CN104831118A - Lead alloy anode material for copper electrolysis and preparation method thereof - Google Patents
Lead alloy anode material for copper electrolysis and preparation method thereof Download PDFInfo
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- CN104831118A CN104831118A CN201510205588.9A CN201510205588A CN104831118A CN 104831118 A CN104831118 A CN 104831118A CN 201510205588 A CN201510205588 A CN 201510205588A CN 104831118 A CN104831118 A CN 104831118A
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Abstract
The invention relates to a lead alloy anode material for copper electrolysis and a preparation method thereof, and belongs to the technical field of novel anode materials. The anode material is composed of four elements in percentage by weight: 0.3 to 0.6 wt% of tin, 0.01 to 0.05 wt% of copper, 0.06 to 0.1 wt% of calcium, and the balance being lead, and is prepared by casting. Compared with the prior art, the provided anode material has the advantages that the corrosion resistant performance is strong, the service life is longer when the anode material is applied to copper electrolysis, and thus the production cost of copper electrolysis is reduced.
Description
Technical field
The present invention relates to a kind of electrolytic copper alloy lead anode material and preparation method thereof, the high strength adopted in especially a kind of electrolytic copper process, low-loss anode material, belongs to anode new material technology field.
Background technology
Traditional electrolytic copper technique generally adopts lead antimony alloy (Pb-4 ~ 7wt.%Sb) or lead-calcium-tin alloy (Pb-0.02 ~ 0.2wt.%Ca-1.5 ~ 2wt.%Sn) to be inert anode material.Although these two kinds of alloy lead anode materials can meet the strength demand of current electrolytic copper technique antianode, but still it is high to there is cost, corrosion-prone shortcoming.On the one hand, because the doped element content of two kinds of anode materials is higher, material cost is caused to rise; On the other hand, two kinds of anode materials are easy to corrosion in electrolytic copper process, cause anode service life short, increase electrolytic copper production cost.
Therefore be badly in need of a kind of cost low, high anti-corrosion lead base inert anode material substitutes now widely used plumbous antimony or lead-calcium-tin alloy anode material.
Summary of the invention
The invention provides a kind of low cost, long lifetime, alloy lead anode novel material of easy processing and preparation method thereof, the alloy lead anode novel material more traditional alloy lead anode material obtained has longer service life in electrolytic copper process, thus is conducive to reducing electrolytic copper production cost.
Technical scheme of the present invention is achieved in that
Electrolytic copper alloy lead anode material of the present invention is elementary composition by lead, tin, copper and calcium four kinds, and the content of tin, copper and calcium three kinds of elements is respectively tin 0.3 ~ 0.6wt.%, copper 0.01 ~ 0.05wt.%, calcic 0.06 ~ 0.1wt.%, and surplus is plumbous.In addition, all >=99.9%, calcium metal is calcium contents is the plumbous calcium mother alloy of 1.5 ~ 6wt.% to the purity of lead, tin and these three kinds of raw material metals of copper.
Alloy lead anode novel material provided by the invention adopts castmethod preparation, and processing step is as follows:
1. make it melt the heating of solid pure lead by component proportions, obtain plumbous liquid;
2. solid-state pure tin, plumbous calcium mother alloy added in the plumbous liquid that step 1 obtains by component proportions, make its completely, uniform melt, form aluminium alloy;
3. by component proportions solid-state fine copper added in the aluminium alloy in step 2, make its completely, uniform melt;
4., by mould and die preheating, cast.(object of preheating prevents in the process of casting, and demixing phenomenon appears in quad alloy material, is unfavorable for following process.)
The alloy lead anode novel material that the present invention obtains is compared with existing electrolytic copper anode material (lead antimony alloy or lead-calcium-tin alloy), there is following advantages and effect: adopt above-mentioned slicker solder calcium copper quad alloy material, not only there is the advantage that cost is low, but also there is raising anode surface solidity to corrosion, increase the effects such as physical strength.
Accompanying drawing explanation
Fig. 1 is the anode surface corrosion product shape appearance figure of slicker solder calcium copper alloy anode material embodiment 1 in electrolyte plating solution after electrolysis 72h of traditional lead antimony alloy anode in the specific embodiment of the invention, lead-calcium-tin alloy anode and invention
Embodiment
The present invention is further illustrated below by specific embodiment.These embodiments are not the restrictions to summary of the invention, and any equivalent replacement or known change all belong to scope.
