CN101781780B - Method for improving corrosion resistance of cathode aluminum plate for zinc electrolysis - Google Patents
Method for improving corrosion resistance of cathode aluminum plate for zinc electrolysis Download PDFInfo
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- CN101781780B CN101781780B CN2010101397922A CN201010139792A CN101781780B CN 101781780 B CN101781780 B CN 101781780B CN 2010101397922 A CN2010101397922 A CN 2010101397922A CN 201010139792 A CN201010139792 A CN 201010139792A CN 101781780 B CN101781780 B CN 101781780B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for improving the corrosion resistance of a cathode aluminum plate for zinc electrolysis, which comprises the steps of rolling with rolling oil of particular composition formula and treatment after rolling the aluminum plate. The composition formula of the rolling oil consists of basic oil and additives, wherein the basic oil is of lubricant with the boiling range of 225.7 to 243.3 DEG C, flash point of the lubricant is 95 DEG C, the viscosity (at the temperature of 40 DEG C) is 1.9 to 2.0 mm2/s, the additives are of methyl alkanes and dodecyl phosphate, the composition ratio of the basic oil, the methyl alkanes and dodecyl phosphate is 100: 3: 1 to 100: 8:1, the aluminum plate after being rolled is processed by sodium silicate solution with the concentration of 0.5 to 2 percent at the temperature of 70 to 0 DEG C for 2 to 10 minutes, and the service life can be improved by more than three times.
Description
Technical field
The invention belongs to the metal material surface process field, be specifically related to a kind of method that improves corrosion resistance of cathode aluminum plate for zinc electrolysis.
Background technology
Electrolytic deposition zinc metallurgy is to produce one of smart zinc main method at present, during electrolytic deposition zinc metallurgy negative plate and positive plate is immersed in the solution of zinc sulfate, and when feeding direct current, positively charged ion is shifted to negative electrode, positively charged Zn
2+Accept two electronics and on negative electrode, discharge and become element zinc, and separate out with crystalline state at cathode surface.
Cathodic reaction: Zn
2++ 2e=Zn (1)
Negatively charged ion is shifted to anode, electronegative OH simultaneously
-Lose two electronics at anode discharge, and precipitated oxygen.
Anodic reaction: H
2O-2e=0.5O
2+ 2H
+(2)
Total electrochemical reaction formula is:
ZnSO
4+H
2Of Zn+H
2SO
4+O
2 (3)
Negative plate is with the pure aluminum plate manufacturing, is of a size of 1000 * 666 * 4mm, and positive plate is generally then with Pb-Ag alloy or multicomponent alloy manufacturing.Acid content in electrolyte 100～130g/L, other principal element consists of in the solution: Zn 50-70g/L, Cd≤0.2g/L, Fe≤1.5g/L, F≤50mg/L, Cl≤100mg/L.In electrolytic process, the aluminium negative plate is immersed in the acid electrolyte always, and aluminium sheet can be subjected to a certain degree corroding and attenuation gradually.Generally speaking, the surface corrosion of aluminium negative plate is not a uniform corrosion, its corrosion surface unfairness, thus influence electrolytic efficiency and electrolytic zinc quality, in addition, the corrosion of aluminium negative plate consumes and also can make the aluminium negative plate change the frequency quickening, thereby increases enterprise's production cost.In recent years, because zinc smeltery raw material sources diversification, various assorted ore deposits ratio increases, zinc sulphate electrolyte is formed fluctuation and is strengthened, cause in the zinc sulphate electrolyte body chlorion fluorion exceed standard, cause the aggravation of aluminum cathode extent of corrosion, therefore, improving aluminium negative plate corrosion resistance nature, increasing its work-ing life is one of difficult problem of zinc smeltery concern.
The raising aluminium negative plate life-span has two approach at present, and the one, improve the zinc sulphate electrolyte performance, the 2nd, the corrosion resistance nature of raising aluminium negative plate.Most researchs think, the aluminium negative plate be corroded mainly be since exist in the zinc sulphate electrolyte body chlorion fluorion, chlorion fluorion can destroy the zone of oxidation of aluminium negative plate surface compact, thereby cause inner layer metal aluminium to be corroded.The zinc smeltery by remove control the solution of zinc sulfate chlorion fluorinion concentration.Fluorine, chlorine removal methods commonly used have: (Guizhou University of Technology's journals (natural science edition) 2004 such as thorium salt defluorination, silica gel defluorination, the dechlorination of Sulfuric acid disilver salt precipitation, copper-cadmium slag dechlorination, lime defluorination, a nitric hydrate mercurous dechlorination, ion-exchange, 33 (1): 15-17,22).Patent CN2887892 has introduced a kind of wet method electrolytic zinc with corrosion-resistant positive plate and negative plate, it is characterized in that scribbling preservative coat in the plate neck surface of positive plate and negative plate, makes on average prolong 60 days its work-ing life.Improve aluminium and aluminum alloy surface corrosion resistance nature and also have some other method, patent CN 101356300A uses (chromium nitrate+ammonium vanadate+hydrofluotitanic acid+lithium fluoride) salpeter solution to handle aluminium alloy, patent CN100513639C proposes to adopt processing aluminum pipes such as alkyl phosphate, makes its surface form a corrosion resistant film.
