
| CN106756228A (en) * | 2016-12-02 | 2017-05-31 | 北京有色金属研究总院 | A kind of method for extending the calendering alloy lead anode material military service life-span |
| 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 |
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| CN114232035A (en) * | 2021-12-21 | 2022-03-25 | 贵州省新材料研究开发基地 | Modified anode for hydrometallurgy and preparation method thereof |
| CN115354190A (en) * | 2022-07-07 | 2022-11-18 | 水口山有色金属有限责任公司 | Ternary lead-based alloy and preparation method and application thereof |
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Denomination of invention: Preparation method of low-silver lead alloy multi-element anode material for non-ferrous metal electrodeposition Effective date of registration: 20200407 Granted publication date: 20160824 Pledgee: Pudong Shanghai Development Bank Limited by Share Ltd. Kunming branch Pledgor: KUNMING HENDERA SCIENCE AND TECHNOLOGY Co.,Ltd. Registration number: Y2020530000009 |
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