CN104831094A - Method for raising corrosion resistance of cathode aluminium plate for electrolytic zinc - Google Patents
Method for raising corrosion resistance of cathode aluminium plate for electrolytic zinc Download PDFInfo
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- CN104831094A CN104831094A CN201510221510.6A CN201510221510A CN104831094A CN 104831094 A CN104831094 A CN 104831094A CN 201510221510 A CN201510221510 A CN 201510221510A CN 104831094 A CN104831094 A CN 104831094A
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- aluminum plate
- cathode aluminum
- rolling
- electrolytic zinc
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Abstract
The invention relates to a method for raising corrosion resistance of a cathode aluminium plate for electrolytic zinc. Requirements of the cathode aluminium plate are as follows: purity of aluminium is greater than or equal to 99.7%; and impurity contents: 0.10-0.13% of Fe and 0.06-0.09% of Si. The cathode aluminium plate is prepared by the following steps: smelting, online refining, casting and cold rolling. During online refining, external online refining is adopted. Al-Ti-B filaments are used as a refiner and dosage of the refiner is 3.0-5.0kg/t. On-line refining time is 10-20s. Cold rolling and cold working amount is 57-67%.Mass percentage of an antioxidant in rolling oil used during rolling is 0.5-1.0%. By the method, corrosion resistance of the cathode aluminium plate can be remarkably raised, service life can be prolonged to 6-9 months, and the longest service life reaches up to more than one year. According to the method, original technological process is not changed. The technology is simple; cost is low; and work efficiency is high.
Description
Technical field
The invention belongs to electrolysis tech field, be specifically related to a kind of method improving electrolytic zinc cathode aluminum plate erosion resistance.
Background technology
The main composition part of negative electrode used when cathode aluminum plate is electrolytic zinc.Anode lead silver alloys plate and cathode aluminum plate, paralleling and interleaving hangs in groove, passes to direct current, and on cathode aluminum plate, precipitating metal zinc (claim cathode zinc or separate out zinc), then releases oxygen at anode.After electrodeposition certain hour, propose cathode aluminum plate, the precipitation zinc metal sheet peeled on cathode aluminum plate is sent to founding operation, anticathode aluminium sheet carry out scrubbing clean after, then return electrolyzer and continue to use.
Due to main raw material(s) used when cathode aluminum plate is electrolytic zinc, the length in its work-ing life, just determines production cost and the quality of electrolytic zinc.Because containing Cl in electrolytic solution
-and F
-, the surface being just easy to anticathode aluminium sheet forms spot corrosion.The spot corrosion defect that cathode aluminum plate surface occurs, one is the increase in the difficulty that zinc shelled by machinery, does not even shell zinc; Two is have impact on work-ing life, when not shelling zinc, can only scrap.
The method of the corrosion resistance nature of traditional raising cathode aluminum plate: one is the purity improving cathode aluminum plate.Require purity >=99.7% of aluminium, owing to improving the purity of aluminium, have it limiting, also can increase production cost simultaneously.Two is add coating on the surface of cathode aluminum plate to improve its surperficial erosion resistance.Because coating easily comes off when shelling zinc, operation more complicated, and have certain pollution when subsequent processes to environment.
Summary of the invention
Improve the defect of cathode aluminum plate erosion resistance method for above-mentioned tradition, in conjunction with processing condition during electrolysis, the invention provides a kind of method of further raising electrolysis cathode aluminium sheet erosion resistance, cost is low, simple to operate.
Technical scheme of the present invention is: a kind of method improving electrolytic zinc cathode aluminum plate erosion resistance, and cathode aluminum plate requires aluminium purity >=99.7%, foreign matter content: Fe 0.10 ~ 0.13%; Si 0.06 ~ 0.09%; Cathode aluminum plate obtains through comprising following step: melting, in line thinning, casting, hot rolling and cold rolling; Described at the external line thinning of line thinning employing stove, fining agent is aluminium titanium boron wire, and consumption is 3.0 ~ 5.0kg/t, is 10 ~ 20s in the line thinning time; Described cold rolling cold working amount is 57 ~ 67%; In ROLLING OIL during rolling, the mass percent of antioxidant is 0.5 ~ 1.0%.
The present invention improves electrolysis cathode aluminium sheet erosion resistance by following several aspect, it should be noted that, following measures non-individual just can improve electrolysis cathode aluminium sheet erosion resistance, and be through lot of experiments and grope, only have and take following measures could improve electrolysis cathode aluminium sheet erosion resistance significantly simultaneously.
1) while requiring aluminium purity >=99.7%, not improve the purity of aluminium simply further, but change the content of major impurity Fe and Si of aluminium, require Fe:0.10 ~ 0.13%; Si:0.06 ~ 0.09%; Because the content of adjustment Fe and Si is less than the purity technology difficulty improving aluminium, production cost is low; The most important thing is to change the nucleating mechanism in aluminium water fusion process, the content of Fe and Si is controlled in above-mentioned scope, it is corrosion-resistant maximum mutually that it is formed, and its product produced is the most corrosion-resistant.