Aluminium is an active metal, and why there is one deck compact oxidation layer on corrosion-resistant its surface that is to aluminium, and different method of processing and treatment directly influences surface oxide layer structure and thickness, thereby influences the corrosion resistance nature of aluminium negative plate.Consider of special environment for use and the requirement of aluminium negative plate at the solution of zinc sulfate electrolytic process, the present invention is conceived to aluminium negative plate press process process and subsequent disposal, obtain the aluminium negative plate of surfacing, and generate thickness more greatly, comparatively fine and close oxide surface layer, thereby improve its corrosion resistance nature; Improve more than three times its work-ing life.。
Summary of the invention
The object of the present invention is to provide a kind of simple to operately, can effectively improve the method for corrosion resistance of cathode aluminum plate for zinc electrolysis.
The present invention adopts special ROLLING OIL, utilize conventional irreversible, the intermittent type mill milling of two rollers, adopt the processing sodium silicate solution to carry out subsequent disposal after rolling immediately, obtain the aluminium negative plate of surfacing, and generate thickness more greatly, comparatively fine and close oxide surface layer, thereby improve its corrosion resistance nature.
The detailed process of the inventive method: comprise that the ROLLING OIL that adopts special compositing formula is rolled and the rolling follow-up processing of aluminium sheet.Adopting special ROLLING OIL purpose is to obtain smooth aluminium material surface and form a corrosion resistant passivation layer, ROLLING OIL is made up of base oil and additive, base oil is the lubricating oil of 225.7～243.3 ℃ of scopes of boiling range control, and its close flash point is 95 ℃, and viscosity (40 ℃) is 1.9～2.0mm
2/ s, density is 0.8092g/cm
3Additive is straight chain alkanoic acid methyl esters and 1-isobutyl-3,5-dimethylhexylphosphoric acid; the carbon chain lengths of straight chain alkanoic acid methyl esters is 14,16 or 18; by they adsorption and tribo-chemistry effects in the operation of rolling; form layer protecting film in the processing aluminum materials metallic surface, thereby obtain high-quality lubricant effect and finished surface.Base oil: straight chain alkanoic acid methyl esters: 1-isobutyl-3,5-dimethylhexylphosphoric acid three's quality ratio of components is 100: 3: 1～100: 8: 1.Aluminium sheet after rolling in being 70～90 ℃ 0.5-2wt% sodium silicate solution, temperature was soaked 2～10 minutes.Described aluminium sheet is a pure aluminum plate.
Aluminium is an active metal, aluminium is why corrosion-resistant be forming materials after, its surface forms one deck compact oxidation layer immediately, different outside atmospheres and processing and treating method directly influence surface oxide layer structure and thickness, just the Rolling Aluminium Plate after the processing has 70～90 ℃ of temperature, it is immersed in generates in the hot sodium silicate solution, thereby improve its corrosion resistance nature than thicker in the air and compact oxide more.
The aluminium negative plate is the vitals in the electrolytic zinc production facility, not only concerns the production cost of electrolytic zinc in aluminium negative plate corrosion resistance nature and work-ing life, also influences electrolytic efficiency and electrolytic zinc quality simultaneously.This research is started with from improving aluminium negative plate surface quality, improves its corrosion resistance nature by changing ROLLING OIL prescription and post-process treatment operation, and its process simply can be utilized original rolling equipment.
Embodiment
Following examples are intended to further specify the present invention, rather than restriction the present invention.