Comparative example 1
The as cast condition plumbous antimony binary alloy plate that market is bought, dimensions is 250 × 100 × 8mm, and chemical constitution is: antimony 4.1wt.%, remaining lead.
Comparative example 2
The as cast condition plumbous calcium tin ternary alloy plate that market is bought, dimensions is 250 × 100 × 8mm, and chemical constitution is: calcium 0.09wt.%, tin 1.7wt.%, remaining lead.
Embodiment 1
1. be in the lead 2452g input melting pot of 99.99% by purity, be heated to 380 ~ 420 DEG C, make it melt.
2. after lead melts completely, adding 7.5g purity in the plumbous liquid in step 1 is the tin of 99.9% and the plumbous calcium mother alloy of 40g calcic 5wt.%, is warming up to 500 DEG C and machinery and is stirred to solid metal or metallic compound dissolves completely.
3. after the aluminium alloy of step 2 dissolves completely, in above-mentioned aluminium alloy, add 1.25g purity is 99.9% bronze medal, is warming up to 550 DEG C and machinery and is stirred to solid metal or metallic compound dissolves completely.
4. steel die is preheated to 220 ~ 280 DEG C, and the aluminium alloy temperature of step 3 is down to 360 ~ 400 DEG C.
5. the plumbous calcium gun-metal liquid melted completely is poured in mould, take out after air cooling to room temperature.
Embodiment 2
1. be in the lead 2412g input melting pot of 99.99% by purity, be heated to 380 ~ 420 DEG C, make it melt.
2. after lead melts completely, in the plumbous liquid in step 1, add the plumbous calcium mother alloy that 12.5g purity is 99.9% tin and 75g calcic 2wt.%, be warming up to 500 DEG C and machinery and be stirred to solid metal or metallic compound dissolves completely.
3. after the aluminium alloy of step 2 dissolves completely, in above-mentioned aluminium alloy, add 1g purity is 99.9% bronze medal, is warming up to 550 DEG C and machinery and is stirred to solid metal or metallic compound dissolves completely.
4. steel die is preheated to 220 ~ 280 DEG C, and the aluminium alloy temperature of step 3 is down to 360 ~ 400 DEG C.
5. the plumbous calcium gun-metal liquid melted completely is poured in mould, take out after water-cooled to room temperature.
Because lead density is large, intensity is low, and when hanging, anode easily produces creep strain, can cause short circuit time serious, brings totally unfavorable impact to production, and therefore intensity evaluates the important index of of positive plate performance quality.
The tensile strength test of the lead based alloy anodes material in above-mentioned comparative example and following examples completes in MTS800 material-testing machine.Four kinds of lead 2-base alloy sheet material linear cutter are become the tension specimen of tabular, sample size meets GB/T228.1-2010 standard.Then be placed on universal testing machine by obtained stretching sample and at room temperature carry out Elongation test, loading rate is 0.5mm/min.
The electric conductivity height of anode material affects the voltage in anode use procedure, and the voltage in the anode use procedure that electric conductivity is high is low, also reduces bath voltage and energy consumption.Therefore, electric conductivity is one of important performance indexes of alloy lead anode material.Four kinds of lead alloy plates are cut into and is of a size of 200mm × 10mm × 3mm, on the dual-purpose electric bridge of QJ19 type list both arms, adopt voltammetry to test its resistivity.Then electric conductivity e is calculated as follows:
e＝ρ
Cu/ρ
In formula: ρ is resistivity (Ω mm
2m
-1); ρ
curesistivity (the 0.017241 Ω mm of fine copper
2m
-1).
In electrolytic copper process, the corrosive nature quality of lead based alloy anodes material determines the work-ing life of anode on the one hand, also closely related with electrolytic copper quality product on the other hand, because anode surface is oxidized the PbO split away off
2be partially converted into Pb in the electrolytic solution
2+separate out or PbO at cathodic discharge
2particle is mingled with or sticks to electrolytic copper surface in electrolytic copper, all can make in electrolytic copper leaded, reduces electrolytic copper quality.Therefore, anode corrosion resistance nature evaluates the very important index of of electrolytic copper anode alloy property quality.