2) adjustment makes the melting process for refining of cathode aluminum plate: adopt the external line thinning of stove, fining agent is aluminium titanium boron wire, and consumption is 0.3 ~ 0.5%; Be 10 ~ 20s in the line thinning time; By changing its process for refining (change in stove and be refined as the outer refinement of stove) and fining agent (changing block titanium agent is aluminium titanium boron wire), effectively can improve the thinning effect of aluminium water at castingprocesses, in billet, form the evenly cast structure of refinement, its corrosion resistance nature improves greatly.
3) cathode aluminum plate cold working amount is between 57 ~ 67%, facts have proved that this interregional corrosion resistance nature is best; Aluminium sheet cold working amount controls between 57 ~ 67%, the fibrous tissue that its cold deformation is formed, the most corrosion-resistant when electrolytic zinc.
4) cathode aluminum plate processes the per-cent of antioxidant in the ROLLING OIL of rolling process use is 0.5 ~ 1.0%.When the per-cent of antioxidant is 0.5 ~ 1.0%, the aluminium sheet top layer protective membrane toughness that it is formed is best, and film is the finest and close, and the passive film simultaneously impelling surface of aluminum plate to form rapidly a kind of densification in the electrolytic solution becomes easy.
Adopt the inventive method, cathode aluminum plate can be made when electrolytic zinc, form rapidly a kind of passive film of densification, stop Cl in electrolytic solution
-and F
-directly and reactive aluminum and by spot corrosion, corrosion resistance nature significantly improves.And passive film does not come off when machinery stripping zinc, makes stripping zinc become and is easy to.Thus work-ing life of cathode aluminum plate less than three months, brings up to six to nine months by original, the longest up to more than 1 year.
In addition, adopt this processing method to produce cathode aluminum plate, can apply as long as do suitable improvement on original aluminium sheet negative electrode production line, not change original technical process.Technique is simple, and cost reduces, and working efficiency is high, alleviates working strength, not only economy but also environmental protection.
Embodiment
ROLLING OIL in the present invention during rolling can control the content of antioxidant on existing ROLLING OIL basis.As preferably, rolling process in the inventive method can adopt ROLLING OIL, rolling process and rolling last handling process in ZL201010139792.2 (a kind of method improving corrosion resistance of cathode aluminum plate for zinc electrolysis), and difference is the oxidation preventive content in controlled rolling oil.For the requirement that the step the present invention such as melting, online degasification, on-line filtration, casting are not special.Below by way of concrete case study on implementation, the present invention will be described in detail.
Embodiment 1
The electrolytic zinc cathode aluminum plate adopting following step to obtain erosion resistance greatly to improve:
1) batching also melting, requires Al purity >=99.7wt%, Fe:0.12wt%; Si:0.08wt%, other foreign matter content meets the requirement of 1070 trade mark aluminium sheets, and smelting temperature is 695 ~ 725 DEG C;
2) melting thing is carried out the external line thinning of online degasification, on-line filtration and stove, obtain online treatment product (aluminium water); The external line thinning of stove is taked: by the amount of 3kg/t (0.3%) add aluminium titanium boron wire (Ti:5%, B:1%,
), be 20s in the line thinning time;
3) online treatment product (aluminium water) is cast as aluminium ingot casting, is then hot-rolled down to the slab of 9.50mm;
4) by bar plate cold rolling to 4.0mm, cold working amount 57%, adopt ROLLING OIL, rolling process and the rolling last handling process in ZL201010139792.2 embodiment 1, difference is that the antioxidant in controlled rolling oil accounts for 0.5 ~ 1.0wt%.
By step 4) the finished product cathode aluminum plate that obtains, detect its surface oxidation-resistant corrosion resistance nature, detection method is: the electrolytic zinc solution (normal temperature) that zinc abstraction factory fetches at scene soaks, record surface of aluminum plate starts to occur that the time of corrosion pit is 24 hours, and adopt the aluminium sheet that in ZL201010139792.2 method, ROLLING OIL used is produced to soak at same electrolytic zinc solution (normal temperature), record surface of aluminum plate starts to occur that the time of spot is 16 hours, and its surface oxidation-resistant corrosion resistance nature improves more than 30% than ZL201010139792.2.
Embodiment 2
Step is with embodiment 1, and difference is: foreign matter content Fe:0.10wt%; Si:0.09wt%, aluminium titanium boron wire add-on 5kg/t, at line thinning time 10s, cold working amount 67%.Detect its surface oxidation-resistant corrosion resistance nature by embodiment 1 method, surface of aluminum plate starts to occur that the time of passive film is 24 hours.
Comparative example 1
Contrast with embodiment 1, difference is: cathode aluminum plate cold working amount 47%, is hot-rolled down to the slab of 7.5mm, by bar plate cold rolling to 4.0mm.The cathode aluminum plate adopting embodiment 1 step to produce is placed on (20 DEG C) in the dilute sulphuric acid of 20% and soaks, and detect surface oxidation-resistant corrosion resistance nature, surface of aluminum plate starts to occur that the time of spot is 10h; And the cathode aluminum plate adopting this step to produce soaks in same solution, surface of aluminum plate starts to occur that the time of corrosion pit is 4h.
