CN103757624B - Aluminium alloy non-chromium passivator and aluminium alloy non-chromium Passivation Treatment system - Google Patents
Aluminium alloy non-chromium passivator and aluminium alloy non-chromium Passivation Treatment system Download PDFInfo
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- CN103757624B CN103757624B CN201310739489.XA CN201310739489A CN103757624B CN 103757624 B CN103757624 B CN 103757624B CN 201310739489 A CN201310739489 A CN 201310739489A CN 103757624 B CN103757624 B CN 103757624B
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 120
- 238000002161 passivation Methods 0.000 title claims abstract description 86
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 52
- 239000011651 chromium Substances 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000002253 acid Substances 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims abstract description 59
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 55
- 239000011737 fluorine Substances 0.000 claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000003352 sequestering agent Substances 0.000 claims abstract description 16
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims description 125
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 69
- 230000009849 deactivation Effects 0.000 claims description 67
- 238000005260 corrosion Methods 0.000 claims description 64
- 230000007797 corrosion Effects 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 32
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002351 wastewater Substances 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 21
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- 238000004064 recycling Methods 0.000 claims description 17
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 16
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 6
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 5
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
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- 230000008901 benefit Effects 0.000 description 5
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- 229910052684 Cerium Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
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- 150000000703 Cerium Chemical class 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a kind of aluminium alloy non-chromium passivator, comprise hydrofluotitanic acid, fluorine zirconic acid, inhibiter and sequestrant, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) concentration are 2.0-3.0g/L, and described inhibiter is concentration is 4.0-6.0g/L, and the concentration of described sequestrant is 6.0-8.0g/L.Aluminium alloy non-chromium passivator of the present invention, completely eliminates the pollution of chromic salts to water quality from source; Reduce molten aluminum amount, reduce powder in aluminum alloy surface, extend the passivating solution life-span; Passivation speed is more than three times of chromic salts, improves production efficiency.Aluminium alloy non-chromium Passivation Treatment system of the present invention, simple to operate simultaneously, energy-conserving and environment-protective, and wastewater treatment is easy, is easy to scale operation.The present invention thoroughly finishes the pollution of chromium of architectural aluminum section surface treatment, use and waste treatment process, solves the bottleneck problem restricting industry development for many years.
Description
Technical field
The present invention relates to metal surface treatment technology, be specifically related to a kind of aluminium alloy non-chromium passivator and aluminium alloy non-chromium Passivation Treatment system.
Background technology
China is the first in the world great Lv producing country and country of consumption.There is due to aluminium alloy the performances such as excellent physical chemistry and mechanical workout, the fields such as aerospace, communications and transportation, light industry building materials are widely used in, the annual processing treatment aluminium alloy about 1,300 ten thousand tons in the whole nation, the aluminium alloy that only Foshan City processes every year just reaches 3,500,000 tons, and the output value is more than 1,000 hundred million yuan.But, aluminium alloy moist, containing environment such as industrial gasses, fuel gas, salinity and dust air in use time very easily there are spot corrosion, crevice corrosion, stress corrosion and corrosion fatigue etc., limit its range of application, shorten the work-ing life of aluminium alloy.For the difference of satisfied industry requires and extends its work-ing life, metallic surface often needs to carry out decoration and protectiveness process.Up to now for technology the most successful in metal finishing, be a kind of conventional machining process having one-hundred-year history always---chromic salt chemical conversion (passivation), this technology is widely used in the various metals of industrial circle and the protections of alloy such as space flight and aviation, electronics, automobile, pharmacy, printing, machinery, chemical industry, food-processing.
Research in recent years shows, chromic salt easily causes the various diseases such as skin ulcer, squamous cell carcinoma, sarcoma and mammary cancer accumulated in creatures, it is the extremely strong carcinogenic substance of a kind of toxicity, especially chromic salt easy process that is decomposed unlike prussiate, metallic surface chromic salt treatment technology uses each link to produce strong and fatal Health hazard to environment and the mankind at production, discharge of wastewater, waste residue, product.
Find the Occupational health investigation of chrome-plating plant work workman according to China, owing to sucking a large amount of chromium (acid) mist, some workman's bridge of the nose cartilages rot, and some workmans are found suffers from leukemia.One kilogram of chromic acid permeates the ground, and can be subject to polluting by the underground water made in five kilometer radius becomes carcinogenic malicious water.The quickening of fast development of the electric industry in the world today and products thereof renewal and renovation of equipment replacement speed, the generation of a large amount of electronic waste causes serious harm to the regeneration of global ecological environment and non-sustainable resource.In this respect, the impact of reject product on environment and human health of metallic surface chromic salt process shows especially serious.
Metallic corrosion has extensive and important impact to the operational performance of weaponry, security, reliability and work-ing life and national defense construction.Chromic salt process is that metallic corrosion protects modal chemical conversion treatment technique, widespread use in national defense industry.Especially under extreme condition and the torrid zone and oceanic climate environment, the corrosion protection of weaponry and various metal parts, chromate metal surface treatment technology is widely used.Such as, United States Navy adopts chromic salt process maintenance cost more than 1,000,000,000 dollars for air fighter corrosion protection every year.Therefore, United States Navy all drops into a large amount of funds every year and studies for the zero waste water discharge of aldural.
Compared with ferrous materials, aluminum alloy materials has the advantage that intensity is high, solidity to corrosion is good, the usage quantity thus on aviation field accounts for very large ratio.Chromic salt chemical conversion treatment improves metallic substance corrosion proof processing method as one, be always in flyer Al and Al-alloy use the most generally, one of the most effective and the most most economical method.
Aluminium alloy chromic salt chemistry conversion treatment process is applied very extensive in aircraft industry, and be no matter the manufacture of external or domestic air fighter, this technique is all in a large amount of use.Such as, severe due to environment for use, is used to the aldural that fuselage builds and chromic salt must be adopted to carry out surface treatment.1,400,000 gallons of Surface Treatment Industry waste water containing chromium are produced every day in the Tinker base air depot in U.S. Oklahoma state.Xi'an is as state aviation Space Industry base, and its space flight and aviation aluminum alloy surface process adopts chromic salt Conversion Coating Technology always.Therefore, the exploitation of the aluminum alloy surface chromiumfree conversion membrane technology of advanced technology, environmental protection and energy saving, application and popularization for save energy, promote that the Sustainable development tool of society is of great significance.