The corrosive nature of the lead based alloy anodes material in above-mentioned comparative example and following examples detects and all adopts weight-loss method to test, method is as follows: polished flat by test electrode abrasive paper for metallograph, clean, weigh after dry 12h in vacuum drying oven again, obtain electrolytic copper alloy lead anode net weight, be designated as m
1.Sample after weighing is carried out galvanostatic polarization in three-electrode system, and (electrolytic solution is H
2sO
4180g/L, Cu
2+45g/L, temperature 60 C, current density 250A/m
2), the anode after polarization 72h is taken out, in sugared alkaline solution, removes surperficial plumbous oxide film, weigh after dry 12h in loft drier after cleaning, obtain anode net weight m after electrolysis
2, the difference of the anode weight before and after electrolysis is weightless, i.e. the etching extent of anode, and calculates erosion rate with following formula.
V
c＝(m
1-m
2)/(S×t)
In formula: V
cerosion rate, g/ (m
2h); m
1the weight before anodic polarization, g; m
2the weight after anodic polarization, g; S is anode working area, m
2; T is the anodic polarization time, h.
The performance test results of all alloy lead anode materials sees the following form.
Table 1: slicker solder calcium copper anode material and plumbous antimony, the physics of plumbous calcium tin anode material, chemical property contrast
As can be seen from the experimental data in table 1, the lead antimony alloy anode material that the pull resistance of slicker solder calcium copper anode material, electric conductivity and erosion resistance are more traditional and lead-calcium-tin alloy anode material have lifting by a relatively large margin.
By three kinds of lead alloy plate (H in electrolyte plating solution of comparative example 1, comparative example 2 and embodiment 1
2sO
4180g/L, Cu
2+45g/L, temperature 60 C, current density 250A/m
2) after galvanostatic polarization 72h, the surface topography of anode as shown in Figure 1.As shown in Figure 1, the surface topography map of the slicker solder calcium copper alloy positive plate that (a) is the embodiment of the present invention 1 in figure, the surface topography map of b slicker solder calcium alloy panel material that () is comparative example 2, the surface topography map of the lead antimony alloy positive plate that (c) is comparative example 1.
As shown in Figure 1, the surface corrosion product of the slicker solder calcium copper alloy positive plate adopting the present invention to prepare is with matrix in conjunction with relatively good, and structure is finer and close, even.Comparatively speaking, the surface corrosion product porous of plumbous antimony, lead-calcium-tin alloy positive plate, in electrolytic process, the corrosion layer on the oxygen antianode surface that anode surface generates has impact and stirring action, makes the PbO that lead antimony alloy anode surface is loose
2and PbSO
4corrosion scales easily comes off, and then " fresh " lead alloy matrix of corrosion bottom, therefore their corrosion resistance is not as slicker solder calcium copper alloy positive plate.
Claims (4)
1. an electrolytic copper alloy lead anode material, comprise lead, tin, copper and calcium four kinds of elements, it is characterized in that, the mass percentage of four kinds of metals is as follows: tin 0.3 ~ 0.6wt.%, copper 0.01 ~ 0.05wt.%, calcium 0.06 ~ 0.1wt.%, and all the other are plumbous.
2. electrolytic copper alloy lead anode material according to claim 1, preparation method is as follows: the heating of solid metal lead makes it be molten into plumbous liquid by component proportions by (1); (2) by component proportions, solid metal tin, calcium metal are added in the plumbous liquid described in step 1, heat up make its completely, uniform melt, form aluminium alloy; (3) by component proportions, solid metal copper is added in the aluminium alloy described in step 2, heat up make its completely, uniform melt; (4) by mould and die preheating, cast.
3. the preparation method of electrolytic copper alloy lead anode material according to claim 2, is characterized in that, the purity of described metallic lead, metallic tin and metallic copper all >=99.9wt.%.
4. the preparation method of electrolytic copper alloy lead anode material according to claim 2, is characterized in that, described calcium metal is plumbous calcium mother alloy, and wherein calcium contents is 1.5 ~ 6wt.%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763021A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of low Ag metal composite anode materials preparation method |
-
2015
- 2015-04-27 CN CN201510205588.9A patent/CN104831118A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763021A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of low Ag metal composite anode materials preparation method |
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Application publication date: 20150812 |
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