Comparative example 2
For contrasting with embodiment 2, change its major impurity content: Fe:0.07%; Si:0.03%; Other step parameters are consistent with embodiment 2.The cathode aluminum plate produced by embodiment 2 step with to be placed in the electrolyzer of electrolytic zinc energising by the cathode aluminum plate that present case is produced and within 24 hours, to do corrosion resistance nature experiment (Electrolytic conditions: electrolytic solution chemical composition: Zn simultaneously
2+50 ~ 60g/l, H
2sO
4160 ~ 200g/l, Cl
-< 400mg/l, F
-< 20mg/l, Mn2.5 ~ 5g/l, temperature 32 ~ 38 DEG C, average current density 300A/m
2).Detect surface oxidation-resistant corrosion resistance nature, after the cathode aluminum plate corrosion resistance nature experiment in 24 hours that embodiment 2 step is produced, its Surface Creation passive film of one deck densification, the corrosion-free spot of surface of aluminum plate; And after testing by cathode aluminum plate 24 hours corrosion resistance natures that present case is produced, its surface does not form passive film, and surface of aluminum plate has corrosion pit, electrolytic zinc cathode aluminum plate can not be done and use.
Claims (5)
1. improve a method for electrolytic zinc cathode aluminum plate erosion resistance, it is characterized in that:
Cathode aluminum plate requires aluminium purity >=99.7%, foreign matter content: Fe 0.10 ~ 0.13%; Si 0.06 ~ 0.09%;
Cathode aluminum plate obtains through comprising following step: melting, in line thinning, casting, hot rolling and cold rolling;
Described at the external line thinning of line thinning employing stove, fining agent is aluminium titanium boron wire, and consumption is 3.0 ~ 5.0kg/t, is 10 ~ 20s in the line thinning time;
Described cold rolling cold working amount is 57 ~ 67%; In ROLLING OIL during rolling, the mass percent of antioxidant is 0.5 ~ 1.0%.
2. improve the electrolytic zinc method of cathode aluminum plate erosion resistance according to claim 1, it is characterized in that cathode aluminum plate other foreign matter content except Fe and Si meets the requirement of 1070 trade mark aluminium sheets.
3. improve the electrolytic zinc method of cathode aluminum plate erosion resistance according to claim 2, it is characterized in that cathode aluminum plate foreign matter content: Fe 0.10 ~ 0.12%; Si 0.08 ~ 0.09%.
4. improve the electrolytic zinc method of cathode aluminum plate erosion resistance according to claim 1, it is characterized in that aluminium titanium boron wire is Al-5Ti-B.
5. improve the method for electrolytic zinc cathode aluminum plate erosion resistance according to claim 1, it is characterized in that the slab being hot-rolled down to 9.5 ~ 12.5mm after casting, then by bar plate cold rolling to 4.0 ~ 6.0mm.
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|---|---|---|---|
| CN201510221510.6A CN104831094B (en) | 2015-05-05 | 2015-05-05 | A kind of method for improving electrolytic zinc cathode aluminum plate corrosion resistance |
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|---|---|---|---|
| CN201510221510.6A CN104831094B (en) | 2015-05-05 | 2015-05-05 | A kind of method for improving electrolytic zinc cathode aluminum plate corrosion resistance |
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| CN104831094B CN104831094B (en) | 2017-10-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220024A (en) * | 2015-11-10 | 2016-01-06 | 昆明理工大学 | A kind of electrowinning zinc negative electrode aluminium alloy and preparation method thereof |
| CN109022932A (en) * | 2018-08-29 | 2018-12-18 | 昆明理工大学 | A kind of hydrometallurgy electrowinning zinc anticorodal cathode material and preparation method thereof |
| CN111020323A (en) * | 2019-12-31 | 2020-04-17 | 湖南恒佳新材料科技有限公司 | Rolling method of ultrahigh-strength aluminum alloy plate |
| CN114134538A (en) * | 2021-12-08 | 2022-03-04 | 昆明理工恒达科技股份有限公司 | Zinc electrodeposition system suitable for high current density |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220024A (en) * | 2015-11-10 | 2016-01-06 | 昆明理工大学 | A kind of electrowinning zinc negative electrode aluminium alloy and preparation method thereof |
| CN109022932A (en) * | 2018-08-29 | 2018-12-18 | 昆明理工大学 | A kind of hydrometallurgy electrowinning zinc anticorodal cathode material and preparation method thereof |
| CN111020323A (en) * | 2019-12-31 | 2020-04-17 | 湖南恒佳新材料科技有限公司 | Rolling method of ultrahigh-strength aluminum alloy plate |
| CN114134538A (en) * | 2021-12-08 | 2022-03-04 | 昆明理工恒达科技股份有限公司 | Zinc electrodeposition system suitable for high current density |
| CN114134538B (en) * | 2021-12-08 | 2024-03-26 | 昆明理工恒达科技股份有限公司 | Zinc electrowinning system suitable for high current density |
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Granted publication date: 20171003 Termination date: 20180505 |