Up to now, Aluminum-aluminum alloy section bar for building generally protects its surface (Passivation Treatment) by forming chemical conversion film.The surface chemical conversion film of the Aluminum-aluminum alloy be most widely used at present remains the sexavalent chrome conversion film (chromate film) of last 100 years history, as shown in Figure 1, for the passivation technology schematic flow sheet of prior art, comprise oil removing, washing 1, washing 2, chromaking, washing 3, washing 4 and baking step, this passivation process adopts chromic salt to be passivating solution, adopt fluorine-containing promotor, there is chromic salt with low cost, passive film has good sticking power and resistance to corrosion, the advantages such as technical maturity, usually also as the criterion [aluminium alloy GB GB-5237.4-2004] of other conversion film technology.But, owing to containing the poisonous carcinogenic elements sexavalent chrome be very harmful to human body and environment in chromating treatment solution, not only can cause serious environmental pollution and human injury in Metal surface anti-corrosion treating processes, and the sexavalent chrome in passive film also will cause processed product to use in the future and discarded time secondary pollution is caused to environment.Therefore, American-Europeanly wait developed country to prohibite use in metal finishing process to have chromium process.On February 13rd, 2003, European Union has issued " waste electronic andelectrical equipment instruction " and " using some Hazardous Substances Directive about restriction in electronic electric equipment ", and these two restrictive files are exactly so-called " RoHS instruction ".The use making chromic salt in metal treatment that comes into force of RoHS instruction is prohibited the most at last.The Ministry of Electronics Industry of China also announces on March 6th, 2002, intend carrying out limitation to carcinogenic compound sexavalent chrome (chromic salt) from July, 2002 and use, and before 2006 year July cancel synchronous with European Union uses chromic salt.The appearance of a series of government policy and enforcement, make aluminum and its alloy manufacturing enterprise be absorbed in the condition of final and decisive juncture, also impels the research of aluminum and its alloy chromium-free deactivation technology to become focus.
Research about the chromium-free deactivation technology of aluminum and its alloy has had the history of nearly 30 years, obtains many enthusiasm results, as zirconium titanium system chromium-free deactivation, molybdenum salt system chromium-free deactivation, rare-earth salts system chromium-free deactivation, organosilicon methane series chromium-free deactivation etc.Molybdenum salt system chromium-free deactivation cost is very high, can only be used for special material preparation; The general very thin (100mg/m of passive film that zirconates, titanium salt, cerium salt are formed as passivator
2below), be usually used in the materials very low to passive film requirement such as pop can to prepare; Organosilicon methane series chromium-free deactivation is also in the laboratory desk study stage.For aluminium alloy passive film, GB (GB5237.4-2004) requirement, passivation film thickness will reach 200mg/m
2above, meet the index requests such as resisting salt fog corrosion, humidity resistance, resistance to boiling water, impact, bending, drawing test simultaneously.The chromium-free deactivation result of study of current reported in literature, because passive film sticking power is low or solidity to corrosion is poor or cost is high or the reason such as passivating solution poor stability, all be not suitable for the requirement of extensive aluminium alloy non-chromium passivation, also do not have a kind of non-chromium inactivating technique can replace aluminium alloy chromating technique, make aluminium alloy non-chromium passivating technique fail to realize industrialization at home and abroad.Therefore, environment-friendly type aluminium alloy non-chromium passivation new technology is researched and developed imperative to substitute existing chromating technique.
Two, the state of the art of domestic and foreign current passivation medicine
For a long time, it has been recognized that and to have produced from aluminium alloy containing chromium passivating technology, use and pollution of chromium that waste treatment whole process is serious, realizing aluminum alloy surface chromium-free deactivation process is the target that aluminium alloy production is pursued.For meeting the demand of industry member to chromium-free deactivation technology, researchist has carried out a large amount of research work, in the Study on Process of the Aluminum-aluminum alloy surface chromium-free passivation of nearly 30 years, create the result of study of multiple Al and Alalloy chromium-free deactivation process, as zirconium titanium system chromium-free deactivation, molybdenum salt system chromium-free deactivation, rare-earth salts system chromium-free deactivation, organosilicon methane series chromium-free deactivation etc.These domestic and international existing reports, or only carried out laboratory study, although or carried out pilot scale, because result is undesirable and abandon.Also do not have a kind of result of study can realize the mass-producing application of aluminium alloy at present.
1) zirconium titanium system chromium-free deactivation technology:
First proposed in early 1980s by U.S. AmchemProductsInc. etc., the company such as German Henkel, Japanese Parker has carried out large quantity research subsequently.Zirconium titanium base chromium-free passivation liquid is mainly containing H
2zrF
6and H
2tiF
6.There is a series of chemical reaction and hydrolytic action at this treatment solution in aluminium alloy, the conversion film of generation is the mixing inclusion film of zirconium and the composition such as titanium, fluorine aluminium chromium complex, thus strengthens the bonding force of coating and matrix, and improves corrosion resistance nature.
During zirconium titanium system process aluminium alloy, the corrosion resistance of its chemical conversion film is close with chromate film, can prevent the corrosion of aluminium alloy.The zirconium system chromium-free passivation liquid of weapons portion the five or nine Research Institute shows aluminium alloy wheel hub plated film, and the bonding force of paint film and aluminium base reaches one-level, the 500h of resistance to neutral salt spray test.Guo Rui light etc. have studied the Corrosion Protection of titanate solution at aluminum alloy surface conversion film.Aluminium alloy through titanium base Passivation Treatment occurs without spot corrosion through the salt mist experiment rear surface of 336h, shows that titanate chemical conversion film has good corrosion protection effect to aluminum alloy surface.
Current research shows, when being used alone zirconium or titanium system inorganic salt, because passivating solution is fluorine-containing system, unstable in production process, the easy decomposition failure of tank liquor; Need to be studied further as mass-producing chromium-free deactivation film technique process aluminium alloy.
