CN101956192B - Method for treating aluminum alloy trivalent chromium passivation solution waste - Google Patents
Method for treating aluminum alloy trivalent chromium passivation solution waste Download PDFInfo
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- CN101956192B CN101956192B CN2010105334509A CN201010533450A CN101956192B CN 101956192 B CN101956192 B CN 101956192B CN 2010105334509 A CN2010105334509 A CN 2010105334509A CN 201010533450 A CN201010533450 A CN 201010533450A CN 101956192 B CN101956192 B CN 101956192B
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Abstract
The invention discloses a method for treating aluminum alloy trivalent chromium passivation solution waste. The method is implemented by a series of steps of: collecting waste residues and waste liquid produced in the process of passivation production; settling and filtering; then treating the waste residues and the waste liquid with a precipitant and a flocculant; washing the residues with a mixed acid; and the like. By the method, the passivated waste of the aluminum alloy trivalent chromium passivation solution is recycled; a novel raw material, namely cryolite is produced; environmental pollution is avoided, and treated waste water completely meets a discharge standard, so that the waste water can be discharged directly; and the treatment cost of the waste water can be saved, the production cost of the passivation solution can be saved because of recycling of the waste, and the economic benefit of an enterprise is increased.
Description
Technical field
The present invention relates to chemical industry and environmental protection technical field, particularly relate to a kind of aluminum alloy trivalent chromium passivating solution waste treatment method.
Background technology
Duraluminum has plurality of advantages, and, heat conduction and good conductivity high like specific tenacity, reflective is strong, color and luster is attractive in appearance, nonmagnetic and plasticity is good etc., so duraluminum is used widely in industry such as automobile, motorcycle, aircraft and boats and ships.Though duraluminum can form one deck natural sull (about 0.4-0.5 nm) as thin as a wafer automatically in atmospheric environment; But not tight, the many space of this layer sull structure, tarnish, intensity are low, resistance to corrosion a little less than; Therefore anti-corrosive treatment being carried out on its surface is essential technology, and domestic the most frequently used aluminum alloy surface treatment technology is the sexavalent chrome passivation at present.Yet sexavalent chrome is acknowledged as strong carcinogen, and its toxicity is very big, approximately is chromic 100 times, and sexavalent chrome can not be at the nature natural degradation, and it can cause the harm of chronicity in biological and human body accumulated.And American-European countries puts into effect decree in succession, ban use of the chromyl metal product of sexavalent chrome passivation technology and import prohibition, so the application of sexavalent chrome passivating technique has received unprecedented restriction.
The present unique chemically transformed film technique that is based on the trivalent chromium composition that can compete mutually with the sexavalent chrome passivating technique at aspects such as technology, treating processes, cost and application flexibility.The passivation layer hardness that the trivalent chromium passivation obtains is high, good mechanical performance, and dispersing property and covering power all are higher than sexavalent chrome.The topmost advantage of trivalent chromium passivation is that its toxicity has only chromic 1 %, be a kind of replace the sexavalent chrome passivation have one of passivation technology of future most.
Yet although aluminum alloy trivalent chromium passivating technique unusual clean environment firendly, its sexavalent chrome discharging is up to standard fully, always chromium quantity discharged exceed standard to a certain extent (reaching more than 3.0 mg/L).Standard (referring to " chromium and compound industry pollutant emission standard thereof " (exposure draft in 2008 the)) regulation that Environmental Protection in China portion is up-to-date, total chromium quantity discharged of each enterprise should be lower than 1.5 mg/L, and this has brought the heavy three wastes to handle burden to enterprise.
Summary of the invention
Above-mentioned defective in view of the prior art existence; In order thoroughly to solve problem of environmental pollution; Accomplish real cleaner production, applicant of the present invention develops new waste treatment of aluminum alloy trivalent chromium passivating solution and the resource regeneration method of a cover, has both avoided environmental pollution; Realize resource regeneration, greatly reduce the production cost of enterprise again.
