CN101654750B - Non-aluminium low-calcium lead-silver-calcium rare earth alloy and preparation method thereof - Google Patents
Non-aluminium low-calcium lead-silver-calcium rare earth alloy and preparation method thereof Download PDFInfo
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- CN101654750B CN101654750B CN2009101027797A CN200910102779A CN101654750B CN 101654750 B CN101654750 B CN 101654750B CN 2009101027797 A CN2009101027797 A CN 2009101027797A CN 200910102779 A CN200910102779 A CN 200910102779A CN 101654750 B CN101654750 B CN 101654750B
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- calcium
- lead
- silver
- rare earth
- aluminium
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- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 52
- 239000011575 calcium Substances 0.000 title claims abstract description 52
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 23
- 239000004411 aluminium Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011133 lead Substances 0.000 claims abstract description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 4
- -1 calcium rare earth Chemical class 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 6
- 239000000155 melt Substances 0.000 abstract 3
- 239000010407 anodic oxide Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 238000005363 electrowinning Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a non-aluminium low-calcium lead-silver-calcium rare earth alloy and a preparation method thereof; the non-aluminium low-calcium lead-silver-calcium rare earth alloy comprises the following components by weight percent: 0.15 to 0.7 percent of silver, 0.03 to 0.09 percent of calcium, 0.02 to 0.08 percent of rare earth metal, and the balance lead. The preparation method comprises the following steps: raising the temperature to 400 to 500 DEG C, to melt the lead in a lead-melting furnace and then holding the temperature; adding the silver, calcium and rare earth metal with weight ratio in lead solution, stirring, and applying a direct-current potential difference of 3 to 36V between a melt and the furnace in the stirring process; standing 30 to 50 minutes after the melt is evenly alloyed, removing oxidizing slag on the surface of the melt and obtaining the non-aluminium low-calcium lead-silver-calcium rare earth alloy. The invention is characterized by low impedance of an anodic oxide film, good corrosion resistance and long service life.
Description
Technical field
The present invention relates to the material technology field, relate in particular to a kind of lead, silver, calcium rare earth alloy that does not have the low calcium of aluminium, also relate to its preparation method simultaneously.
Background technology
The eighties in 20th century, Canadian Ke Mingke company researches and develops successful lead-Yin-calcium multicomponent alloy (argentiferous: 0.25%; Calcic 0.1%; Contain aluminium 0.05%; Surplus lead) rolling anode is used for the electrowinning metallic zinc, and this kind alloy is as traditional lead-silver alloys (argentiferous 1%; Surplus lead) regeneration product of cast anode and be widely used in electrowinning metallic zinc field in the sulfate solution, it is compared with the lead-silver alloys cast anode of traditional argentiferous 1% has the outstanding advantage in following three aspects: the one, save silver 80%, and reduce cost of alloy; The 2nd, alloy strength height (tensile strength δ
b=4.4-4.9kgf/mm
2), the supporting anodes own wt makes anode in use be difficult for producing flexural deformation fully; The 3rd, the operation of rolling has been eliminated pin hole, casting flaw such as loose, and the alloy structure density is improved, and solidity to corrosion improves under the electrowinning zinc technology condition in the aqueous solution, and can reach 1 year work-ing life.
But, mainly there is the shortcoming of following two aspects in the rolling anode of lead-Yin-calcium multicomponent alloy through finding it after the industrial application of more than ten years: the one, and 3-5 month result of use is better before the anode, but later stage degradation, the corrosion aggravation, cause the lead tolerance in the gained cathode zinc very easily to surpass 0.005%, make 1 grade of product rate of product many, 0 grade of product rate is few, and product hierarchy descends; The 2nd, for making not loss of calcium, need to add the protective material of a certain amount of aluminium down in the alloy melting process as calcium at high temperature (680-720 ℃), high temperature makes plumbous vapor pressure increase, and causes Lead contamination increasing and energy consumption to increase, and also makes complete processing become complicated simultaneously.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming and provide a kind ofly have that the anodic oxidation membrane impedance is low, solidity to corrosion is good, the lead, silver, calcium rare earth alloy of the low calcium of the no aluminium of long service life.
Another object of the present invention is to provide this no aluminium to hang down the preparation method of the lead, silver, calcium rare earth alloy of calcium.
A kind of lead, silver, calcium rare earth alloy that does not have the low calcium of aluminium of the present invention, its composition weight ratio is:
The silver that contains 0.15-0.7% contains the calcium of 0.03-0.09%, contains the rare earth metal of 0.02-0.08%, and surplus is plumbous.