2) molybdate series chromium-free deactivation technology:
Molybdenum and chromium belong to VIA race together, have close physicochemical property.Molybdate is a kind of low toxicity inorganic acid salt, utilizes molybdate to substitute traditional chromium hydrochlorate and has carried out large quantity research.Aluminium alloy dipping in sodium molybdate solution, is produced the blue Molybdate Conversion Film of a kind of golden yellow colour band, to improve the barrier propterty of aluminium alloy by Hinton etc.Wang Cheng etc. adopt same pickling process to obtain the anti-corrosion conversion film of molybdate of deep yellow in LY12 aluminum alloy surface.In 3.5wt%NaCl solution, extent of corrosion reduces greatly, occurs after within 21 days, soaking without spot corrosion.Yang Yuxiang etc. have studied the molybdate black conversion film of cast aluminium alloy.Potassium bichromate spot test shows, the solidity to corrosion of film is 40s.
Although these researchs show that molybdate substitute chromium hydrochlorate film forming has certain anti-corrosion effect; but compared with chromate conversion membrane technique; be used alone molybdate film forming barrier propterty poor; and molybdenum salt system chromium-free deactivation cost is very high; the special material preparations such as military project can only be used for, be unsuitable for the surface passivating treatment of mass-producing aluminium alloy.
3) rare-earth salts chromium-free deactivation technology:
Australia Hintom and Arnott etc. uses Ce
3+as the inhibiter of AA7075 aluminium alloy in NaCl solution, the erosion rate of AA7075 aluminium gold has been reduced to original 1/10.If in advance sample is put into 1g/LCeCl
3dip treating certain hour in solution, then proceed in 0.1mol/LNaCl solution, the corrosion of sample equally greatly alleviates.Erosion rate without the AA7075 aluminium alloy of cerium Ficus caricaL is 5.9 μ g/ (m
2s), after cerium Ficus caricaL, be only 0.2 μ g/ (m
2s), this is due to aluminum alloy surface generation passivation, defines the cause of corrosion resistant rare-earth salt passive film.The Mansfeld of the U.S. etc. have developed cerium – molybdenum associating passivation process, and the aluminium alloy successive soaking in 0.5mol/LNaCl solution through this art breading still spot corrosion does not occur in 60 days, and its solidity to corrosion has exceeded traditional chromating process.Research on AA2014 aluminium alloy, AA2024 aluminium alloy, AA5083 aluminium alloy, AA2090 and AA8090 aluminium alloy also demonstrate that the validity of rare-earth conversion coatings to these material corrosion protection.Through the aluminium alloy of rare earth Passivation Treatment, not only the ability of anti-uniform corrosion enlarges markedly, and the ability of anti-local corrosion also significantly improves.Domestic research in aluminum alloy rare earth passivation is started late.Li Jiuqing etc. develop three kinds of rare earth passivation technologies of P5, SRE and T2/T7 aluminium alloy.After SRE art breading, solidity to corrosion can stand the neutral salt spray test of 360h.Through the commercial-purity aluminium of T2/T5 art breading and the corrosion polarization resistance of LF6 aluminium alloy than improving more than ten times time untreated, in 3.5wt%NaCl solution, soak 21d spot corrosion does not occur, and the neutral salt spray test of more than 504h can be born, and the neutral salt spray test bearing 336h only required at most by the aluminium alloy usually after chromic salt process, therefore exceed the solidity to corrosion standard of chromating process through the aluminium alloy of this rare earth passivation technology process.Shi Tie etc. define the cerium-based conversion coating of the neutral salt spray test that can bear more than 400h on the surface at LF21.Carried out the research of rare earth secondary passivity in promote culture etc. to LY12 aluminium alloy, the solidity to corrosion of the rare earth duplicature obtained obviously is better than the unitary film of a passivation.
Although rare earth chromium-free deactivation technology achieves certain progress, because the toxicity on inorganic salt of rare earth and the impact on environment thereof cannot effectively solve always.
4) organosilicon methane series chromium-free deactivation technology:
The surface film that the process of organosilicon methane series produces is better than chromate film.Pure Al is soaked 15min by Beccaeia etc. in the aqueous solution of 80 DEG C of inclined oxygen propylmethoxysilane (MAOS) containing 0.5wt%, improves the suppression of general corrosion to Al and local corrosion.Wang Xiuhua etc. have successfully prepared Union carbide A-162 (MTEOS)/tetraethoxy (TEOS) hybridized film at LY12 aluminium alloy matrix surface.This hybridized film has excellent corrosion resistance nature, and during n (MTEOS): n (TEOS)=3:1, the corrosion resistance nature of coating is best.Su Hong to come etc. to have studied different silane treatment LY12 aluminium alloy corrosion resisting property.Point out that silane improves the Corrosion Protection of film and aluminum substrate bonding force and aluminium alloy.The bonding force that the research such as Chu finds the density that GPTMS can increase film and improves between polymeric matrix.Metrok etc. study GPTMS – TEOS film, point out that organic content and the corrosion resisting property of hydrolysing rate to the silicate films (Ormosil film) of organic amendment have material impact.But spot corrosion makes film define hydrophilic radical, the salt spray resistance of silane film is poor.VanOoij etc. think that adding glue connects agent and can form denser silicone film, reduce the reaction with moisture.Zandi-zand etc. are that glue connects agent and obtains uniform, flawless, dense GPTMS – TEOS film with dihydroxyphenyl propane, improve the solidity to corrosion of aluminium alloy.
Current research shows, many reasons such as have that cost is high, solvent is volatile due to organosilicon methane series chromium-free passivation liquid or corrodibility is strong, and its final industrialization also faces many difficulties to be needed to solve.