A kind of aluminum alloy trivalent chromium passivating solution of the present invention waste treatment method, realize through the following step:
(1) collect waste residue and the waste liquid that produces in the passivation production, through the sedimentation after-filtration, a and filter residue a must filtrate;
(2) in filtrating a, add precipitation agent and flocculant mixture, the pH value that adds to filtrating a is pH 8～9, leaves standstill, and precipitates, filters, and b and filter residue b must filtrate;
(3) filter residue a gets filter residue c after pulverizing, magnetic separation separate;
(4) filter residue c mixes the mixing acid washing of back with 5 times of filter residue volumes with filter residue b, and elutriant a directly send the passivating solution production line to recycle, and insolubles filter residue d oven dry back is as the raw material of producing sodium aluminum fluoride;
Precipitation agent is the sodium hydroxide solution of quality than concentration 25 % in the aforesaid method step (2), and flocculation agent is the SEPIGEL 305 of quality than concentration 0.1 %, and precipitation agent and flocculation agent volume ratio are 3:1～5:1; Mixing acid is the mixture of boric acid, Hydrocerol A and hydrofluoric acid in the step (4), and its quality is respectively than concentration: 5 %～10 %, 3 %～5 % and 5 %～10 %.
The inventive method has following advantage: can the passivation refuse of aluminum alloy trivalent chromium passivating solution be realized the regenerated using of resource, produce new starting material---sodium aluminum fluoride, avoid environmental pollution simultaneously, reach emission standard after the WWT fully, can directly discharge.Both can practice thrift cost of sewage disposal, the recycling of waste also can be practiced thrift the passivating solution production cost, improves economic benefit of enterprises.
Description of drawings
Fig. 1 is waste treatment of the present invention and reprocessing cycle system schematic.
Embodiment
Embodiment 1:
(1) sedimentation and filtration: collect the passivation refuse, leave standstill, treat the waste residue sedimentation after, (filtrating a) is retracted to the filtrating treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrating a separates: adding volume ratio in the filtrating a is precipitation agent and the flocculant mixture of 3:1, is pH 8 until the pH value of filtrating a, after stirring, leave standstill, and filtration, b and filter residue b must filtrate.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the SEPIGEL 305 of quality than concentration 0.1 %;
(3) filtrating b discharging: total chrome content is lower than 1.5 mg/L among the filtrating b, and the pH value is 8, and suspended substance (SS) is lower than 70 mg/L, all can reach emission standard, can directly discharge.Filter residue b is pending;
(4) filter residue a separates: after filter residue a is pulverized, cross magnetic separator, remove the iron filings/steel cuttings in the filter residue, get filter residue c;
(5) mixing acid washing: after filter residue c and filter residue b mixing, in the chromatography column of packing into, add mixing acid and wash; With the trivalent chromium in the filter residue, cerium, lanthanum; Zirconium, effective constituents such as nickel are come out with the form wash-out of organic complex and fluorinated complex, get elutriant a and filter residue d.Mixing acid is boric acid, the mixture of Hydrocerol A and hydrofluoric acid, and its concentration is respectively: 5 %, 3 % and 5 %.Eluting temperature is a normal temperature, and eluent flow velocity 0.5 L/min, eluent consumption are 5 times of filter residue volume.
(6) elutriant a recycles: elutriant a can directly send the passivating solution production line to recycle, and realizes resource regeneration.
(7) filter residue d oven dry: filter residue d after 110 ℃ of oven dry, can directly be used as the raw material of producing sodium aluminum fluoride.
Embodiment 2:
(1) sedimentation and filtration: collect the passivation refuse, leave standstill, treat the waste residue sedimentation after, (filtrating a) is retracted to the filtrating treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrating a separates: adding volume ratio in the filtrating a is precipitation agent and the flocculant mixture of 4:1, is pH 8.5 until the pH value of filtrating a, after stirring, leave standstill, and filtration, b and filter residue b must filtrate.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the SEPIGEL 305 of quality than concentration 0.1 %;
(3) filtrating b discharging: total chrome content is lower than 1.5 mg/L among the filtrating b, and the pH value is 8.5, and suspended substance (SS) is lower than 70 mg/L, all can reach emission standard, can directly discharge.Filter residue b is pending;
(4) filter residue a separates: after filter residue a is pulverized, cross magnetic separator, remove the iron filings/steel cuttings in the filter residue, get filter residue c;
(5) mixing acid washing: after filter residue c and filter residue b mixing, in the chromatography column of packing into, add mixing acid and wash; With the trivalent chromium in the filter residue, cerium, lanthanum; Zirconium, effective constituents such as nickel are come out with the form wash-out of organic complex and fluorinated complex, get elutriant a and filter residue d.Mixing acid is boric acid, the mixture of Hydrocerol A and hydrofluoric acid, and its concentration is respectively: 8 %, 4% and 8 %.Eluting temperature is a normal temperature, and eluent flow velocity 0.5 L/min, eluent consumption are 5 times of filter residue volume.