The lead, silver, calcium rare earth alloy of the low calcium of above-mentioned no aluminium, it is formed preferable weight ratio and is: contain 0.19% silver, contain 0.05% calcium, contain 0.07% rare earth metal, surplus be a lead.
The lead, silver, calcium rare earth alloy of the low calcium of above-mentioned no aluminium, wherein: lead is No. 1 electrolytic lead, rare earth metal is No. 40 noriums or No. 45 noriums.
The preparation method of the lead, silver, calcium rare earth alloy of the low calcium of no aluminium of the present invention comprises the steps:
(1) is warming up to 400-500 ℃ the fusing of the lead in lead smelting furnace back insulation;
(2) silver, calcium and the rare earth metal with above-mentioned weight ratio adds in the plumbous liquid and stirring, applies the DC potential difference that a 3-36 lies prostrate at melt and furnace room in the whipping process;
(3) treat the even back of melt alloying static 30-50 minute, remove the bath surface oxidation sludge promptly.
The present invention compared with prior art, has tangible advantage, as can be known from the above technical solutions, alloy of the present invention supports under the required fundamental strength of own wt guaranteeing that anode has, and reduces calcium contents in the alloy more than 50%, and does not contain aluminium element, and interpolation trace rare-earth metal, improve the microstructure of alloy effectively, reduced the intergranular corrosion tendency of alloy, improved the anodic solidity to corrosion; In air during melting preparation alloy of the present invention, do not need to add the protective material of aluminium as calcium, only need to apply the DC potential difference that a 3-36 lies prostrate and to reach the purpose that makes calcium stable at lead alloy melt and furnace room, make 1 ton of alloy of every melting save metallic aluminum material and consume 0.5 kilogram, and simplified the melting technology flow process, reduced the melting cost; Under low temperature 400-500 ℃, carry out the disposable melting that feeds intake of alloy, avoided having significantly reduced the pollution of lead steam and plumbous oxide at high temperature 680-720 ℃ of following molten alloy.The anode of this alloy preparation has low anodic oxidation membrane impedance, good solidity to corrosion, longer work-ing life, and manufacturing process is easy, and Lead contamination is little.
Embodiment
Embodiment 1
No. 1 electrolytic lead that takes by weighing 99.70 kilograms is heated to 450 ℃ in smelting furnace, treat plumbous fusing back insulation; Take by weighing 0.09 kilogram of calcium, 0.15 kg silver and 0.06 kilogram of No. 45 norium respectively, all pack into then in the feeding device, this feeding device is sunken to rapidly in the plumbous liquid stirs, between melt and stove, apply simultaneously one 36 volts DC potential difference, stop after 40 minutes stirring, remove the bath surface oxidation sludge after static 30 minutes, the beginning tapping casting, treat to open mould taking-up anode blanket behind the alloy graining, be rolled, cut into 960 * 620 * 6 millimeters positive plate again.Consisting of of this positive plate after testing: argentiferous 0.149%, calcic 0.089%, contain rare earth metal 0.058%.
Resulting positive plate tested show positive plate tensile strength δ
b=4.9kgf/mm
2, can support own wt fully, warpage, distortion can not take place in electrolyzer and cause short circuit.Positive plate in concentration of electrolyte solutions is: Zn
2+56g/l, H
2SO
4140g/l, Mn
2+5g/l, negative electrode are that its corrosion potential is than the low 50mV of existing lead-Yin-calcium multicomponent alloy anode plate under the electrowinning zinc technology condition of 35 ℃ of pure aluminum plate and temperature, and bath voltage hangs down 30mV, and can reach more than 14 months mean life.
Embodiment 2
No. 1 electrolytic lead that takes by weighing 99.69 kilograms is heated to 460 ℃ in smelting furnace, treat plumbous fusing back insulation; Take by weighing 0.05 kilogram of calcium, 0.19 kg silver and 0.07 kilogram of No. 45 norium respectively, all pack into then in the feeding device, this feeding device is sunken to rapidly in the plumbous liquid stirs, between alloy melt and stove, apply simultaneously one 15 volts DC potential difference, stop after 30 minutes stirring, remove the bath surface oxidation sludge after static 30 minutes, the cast of coming out of the stove enters in the mould, treat to open mould taking-up anode blanket behind the alloy graining, be rolled, cut into 960 * 620 * 6 millimeters positive plate again.Consisting of of this positive plate after testing: argentiferous 0.189%, calcic 0.048%, contain rare earth metal 0.067%.