5) organism-inorganic salt compound chromium-free deactivation technology:
Organic-inorganic composite passivating solution, compared with using the passivating solution of one-component, effectively can improve corrosion resisting property.Deck etc. have studied the impact on the corrosion resisting property of hydrofluotitanic acid and fluorine zirconic acid conversion film of vinylformic acid and Acrylic polymer.Result shows, minimum with the corrosion current that 7:3 vinylformic acid/acrylamide polymkeric substance mixes with fluorine zirconic acid the passive film obtained, and corrosion resisting property is equivalent to phosphorus chromium film.The research such as Smit points out to add polyacrylic acid in hydrofluotitanic acid and fluorine zirconic acid or Weibull can obtain good corrosion resisting property.Paloumpa etc. report the hydrofluotitanic acid that adds polyvinyl pyrrole and fluorine zirconic acid and can obtain fabulous corrosion inhibition.But current above-mentioned research is still in the laboratory study stage.
6) manganate chromium-free deactivation technology
Lin Shengling etc. have studied the chemically composited conversion film of fine aluminium and LY12 aluminum alloy surface manganate and molybdate.Result Al, the LY12Al Corrosion Protection in 3.5wt%NaCl solution greatly improves.Old east is elementary have studied the corrosion resisting property of aluminium alloy LY12 chemical conversion film using molybdate, permanganate as film forming oxygenant, and conversion film only has and loses a little on a small quantity in 3.5wt%NaCl solution corrosion medium after 70h soaks.Al alloy is at KMnO
4also good conversion film can be formed through suitable process in the solution mixed with zirconium titanium system inorganic salt.Japanese Patent Laid-Open 11236082 describes the aluminium alloy inactivating treatment liquid that can provide good corrosion resistance and coating adhesion, and main component is permanganate, water-soluble zirconium compound and water-soluble titanium compound.After Passivation Treatment, alloy matrix aluminum can be formed the inorganic compounding passive film containing two or more heavy metal element compounds such as manganese.Inventor thinks that this is the key that passive film solidity to corrosion is able to improve further.
Following aluminum alloy surface chromium-free deactivation technological development direction by turn to the inorganic compounding conversion film of research various metals salt formation, organism and metal-salt to be formed You Ji – inorganic compounding conversion film, based on the organic composite conversion film etc. of organism as silane coupling agent.But, applicant thinks: compare inorganic salt compound conversion film, although organism passive film is a kind of directivity technology of following surface preparation, it becomes mainstream technology and also there is the such as many factors such as cost, solvent evaporates pollution restriction, has a long way to go.Development is more suitable for the current national conditions of China by the inorganic compounding conversion film new technology of various metals salt formation.
The present invention proposes a kind of aluminium alloy non-chromium passivation new technology, adopt the composite passivating solution containing zirconate-titanate-sequestrant-inhibiter, passivation operation temperature is at the wide region of 5-35 DEG C, passivating solution stable performance, not containing chromium element, aluminium alloy through this technical finesse can reach the requirement of GB (GB5237.4-2004) to indexs such as passive film resisting salt fog corrosion, humidity resistance, resistance to boiling water, impact, bending, drawing tests completely, and cost reduces than existing passivation technology.The development and application of this technology, by solving the pollution of chromium problem of aluminium alloy passivation, use and waste treatment process, realizes the chromium-free deactivation new technological industry of energy-saving and environmental protection, low cost.Technical characterstic is: produce chromium-free passivating film by the synergy of zirconate-titanate-sequestrant-inhibiter, and in process of production, passivating solution containing the chromium element of high pollution, can not reduce pollution; Passivating solution stable performance, can life-time service; Passivation operation temperature is at the wide region of 5-35 DEG C, and suitability is wide, and general chromaking service temperature is more than 20 DEG C, and therefore, new technology without the need to heating, saves mass energy in comparatively cold environment operation; Technological operation is simple, and wastewater treatment is easy, more easily accomplishes scale production; Cost, lower than existing chromic salts passivation technology, is energy-conserving and environment-protective, has the new technology of great strategic significance.
Research and development of the present invention and industrialization, have very great strategic importance.First, thoroughly solve aluminum alloy surface process and to use in the future and discarded time pollution of chromium history, achieve real chromium-free deactivation pre-treatment, solve world-famous puzzle in decades, will industry development be led, produce far-reaching social benefit; Secondly, enforcement of the present invention, will produce huge economic benefit.Along with the output without Ohmax strengthens, product progressively can enter world market, expands economic benefit; The generation of this technology, makes the process for treating surface of China's aluminium alloy be in rank first, completely eliminates the technology barriers of developed country, promotes the competitive power of China's Al and Alalloy product in world market, makes China become the power of world aluminum alloy manufacture.
Research of the present invention shows, zirconate-titanate passive film corrosion resistance significantly improves, but still adopts fluorine-containing system, and passivating solution is unstable, occurs muddy, after adding sequestrant and inhibiter, can solve passivating solution stability problem in use procedure.Result of study shows, the present invention can break through aluminium alloy non-chromium passivating technique, realizes low cost, free of contamination chromium-free deactivation large-scale production.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, goal of the invention of the present invention be to provide a kind of reduce pollution, stable performance, not containing the aluminium alloy passivator of chromium element.
The present invention also provides a kind for the treatment of process system adopting aluminium alloy non-chromium agent, water saving, and technological operation is simple, and wastewater treatment is easy, more easily accomplishes scale production.
Technical scheme of the present invention is achieved in that
A kind of aluminium alloy non-chromium passivator, comprise the aqueous solution of hydrofluotitanic acid, fluorine zirconic acid, inhibiter and sequestrant, with the volume of passivator for benchmark, the concentration of described hydrofluotitanic acid is 2.0-3.0g/L, the concentration of described fluorine zirconic acid is 2.0-3.0g/L, the concentration of described inhibiter is 4.0-6.0g/L, and the concentration of described sequestrant is 6.0-8.0g/L.
Preferably, in described passivator, inhibiter is one or more in ethylene glycol, glycerol and sorbyl alcohol.
Preferably, in described passivator, sequestrant is one or more in trolamine, ethylenediamine tetraacetic acid (EDTA), tripoly phosphate sodium STPP, trisodium phosphate, sodium-metaphosphate, Amino Trimethylene Phosphonic Acid, phosphonobutane tricarboxylic acid.