Embodiment 1
Adopt that two rollers are irreversible, the intermittent type milling train, roller diameter is φ 530mm, and roll length is 1550mm, and roll speed is 40m/min.Aluminium is fine aluminium (label 1070), ROLLING OIL base oil and additive are formed, base oil is that boiling range is at 225.7～243.3 ℃ of scope lubricating oil, its close flash point is 95 ℃, additive is methyl palmitate and 1-isobutyl-3,5-dimethylhexylphosphoric acid, base oil: methyl palmitate: it is 100: 3: 1 that 1-isobutyl-3,5-dimethylhexylphosphoric acid is formed mass ratio, and the rolling back of aluminium sheet is with 80 ℃, and concentration is that 1% sodium silicate solution was handled 5 minutes.After the aluminium sheet product sampling, measure its surfaceness and corrosion resistance nature, and compare with the aluminium sheet of former processes with coarse instrument measurement roughness (Ra).Surface roughness Ra (μ m) is improved to 0.065 and 0.060 by original 0.097 and 0.109 respectively along rolling direction and vertical rolling direction.The electrolytic zinc solution (40 ℃) that corrosion resistance nature adopts scene, zinc smeltery to fetch soaks, and the spot time appears in the record surface of aluminum plate, and the result shows that its corrosion resistance nature improves 3.2 times (bringing up to 83.2h by 26h) through this law processing.
Embodiment 2
Adopt above rolling condition and aluminium, base oil is constant, additive is octadecanoic acid methyl esters and 1-isobutyl-3,5-dimethylhexylphosphoric acid, the ROLLING OIL proportion of composing is: base oil: the octadecanoic acid methyl esters: it is 100: 5: 1 that 1-isobutyl-3,5-dimethylhexylphosphoric acid is formed mass ratio, the rolling back of aluminium sheet is with 90 ℃, and concentration is that 2% sodium silicate solution was handled 3 minutes.Surface roughness Ra (μ m) is improved to 0.062 and 0.063 by original 0.097 and 0.109 respectively along rolling direction and vertical rolling direction.The aluminium sheet sample soaks with electrolysis zinc solution (40 ℃), and its corrosion resistance nature improves 3.1 times (bringing up to 80.6h by 26h).
Claims (2)
1. method that improves corrosion resistance of cathode aluminum plate for zinc electrolysis, comprise the treating processes of rolling and aluminium sheet after rolling, it is characterized in that, the ROLLING OIL of using when rolling is made up of base oil and additive, base oil is that boiling range is at 225.7～243.3 ℃, close flash point is 95 ℃, and viscosity is 1.9～2.0mm in the time of 40 ℃
2The lubricating oil of/s, additive are straight chain alkanoic acid methyl esters and 1-isobutyl-3,5-dimethylhexylphosphoric acid, and the mass ratio of described base oil, straight chain alkanoic acid methyl esters and 1-isobutyl-3,5-dimethylhexylphosphoric acid is 100: 3: 1～100: 8: 1; The carbon chain lengths of described straight chain alkanoic acid methyl esters is 14,16 or 18; The rolling last handling process of aluminium sheet is: the aluminium sheet after rolling was soaked 2～10 minutes in temperature is 70～90 ℃ the sodium silicate solution of 0.5-2wt%.
2. the method for raising corrosion resistance of cathode aluminum plate for zinc electrolysis as claimed in claim 1 is characterized in that, described aluminium sheet is a pure aluminum plate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101397922A CN101781780B (en) | 2010-04-06 | 2010-04-06 | Method for improving corrosion resistance of cathode aluminum plate for zinc electrolysis |
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|---|---|---|---|
| CN2010101397922A CN101781780B (en) | 2010-04-06 | 2010-04-06 | Method for improving corrosion resistance of cathode aluminum plate for zinc electrolysis |
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| CN101781780B true CN101781780B (en) | 2011-10-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104789995B (en) * | 2015-05-05 | 2017-08-29 | 湖南恒佳新材料科技有限公司 | A kind of electrolytic zinc cathode aluminum plate |
| CN104831094B (en) * | 2015-05-05 | 2017-10-03 | 遵义恒佳铝业有限公司 | A kind of method for improving electrolytic zinc cathode aluminum plate corrosion resistance |
| CN106480478B (en) * | 2016-12-12 | 2018-08-24 | 株洲冶炼集团股份有限公司 | A kind of preparation method of novel corrosion resistant zinc cathode plate |
| CN110079837B (en) * | 2019-04-24 | 2020-10-13 | 北京科技大学 | Method for preparing metal titanium by electrolyzing soluble titanate by using water-soluble fluoride salt system molten salt |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459663A (en) * | 1967-04-06 | 1969-08-05 | Sun Oil Co | Aluminum rolling oil |
| JPS62192496A (en) * | 1986-02-19 | 1987-08-24 | Kao Corp | Cold rolling oil composition for aluminum |
| CN1045102C (en) * | 1996-12-31 | 1999-09-15 | 中国石化兰州炼油化工总厂 | Aluminium rolling oil composition with annealing cleanness |
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