The positive plate of gained tested show positive plate tensile strength δ
b=4.5kgf/mm
2, can support own wt fully, warpage, distortion can not take place in electrolyzer and cause short circuit.Positive plate in concentration of electrolyte solutions is: Zn
2+58g/l, H
2SO
4160g/l, Mn
2+4.0g/l negative electrode is that its corrosion potential is than the low 108mV of existing lead-Yin-calcium multicomponent alloy anode plate under the electrowinning zinc technology condition of 35 ℃ of pure aluminum plate and temperature, bath voltage hangs down 57mV, and can reach more than 15 months mean life.
Embodiment 3
No. 1 electrolytic lead that takes by weighing 99.25 kilograms is heated to 480 ℃ in smelting furnace, treat plumbous fusing back insulation; Take by weighing 0.03 kilogram of calcium, 0.7 kg silver and 0.02 kilogram of No. 40 norium respectively, all pack into then in the feeding device, this feeding device is sunken to rapidly in the plumbous liquid stirs, between alloy melt and stove, apply simultaneously one 3 volts DC potential difference, stop after 40 minutes stirring, remove the bath surface oxidation sludge after static 50 minutes, cast immediately enters in the mould, treat to open behind the alloy graining mould and take out the anode blanket, carry out again cold rolling, cut into 960 * 620 * 6 millimeters positive plate.Consisting of of this positive plate after testing: argentiferous 0.69%; Calcic 0.028%; Contain rare earth metal 0.017%.
The positive plate of gained tested show positive plate tensile strength δ
b=3.8kgf/mm
2, can support own wt fully.Positive plate in concentration of electrolyte solutions is: Zn
2+60g/l, H
2SO
4150g/l, Mn
2+4.5g/l negative electrode is that its corrosion potential is than the low 119mV of existing lead-Yin-calcium multicomponent alloy anode plate under the electrowinning zinc technology condition of 35 ℃ of pure aluminum plate and temperature, bath voltage hangs down 64mV, and can reach more than 16 months mean life.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, any technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (2)
1. a preparation method who does not have the lead, silver, calcium rare earth alloy of the low calcium of aluminium comprises the steps:
(1) is warming up to 400-500 ℃ the fusing of the lead in lead smelting furnace back insulation;
(2) silver, calcium and the rare earth metal with the following weight ratio adds in the plumbous liquid and stirring, applies the DC potential difference that a 3-36 lies prostrate at melt and furnace room in the whipping process;
(3) treat the even back of melt alloying static 30-50 minute, remove the bath surface oxidation sludge promptly;
Wherein: the composition weight ratio of the lead, silver, calcium rare earth alloy of the low calcium of no aluminium is:
The silver that contains 0.15-0.7% contains the calcium of 0.03-0.09%, contains the rare earth metal of 0.02-0.08%, and surplus is plumbous.
2. the preparation method of the lead, silver, calcium rare earth alloy of the low calcium of no aluminium as claimed in claim 1, the preferable weight ratio of lead, silver, calcium rare earth alloy composition of wherein not having the low calcium of aluminium is: contain 0.19% silver, contain 0.05% calcium, contain 0.07% rare earth metal, surplus is plumbous.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101027797A CN101654750B (en) | 2009-09-08 | 2009-09-08 | Non-aluminium low-calcium lead-silver-calcium rare earth alloy and preparation method thereof |
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|---|---|---|---|
| CN2009101027797A CN101654750B (en) | 2009-09-08 | 2009-09-08 | Non-aluminium low-calcium lead-silver-calcium rare earth alloy and preparation method thereof |
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| Publication Number | Publication Date |
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| CN101654750A CN101654750A (en) | 2010-02-24 |
| CN101654750B true CN101654750B (en) | 2011-07-20 |
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| CN107012361A (en) * | 2017-04-10 | 2017-08-04 | 云南驰宏锌锗股份有限公司 | A kind of electrodepositing zinc rare earth alloy anode and preparation method thereof |
| CN110644019A (en) * | 2019-10-28 | 2020-01-03 | 昆明冶金研究院 | Anode plate for high-electric-efficiency zinc electrolysis and preparation method thereof |
| CN114807674A (en) * | 2022-03-31 | 2022-07-29 | 贵州省凯里化冶总厂 | Anode plate alloy and manufacturing method thereof |
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Application publication date: 20100224 Assignee: HUNAN SANLI GROUP Co.,Ltd. Assignor: Su Xiangdong Contract record no.: 2013430000043 Denomination of invention: Non-aluminium low-calcium lead-silver-calcium rare earth alloy and preparation method thereof Granted publication date: 20110720 License type: Exclusive License Record date: 20130428 |
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Granted publication date: 20110720 |