Aluminium alloy non-chromium Passivation Treatment system, comprises production system, heating system, gas agitating system, filtering system, differential concatenation waste water recycling device system and water charging system;
Described production system, form by through the 1# work nest of Corrosion Protection of Fiber Reinforced Plastics process, the washing trough of 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, 5# chromium-free deactivation groove, the washing trough of 6# flowing water and the washing trough of 7# flowing water, described 1# work nest is used for oil removing, deoxidation film, etching and deburring, described 5# chromium-free deactivation groove is main work nest, for the passivation of aluminium alloy, the washing trough of described 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water are for washing the residual aluminum alloy chrome-free tanning agent of aluminum alloy surface;
Described heating system, is made up of steam heating tube and 10# valve, and described steam heating tube is arranged at the both sides of described 5# chromium-free deactivation groove, and described steam heating tube is for heating described 5# chromium-free deactivation groove;
Differential concatenation waste water recycling device system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, described wastewater treatment treatment system, for purifying the washing trough of described 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water, realizes cycling utilization of wastewater;
Described gas agitating system, is made up of air compressor machine, feed channel, 1# valve, 2# valve and 3# valve, and described heating system is used for 1# work nest, 5# chromium-free deactivation groove and 8# settling bath described in uniform stirring;
Described filtering system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 5# deactivation slot, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, described filtering system for filtering described 5# chromium-free deactivation groove, and the washing trough of described 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water.
Described water charging system, is made up of 1# work nest, the washing trough of 2# non-mobile water, 4# check valve and 11# valve, and described water charging system is used for the aluminium alloy non-chromium passivator in the washing trough of 2# non-mobile water to be recycled to 1# work nest, and to 2# non-mobile water washing trough moisturizing.
Preferably, after 5# chromium-free deactivation groove adds aluminium alloy non-chromium passivator, open 2# valve, stir; Before 8# settling bath adds unslaked lime, close 7# valve, 8# valve and 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, survey pH value while stirring while add, to pH value close to 8.0 time, stop adding unslaked lime and stirring.
Preferably, during described 5# deactivation slot heating, open 10# valve, be heated to 15-30 DEG C; By 10# valve, automatically control passivation temperature between 15-30 DEG C.
Preferably, the working method of described differential concatenation waste water recycling device system is: close described 5# valve and 6# valve, opens 7# valve, 8# valve and 9# valve, start acid proof pump, after the water lotion of 8# settling bath is filtered, be evacuated to the washing trough of 7# flowing water, then through the washing trough of 3# flowing water, from flowing back to described 8# settling bath, complete the circulating filtration of washing bath, when water lotion pH value lower than 5.0 time, stop acid proof pump, close described 7# valve, described 8# valve and described 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, limit edged stirs, pH value is surveyed on limit, to pH value close to 8.0 time, stop dosing and stirring, leave standstill 1 hour, restart Waste Water Treatment, complete the recycling of Cleaning Wastewater.
Preferably, the filter regeneration working method of described 5# deactivation slot is: close 7# valve and 8# valve, cleaning acid proof pump, strainer and pipeline; Open 5# valve and 6# valve; Start acid proof pump, circulating filtration 5# chromium-free deactivation groove, to so clear that you can see the bottom, complete passivating solution regeneration.
Preferably, the working method of described water charging system is: when the liquid level in 1# work nest and the washing trough of 2# non-mobile water is inadequate, open 11# valve to 2# non-mobile water washing trough moisturizing, the degreasing fluid of recovery is recycled to 1# work nest through 4# check valve, completes degreasing fluid and reclaims and moisturizing.
Compared to prior art, beneficial effect of the present invention is:
1, aluminium alloy non-chromium passivator of the present invention, completely eliminates the pollution of chromic salts to water quality from source; Reduce molten aluminum amount, reduce powder on the surface, extend bath life; Passivation speed is more than three times of chromic salts, improves production efficiency.
2, aluminium alloy non-chromium Passivation Treatment system of the present invention, simple to operate, energy-conserving and environment-protective, wastewater treatment is easy, be easy to scale operation, thoroughly finish the pollution of chromium of aluminum alloy surface process, use and waste treatment process, solve the bottleneck problem restricting industry development for many years.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the passivation technology schematic flow sheet of prior art;
Fig. 2 is the structural representation of aluminium alloy non-chromium Passivation Treatment system of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
A kind of aluminium alloy non-chromium passivator, comprise hydrofluotitanic acid, fluorine zirconic acid, inhibiter and sequestrant, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) concentration are 2.0-3.0g/L, and inhibiter is concentration is 4.0-6.0g/L, and the concentration of sequestrant is 6.0-8.0g/L.In passivator inhibiter be in ethylene glycol, glycerol and sorbyl alcohol one or more.In passivator, sequestrant is one or more in trolamine, ethylenediamine tetraacetic acid (EDTA), tripoly phosphate sodium STPP, trisodium phosphate, sodium-metaphosphate, Amino Trimethylene Phosphonic Acid, phosphonobutane tricarboxylic acid.
In the present invention, select hydrofluotitanic acid and fluorine zirconic acid as main passivation composition, its ionization, hydrolysis and passivation reaction are (fluorine zirconic acid is roughly the same):
H
2tiF
6=2H
++ TiF
6 2-(hydrofluotitanic acid ionization) (1)
3TiF
6 2-+6H
2O=Ti(OH)
3F
3 2-+Ti(OH)
2F
4 2-+Ti(OH)F
5 2-+6H
++6F
-(2)
(hydrofluotitanic acid hydrolysis)
By (2) formula, hydrofluotitanic acid and fluorine zirconium aqueous acid instability, facile hydrolysis becomes monohydroxy, dihydroxyl and trihydroxy-hydrofluotitanic acid and fluorine zirconate, discharges H simultaneously
+and F
-, tank liquor pH value is declined, F
-concentration increases; If raising pH value, by (2) formula, react and move to the right.When pH value is greater than 4.5, trihydroxy-hydrofluotitanic acid and fluorine zirconic acid are hydrolyzed further, occur turbidity and precipitation:
Ti (OH)
3f
3 2-+ H
2o=Ti (OH)
4↓+H
++ 3F
-(hydrofluotitanic acid decomposes, separate out titanium hydroxide) (3)
When putting into aluminium alloy in tank liquor, hydrofluotitanic acid and fluorine zirconic acid and reactive aluminum, Ti is reduced:
Al
2o
3+ 12F
-+ 3H
2o=2AlF
6 3-+ 6OH
-(oxide film is dissolved, and pH value raises) (4)
4Al+3Ti (OH)
3f
3 2-+ 9H
+=3Ti+AlF
6 3-+ 3F
-+ 3Al
3++ 9H
2o(Ti is reduced) (5)
6F
-+ Al
3+=AlF
6 3-(fluorine and reactive aluminum form hydrofluoaluminic acid root) (6)
In order to ensure aluminium alloy life-time service, passivation and spray treatment must be carried out.The object of passivation spraying is solidity to corrosion, its surface anti-pollution ability and color thereof in order to improve aluminium alloy and fast light, weathering resistance, and the sticking power of therefore passivation is very important sport technique segment.The sexavalent chrome passivating solution that the technique generally used both at home and abroad is at present chromic anhydride is main body, its passivation technology condition is:
PH value: 1.8-2.2
Temperature: 25-35 degree
Time: 2-5 minute
CrO
3：3-8g/L（7）
Water used is deionized water.
