CN101956192A - 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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- CN101956192A CN101956192A CN 201010533450 CN201010533450A CN101956192A CN 101956192 A CN101956192 A CN 101956192A CN 201010533450 CN201010533450 CN 201010533450 CN 201010533450 A CN201010533450 A CN 201010533450A CN 101956192 A CN101956192 A CN 101956192A
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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
Aluminium alloy has plurality of advantages, and as specific tenacity height, heat conduction and good conductivity, reflective is strong, color and luster is attractive in appearance, nonmagnetic and plasticity is good etc., so aluminium alloy is used widely in industry such as automobile, motorcycle, aircraft and boats and ships.Though aluminium alloy can form one deck natural oxide film (about 0.4-0.5 nm) as thin as a wafer automatically in atmospheric environment, but not tight, the many space of this layer oxide film 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 inner 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 been subjected to 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 height that the trivalent chromium passivation obtains, good mechanical performance, 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, the present patent application people develops new waste treatment of aluminum alloy trivalent chromium passivating solution and the resource regeneration method of a cover, 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 steps:
(1) collects waste residue and the waste liquid that produces in the passivation production,, get filtrate a and filter residue a through the sedimentation after-filtration;
(2) add precipitation agent and flocculant mixture in filtrate a, the pH value that adds to filtrate a is pH 8～9, leaves standstill, and precipitation, filtration get filtrate b and filter residue b;
(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 polyacrylamide 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, citric acid 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: the passivation refuse of aluminum alloy trivalent chromium passivating solution can be realized the regeneration of resource, produce new starting material---sodium aluminum fluoride, avoid environmental pollution simultaneously, reach emission standard after the sewage disposal fully, can directly discharge.Both can save cost of sewage disposal, the recycling of waste also can be saved 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, (filtrate a) is retracted to the filtrate treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrate a separates: adding volume ratio in the filtrate a is precipitation agent and the flocculant mixture of 3:1, is pH 8 until the pH of filtrate a value, after stirring evenly, leaves standstill, and filtration must filtrate b and filter residue b.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the polyacrylamide of quality than concentration 0.1 %;
(3) filtrate b discharging: total chrome content is lower than 1.5 mg/L among the filtrate 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 citric acid 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, (filtrate a) is retracted to the filtrate treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrate a separates: adding volume ratio in the filtrate a is precipitation agent and the flocculant mixture of 4:1, is pH 8.5 until the pH of filtrate a value, after stirring evenly, leaves standstill, and filtration must filtrate b and filter residue b.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the polyacrylamide of quality than concentration 0.1 %;
(3) filtrate b discharging: total chrome content is lower than 1.5 mg/L among the filtrate 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 citric acid 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, (filtrate a) is retracted to the filtrate treating pond with supernatant liquid; After filtering, settling gets filter residue a;
(2) filtrate a separates: adding volume ratio in the filtrate a is precipitation agent and the flocculant mixture of 5:1, is pH 9 until the pH of filtrate a value, after stirring evenly, leaves standstill, and filtration must filtrate b and filter residue b.Precipitation agent is the sodium hydroxide solution of quality than concentration 25 %, and flocculation agent is the polyacrylamide of quality than concentration 0.1 %;
(3) filtrate b discharging: total chrome content is lower than 1.5 mg/L among the filtrate 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 citric acid 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 steps:
(1) collects waste residue and the waste liquid that produces in the passivation production,, get filtrate a and filter residue a through the sedimentation after-filtration;
(2) add precipitation agent and flocculant mixture in filtrate a, the pH value that adds to filtrate a is pH 8～9, leaves standstill, and precipitation, filtration get filtrate b and filter residue b;
(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 polyacrylamide 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, citric acid 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105710106A (en) * | 2016-01-20 | 2016-06-29 | 合肥市吴山固体废物处置有限责任公司 | Treatment method for chromium-containing waste |
| 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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| CN101353210A (en) * | 2008-09-22 | 2009-01-28 | 华南理工大学 | Method for processing aluminum section bar chromizing waste water with calcium sulfite type desulphurization mortar |
| JP2009066570A (en) * | 2007-09-18 | 2009-04-02 | Kajima Corp | Method for reducing cement-based turbid water-derived chromium |
| CN101549919A (en) * | 2008-03-31 | 2009-10-07 | 邵琳 | Method for treating electroplating integrated waste water |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009066570A (en) * | 2007-09-18 | 2009-04-02 | Kajima Corp | Method for reducing cement-based turbid water-derived chromium |
| CN101549919A (en) * | 2008-03-31 | 2009-10-07 | 邵琳 | Method for treating electroplating integrated waste water |
| CN101353210A (en) * | 2008-09-22 | 2009-01-28 | 华南理工大学 | Method for processing aluminum section bar chromizing waste water with calcium sulfite type desulphurization mortar |
Non-Patent Citations (1)
| Title |
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| 《有色金属加工》 20041031 孙兵 铝型材加工厂含铬废水治理 第29-31页 第33卷, 第5期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105710106A (en) * | 2016-01-20 | 2016-06-29 | 合肥市吴山固体废物处置有限责任公司 | Treatment method for chromium-containing waste |
| CN105710106B (en) * | 2016-01-20 | 2018-05-04 | 安徽浩悦环境科技有限责任公司 | The method for the treatment of of wastes produced containing chromium |
| 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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