(6) elutriant a recycles: elutriant a can directly send the passivating solution production line to recycle, and realizes resource regeneration.
(7) filter residue d oven dry: filter residue d after 110 ℃ of oven dry, can directly be used as the raw material of producing sodium aluminum fluoride.
Embodiment 3:
(1) sedimentation and filtration: collect the passivation refuse, leave standstill, treat the waste residue sedimentation after, (filtrating a) is retracted to the filtrating treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrating a separates: adding volume ratio in the filtrating a is precipitation agent and the flocculant mixture of 5:1, is pH 9 until the pH value of filtrating a, after stirring, leave standstill, and filtration, b and filter residue b must filtrate.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the SEPIGEL 305 of quality than concentration 0.1 %;
(3) filtrating b discharging: total chrome content is lower than 1.5 mg/L among the filtrating b, and the pH value is 9, and suspended substance (SS) is lower than 70 mg/L, all can reach emission standard, can directly discharge.Filter residue b is pending;
(4) filter residue a separates: after filter residue a is pulverized, cross magnetic separator, remove the iron filings/steel cuttings in the filter residue, get filter residue c;
(5) mixing acid washing: after filter residue c and filter residue b mixing, in the chromatography column of packing into, add mixing acid and wash; With the trivalent chromium in the filter residue, cerium, lanthanum; Zirconium, effective constituents such as nickel are come out with the form wash-out of organic complex and fluorinated complex, get elutriant a and filter residue d.Mixing acid is boric acid, the mixture of Hydrocerol A and hydrofluoric acid, and its concentration is respectively: 10 %, 5 % and 10 %.Eluting temperature is a normal temperature, and eluent flow velocity 0.5 L/min, eluent consumption are 5 times of filter residue volume.
(6) elutriant a recycles: elutriant a can directly send the passivating solution production line to recycle, and realizes resource regeneration.
(7) filter residue d oven dry: filter residue d after 110 ℃ of oven dry, can directly be used as the raw material of producing sodium aluminum fluoride.
Claims (1)
1. an aluminum alloy trivalent chromium passivating solution waste treatment method is characterized in that, realizes through the following step:
(1) collect waste residue and the waste liquid that produces in the passivation production, through the sedimentation after-filtration, a and filter residue a must filtrate;
(2) in filtrating a, add precipitation agent and flocculant mixture, the pH value that adds to filtrating a leaves standstill for pH 8～9; Deposition, filter, must filtrate b and filter residue b, the b that filtrates reach wherein that total chrome content is lower than 1.5 mg/L; After suspended substance is lower than the emission standard of 70mg/L, can directly discharge;
(3) filter residue a gets filter residue c after pulverizing, magnetic separation separate;
(4) filter residue c mixes the mixing acid washing of back with 5 times of filter residue volumes with filter residue b, and elutriant a directly send the passivating solution production line to recycle, and insolubles filter residue d oven dry back is as the raw material of producing sodium aluminum fluoride;
Precipitation agent is the sodium hydroxide solution of quality than concentration 25 % in the aforesaid method step (2), and flocculation agent is the SEPIGEL 305 of quality than concentration 0.1 %, and precipitation agent and flocculation agent volume ratio are 3:1～5:1; Mixing acid is the mixture of boric acid, Hydrocerol A and hydrofluoric acid in the step (4), and its quality is respectively than concentration: 5 %～10 %, 3 %～5 % and 5 %～10 %.
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| CN2010105334509A CN101956192B (en) | 2010-11-05 | 2010-11-05 | Method for treating aluminum alloy trivalent chromium passivation solution waste |
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| CN2010105334509A CN101956192B (en) | 2010-11-05 | 2010-11-05 | Method for treating aluminum alloy trivalent chromium passivation solution waste |
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| CN101956192B true CN101956192B (en) | 2012-04-11 |
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| CN106544667A (en) * | 2016-12-02 | 2017-03-29 | 机械科学研究总院青岛分院 | A kind of cold-reduced sheet surface passivation technology |
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| CN101353210B (en) * | 2008-09-22 | 2011-05-04 | 华南理工大学 | Method for processing aluminum section bar chromizing waste water with calcium sulfite type desulphurization mortar |
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