Adopt hydrofluotitanic acid and the passivation of fluorine zirconic acid, it is deposited as and is divided into titanium and zirconium, thoroughly nontoxic, just in time adapts to the megatrend that aluminium alloy gos deep into mankind's daily life each side day by day.But how to make good use of hydrofluotitanic acid and fluorine zirconic acid, technical difficulty is very large.
By (3) formula, pH value raises, and hydrofluotitanic acid and fluorine zirconic acid decomposite titanium hydroxide, and tank liquor is muddy.By (2) formula, hydrofluotitanic acid and the hydrolysis of fluorine zirconic acid, ionize out F
-; Fluorine aluminium chromium complex is generated, release OH by (4) (5) reaction
-, pH raises, and when pH value is more than 4.5, generates Ti (OH)
4and Al
2(OH)
3f
3mixture, Surface of profile produces pollen, and tank liquor is muddy.
By (5) and (6) formula, after aluminium alloy enters hydrofluotitanic acid and fluorine zirconic acid tank liquor, aluminium is dissolved, and form fluoaluminate, the replaced reduction of titanium, is deposited on aluminum alloy surface, forms the composite membrane of metal titanium, completes passivation.
In the present invention, select inhibiter and sequestrant, with hydrofluotitanic acid and fluorine zirconic acid compatibility, solve powder and the muddy difficult problem of tank liquor on the aluminium alloy under high fluorine, low pH value; Inhibiter, selects ethylene glycol, glycerol and sorbyl alcohol etc.; Sequestrant, refer to can effectively chelated mineral positively charged ion, make it the class medicament that not easily point to parse from tank liquor, by (3)-(6) formula, after adding sequestrant, Ti (OH)
4and Al
2(OH)
3f
3not easily generate, tank liquor is stablized, and aluminium alloy not easily goes up powder, but can reduce passivation speed.Under the mal-condition that low ph value, high fluorine, aluminum ion constantly raise, tank liquor be kept clear, and chelant ties lives in Al
3+and Ti
4+, difficulty is really not little.When analyzing alkaline etching and oxidation tank liquor, in order to analyze Al
3+concentration, generally adds Potassium monofluoride, uses F
-open Al
3+close key with the chromium of ligand, just measure aluminium ion concentration.So in hydrofluotitanic acid and fluorine zirconic acid tank liquor, because fluorine is too high, general chromium complex and inner complex, bond energy is inadequate, is not enough to chelating and lives in Al
3+and Ti
4+, tank liquor is easily muddy.Can supply at high F
-under condition, chelating lives in Al
3+and Ti
4+sequestrant, being limited in scope of selection.
Embodiment 1
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Ethylene glycol 5.0g/L, tripoly phosphate sodium STPP 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 2
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, tripoly phosphate sodium STPP 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 3
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Sorbyl alcohol 5.0g/L, tripoly phosphate sodium STPP 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 4
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, trolamine 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 5
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, ethylenediamine tetraacetic acid (EDTA) 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 6
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, trisodium phosphate 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 7
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, sodium-metaphosphate 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 8
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, Amino Trimethylene Phosphonic Acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 9
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 10
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.0g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 11
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 3.0g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s;
Embodiment 12
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 4.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 13
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 6.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 14
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 6.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 15
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 8.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 60s.
Embodiment 16
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 5 DEG C, and pH value is 3.5, passivation time 240s.
Embodiment 17
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 15 DEG C, and pH value is 3.5, passivation time 180s.
Embodiment 18
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 35 DEG C, and pH value is 3.5, passivation time 30s.
Embodiment 19
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 2.5, passivation speed passivation time 60s.
Embodiment 20
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 3.5, passivation time 30s.
Embodiment 21
In the present embodiment, hydrofluotitanic acid and fluorine zirconic acid (50wt.%) 2.5g/L; Glycerol 5.0g/L, phosphonobutane tricarboxylic acid 7.0g/L, working temperature is 25 DEG C, and pH value is 4.5, passivation time 60s.
As shown in Figure 2, a kind of aluminium alloy non-chromium Passivation Treatment system of the present invention, it comprises production system, heating system, gas agitating system, filtering system, differential concatenation waste water recycling device system and water charging system; Production system, form by through the 1# work nest of Corrosion Protection of Fiber Reinforced Plastics process, the washing trough of 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, 5# chromium-free deactivation groove, the washing trough of 6# flowing water and the washing trough of 7# flowing water, 1# work nest is used for oil removing, deoxidation film, etching and deburring, 5# chromium-free deactivation groove is main work nest, for the passivation of aluminium alloy, the washing trough of 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water are for washing the residual medicament of aluminum alloy surface; Heating system, is made up of steam heating tube and 10# valve, and steam heating tube is arranged at the both sides of described 5# chromium-free deactivation groove, and steam heating tube is for heating 5# chromium-free deactivation groove; Gas agitating system, is made up of air compressor machine, pipeline, 1# valve, 2# valve and 3# valve, and heating system is used for uniform stirring 1# work nest, 5# chromium-free deactivation groove and 8# settling bath; Differential concatenation waste water recycling device system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, differential concatenation waste water recycling device system, for purifying the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water, realizes cycling utilization of wastewater; Filtering system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 5# chromium-free deactivation groove, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, filtering system for filtering 5# chromium-free deactivation groove, and the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water.Water charging system, is made up of 1# work nest, the washing trough of 2# non-mobile water, 4# valve and 11# valve, and water charging system is used for the aluminium alloy non-chromium passivator in the washing trough of 2# non-mobile water to be recycled to 1# work nest, and to 2# non-mobile water washing trough moisturizing.
In the present invention, after 5# chromium-free deactivation groove adds aluminium alloy non-chromium passivator, open 2# valve, stir, continue to produce; Before 8# settling bath adds unslaked lime, close 7# valve, 8# valve and 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, limit edged stirs, and pH value is surveyed on limit, to pH value close to 7.0 time, stop adding unslaked lime and stirring.
In the present invention, during the heating of 5# chromium-free deactivation groove, open 10# valve, be heated to 15-30 DEG C; By 10# valve, automatically control passivation temperature between 15-30 DEG C.
In the present invention, the working method of waste water recycling device system is: close 5# valve and 6# valve, opens 7# valve, 8# valve and 9# valve, start acid proof pump, after the water lotion of 8# settling bath is filtered, be evacuated to the washing trough of 7# flowing water, then through the washing trough of 3# flowing water, from flowing back to 8# settling bath, complete the circulating filtration of washing bath, when water lotion pH value lower than 5.0 time, stop acid proof pump, close 7# valve, 8# valve, 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, limit edged stirs, pH value is surveyed on limit, to pH value close to 7.0 time, stop adding unslaked lime and stirring, leave standstill 1 hour, restart differential concatenation waste water recycling device system, complete the recycling of Cleaning Wastewater.
In the present invention, the filter regeneration working method of 5# chromium-free deactivation groove is: close 7# valve and 8# valve, cleaning acid proof pump, strainer and pipeline; Open 5# valve and 6# valve; Start acid proof pump, circulating filtration 5# chromium-free deactivation groove, to so clear that you can see the bottom, complete passivating solution regeneration.
In the present invention, the working method of water charging system is: when the liquid level in 1# work nest and the washing trough of 2# non-mobile water is inadequate, open 11# valve to 2# non-mobile water washing trough moisturizing, the degreasing fluid of recovery is recycled to 1# groove through 4# check valve, completes degreasing fluid and reclaims and moisturizing.
In order to ensure life-time service after aluminium alloy anode oxide, surface treatment must be carried out and improve the color of the solidity to corrosion of aluminium alloy, its surface anti-pollution ability and coloring film thereof and fast light, weathering resistance.
The algorithm of aluminium alloy non-chromium Passivation Treatment system of the present invention is as follows:
1, production operation
1) check that the working index of 1# degreasing tank is in working range.Open 10# valve, heating 5# chromium-free deactivation groove, checks and confirms indices:
Hydrofluotitanic acid and fluorine zirconic acid (50wt.%) concentration 2.0-3.0g/L
The concentration 4-6g/L of inhibiter
Chelating agent concentrations 6-8g/L
Temperature 5-35 DEG C
PH value 2.5-4.5;
2) 7# valve, 8# valve and 9# valve is opened, start acid proof pump, confirm that the pH value of 8# settling bath is between 5-7, the water lotion in circulation 8# settling bath to the washing trough of 7# flowing water, the washing trough of 6# flowing water, the washing trough of 4# flowing water, the washing trough of 3# flowing water, then returns settling bath;
3) start to produce:
1# work nest: at normal temperatures, oil removing 5-10 minute, drip 1 minute;
2# non-mobile water washing trough: clean 1 minute, drip 1 minute;
The washing trough of 3# flowing water and the washing trough of 4# flowing water: clean 1 minute, drip 1 minute;
5# chromium-free deactivation groove: passivation 30-240 second, drip 1 minute;
The washing trough of 6# flowing water and the washing trough of 7# flowing water: clean 1 minute, drip 1 minute.
Complete Passivation Treatment, be then handled as follows:
4) drip-dry: charging frame is placed on Drip rack and keeps with ground tilting in 45-60 °, be convenient to moisture and flow out, if desired termination blower fan is opened, accelerate speed of dropping water.
5) dry: be dried to till water parches completely, Control for Kiln Temperature, between 70-100 DEG C, is as the criterion with moisture complete drying, and generally, aniseed required time is 30min-60min, and middle small powder required time is 60min-120min.
6) cool: open the blower fan in lower frame district and accelerate lower frame after half-finished cooling, complete spraying pre-treatment.
2, chromium-free deactivation tank liquor filter regeneration operation
Through long-term production, may there is residue in the passivating solution in 5# chromium-free deactivation groove, can start filtering system, to passivating solution filter regeneration.Working method is as follows: close 7# valve, 8# valve, cleaning acid proof pump, strainer and pipeline; Open 5#, 6# valve; Start acid proof pump, the passivating solution in circulating filtration 5# chromium-free deactivation groove, to so clear that you can see the bottom, complete passivating solution regeneration.
3, wastewater treatment operations
In passivation production process, oil removing and passivation medicament constantly bring washing bath into, reduce the pH value of washing bath.Differential concatenation waste water recycling device system can be started, to water lotion filter regeneration, recycle.Working method is as follows: close 5# valve, 6# valve, opens 7# valve, 8# valve, 9# valve; Start acid proof pump, after being filtered by the water lotion of 8# settling bath, be evacuated to 7# washing bath, then through 3# washing bath, certainly flow back to 8# settling bath, complete the circulating filtration of washing bath.When water lotion pH value lower than 5.0 time, stop acid proof pump, close 7# valve, 8# valve, 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, pH value is surveyed while stirring while add, to pH value close to 7.0 time, stop dosing and stirring, leave standstill 1 hour, restart differential concatenation waste water recycling device system, complete the recycling of Cleaning Wastewater.
4,2# do not flow groove degreaser reclaim water-refilling operation
When 1# work nest, 2# non-mobile water washing trough liquid level are inadequate, open 11# valve to 2# non-mobile water washing trough moisturizing, the degreasing fluid of recovery is recycled to 1# work nest through 4# check valve, completes degreasing fluid and reclaims and moisturizing.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. an aluminium alloy non-chromium passivator, it is characterized in that, comprise the aqueous solution of hydrofluotitanic acid, fluorine zirconic acid, inhibiter and sequestrant, with the volume of passivator for benchmark, the concentration of described hydrofluotitanic acid is 2.0-3.0g/L, the concentration of described fluorine zirconic acid is 2.0-3.0g/L, and the concentration of described inhibiter is 4.0-6.0g/L, and the concentration of described sequestrant is 6.0-8.0g/L; In described passivator, inhibiter is one or more in ethylene glycol, glycerol and sorbyl alcohol.
2. a kind of aluminium alloy non-chromium passivator according to claim 1; it is characterized in that, in described passivator, sequestrant is one or more in trolamine, ethylenediamine tetraacetic acid (EDTA), tripoly phosphate sodium STPP, trisodium phosphate, sodium-metaphosphate, Amino Trimethylene Phosphonic Acid, phosphonobutane tricarboxylic acid.
3. aluminium alloy non-chromium Passivation Treatment system, is characterized in that, comprises production system, heating system, gas agitating system, filtering system, differential concatenation waste water recycling device system and water charging system;
Described production system, form by through the 1# work nest of Corrosion Protection of Fiber Reinforced Plastics process, the washing trough of 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, 5# chromium-free deactivation groove, the washing trough of 6# flowing water and the washing trough of 7# flowing water, described 1# work nest is used for oil removing, deoxidation film, etching and deburring, described 5# chromium-free deactivation groove is main work nest, for the passivation of aluminium alloy, the washing trough of described 2# non-mobile water, the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water are for washing the residual aluminum alloy chrome-free tanning agent of aluminum alloy surface;
Described heating system, is made up of steam heating tube and 10# valve, and described steam heating tube is arranged at the both sides of described 5# chromium-free deactivation groove, and described steam heating tube is for heating described 5# chromium-free deactivation groove;
Differential concatenation waste water recycling device system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, described wastewater treatment treatment system, for purifying the washing trough of described 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water and the washing trough of 7# flowing water, realizes cycling utilization of wastewater;
Described gas agitating system, is made up of air compressor machine, feed channel, 1# valve, 2# valve and 3# valve, and described heating system is used for 1# work nest, 5# chromium-free deactivation groove and 8# settling bath described in uniform stirring;
Described filtering system, be made up of the washing trough of 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water, 5# deactivation slot, 8# settling bath, acid proof pump, strainer, 5# valve, 6# valve, 7# valve, 8# valve, 9# valve and corresponding pipeline, described filtering system for filtering described 5# chromium-free deactivation groove, and the washing trough of described 3# flowing water, the washing trough of 4# flowing water, the washing trough of 6# flowing water, the washing trough of 7# flowing water;
Described water charging system, is made up of 1# work nest, the washing trough of 2# non-mobile water, 4# check valve and 11# valve, and described water charging system is used for the aluminium alloy non-chromium passivator in the washing trough of 2# non-mobile water to be recycled to 1# work nest, and to 2# non-mobile water washing trough moisturizing.
4. aluminium alloy non-chromium Passivation Treatment system according to claim 3, is characterized in that, after 5# chromium-free deactivation groove adds aluminium alloy non-chromium passivator, opens 2# valve, stirs; Before 8# settling bath adds unslaked lime, close 7# valve, 8# valve and 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, survey pH value while stirring while add, to pH value close to 8.0 time, stop adding unslaked lime and stirring.
5. aluminium alloy non-chromium Passivation Treatment system according to claim 4, is characterized in that, during described 5# deactivation slot heating, opens 10# valve, is heated to 15-30 DEG C; By 10# valve, automatically control passivation temperature between 15-30 DEG C.
6. aluminium alloy non-chromium Passivation Treatment system according to claim 4, is characterized in that, the working method of described differential concatenation waste water recycling device system is: close described 5# valve and 6# valve, opens 7# valve, 8# valve and 9# valve, start acid proof pump, after the water lotion of 8# settling bath is filtered, be evacuated to the washing trough of 7# flowing water, then through the washing trough of 3# flowing water, from flowing back to described 8# settling bath, complete the circulating filtration of washing bath, when water lotion pH value lower than 5.0 time, stop acid proof pump, close described 7# valve, described 8# valve and described 9# valve, open gas agitating 3# valve, unslaked lime is added 8# settling bath, limit edged stirs, pH value is surveyed on limit, to pH value close to 8.0 time, stop dosing and stirring, leave standstill 1 hour, restart Waste Water Treatment, complete the recycling of Cleaning Wastewater.
7. aluminium alloy non-chromium Passivation Treatment system according to claim 4, is characterized in that, the filter regeneration working method of described 5# deactivation slot is: close 7# valve and 8# valve, cleaning acid proof pump, strainer and pipeline; Open 5# valve and 6# valve; Start acid proof pump, circulating filtration 5# chromium-free deactivation groove, to so clear that you can see the bottom, complete passivating solution regeneration.
8. aluminium alloy non-chromium Passivation Treatment system according to claim 4, it is characterized in that, the working method of described water charging system is: when the liquid level in 1# work nest and the washing trough of 2# non-mobile water is inadequate, open 11# valve to 2# non-mobile water washing trough moisturizing, the degreasing fluid reclaimed is recycled to 1# work nest through 4# check valve, completes degreasing fluid and reclaims and moisturizing.
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| CN102586770B (en) * | 2012-03-23 | 2013-10-16 | 广东科富科技股份有限公司 | Method for preparing titanium-zirconium/polyhydroxy esterified product composite conversion coating of aluminum alloy surface |
| CN103205738B (en) * | 2013-03-19 | 2016-01-13 | 武汉钢实硅钢浩源润滑油有限公司 | A kind of chromium-free passivation liquid |
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