CN101293717A - Method for processing and recycling wastewater containing fluorine, chromium ion - Google Patents
Method for processing and recycling wastewater containing fluorine, chromium ion Download PDFInfo
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- CN101293717A CN101293717A CNA2008100285462A CN200810028546A CN101293717A CN 101293717 A CN101293717 A CN 101293717A CN A2008100285462 A CNA2008100285462 A CN A2008100285462A CN 200810028546 A CN200810028546 A CN 200810028546A CN 101293717 A CN101293717 A CN 101293717A
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Abstract
The invention discloses a wastewater treatment and recycling technology for aluminum profile production enterprises. According to different pollutants, the wastewater produced by the aluminum profile production enterprises can be divided into three types to be treated: chromium-containing wastewater, high fluorine-containing wastewater and low fluorine-containing wastewater. The three types of wastewater carry out classification treatment and splitting treatment: (1) the chromium-containing wastewater is secondarily processed to remove hexavalent chromium and other harmful impurities; the processed water can be 100 percent recycled; (2) most of the fluorine and aluminum in the high fluorine-containing wastewater can be removed by coagulation precipitation method; part of the first treated wastewater can be recycled and used in the related process which has low requirement to the quality of water; other wastewater is secondarily processed by adopting composite of modified activated carbon and modified zeolite to further remove the fluorine and chemical oxygen demand COD; then part of the wastewater is recycled and the other part achieved standard is discharged; (3) most of the aluminum in the low fluorine-containing wastewater is removed by neutralization precipitation method; then the wastewater is secondarily processed by adopting the composite of the modified activated carbon and the modified zeolite to further remove the pollutants in the wastewater; the wastewater can be all recycled.
Description
Technical field:
The present invention relates to the technical field of waste water processing of aluminium section bar manufacturing enterprise, be meant that especially containing 100% of chromium ion waste water handles and reuse, use modified activated carbon and the compound secondary treatment aluminium section bar of modified zeolite factory effluent, remove the processing recovery method of waste water of a kind of fluorine-containing, the chromium ion of fluorine and chemical oxygen demand COD and reuse in the waste water.
Background technology:
China's owning amount of water resources per capita saves and protection water resources particularly important far below world average level." the national environmental protection Eleventh-Five Year Plan " of issue on November 22nd, 2007; explicitly call for national chemical oxygen demand (COD) (COD) total emission volumn in 2010 to reduce by 10% than 2005; by 1,414 ten thousand tons of 1,270 ten thousand tons of being kept to 2010 in 2005, reducing discharging total amount was 1,440,000 tons.Guangdong Province's re-set target in 2008 is that chemical oxygen demand (COD) (COD) cuts down 3.5%.Guangdong Province's aluminium industry yearly capacity surpasses 2,000,000 tons, and waste discharge surpasses 5,000 ten thousand tons, calculates even press secondary discharge standard (150mg/l), and year chemical oxygen demand (COD) (COD) total emission volumn is above 7500 tons.
The aluminium section bar production process is carried out surface treatment, needs to use great amount of water resources.1 ton of aluminium section bar of every production needs about 25 tons of water approximately, and wherein the overwhelming majority is surface treatment process consumption, and these Cleaning Wastewater are discharged after treatment.The principal pollutant of aluminium factory effluent comprise chemical oxygen demand (COD) (chemical oxygen demand COD), fluorion, ammonia nitrogen, sexavalent chrome, organism, sulfate radical, phosphate radical etc., even secondary discharge standard discharging by requirement at present, still can pollute water body, fail up to standard then harm bigger.
Difference requirement by product has different process of surface treatment, and it is better that the treatment process of employing fluorochemicals is handled the aluminium shape surface effect that obtains, and the market requirement is big.Therefore, domestic 90% aluminium section bar industry is the treatment process that adopts fluorochemicals.In addition, among no chromium process is also being studied, do not obtain mass-producing as yet and use.The waste water that adopts fluorine-containing technology to do surface processing aluminium section bar enterprise mainly comes from following workshop: oxidation workshop, polishing departement and painting workshop.The master operation in each workshop comprises degreasing, acid etching, alkaline etching, neutralization, oxidation, sealing of hole and process such as painted, in these operations, needs a large amount of water to clean, and handles 20～27 tons of aluminium section bar water consumptions per ton, average about 25 tons.These waste water generally adopt in lime or the alkali and adjusting and coagulant sedimentation art breading, and the waste water after the processing is because quality problem also only uses in part operation small amount of recycled than advanced enterprise at present, and all the other are as discharge of wastewater.Foshan Guangcheng Aluminum Co., Ltd. as publicity in November, 2007 shows that in 50,000 tons of aluminium section bar project environments of annual output Impact Report book of building its wastewater discharge reaches 114.68 ten thousand tons/year, about 23 tons of aluminium section bar water consumption per ton.
Present research for the aluminium section bar factory effluent mainly is conceived to how to handle and makes its this problem of emission standard that reaches regulation, and mainly concentrates on the processing of chromate waste water and fluoride waste.Form the multicomponent complex composite salt as employing calcium hydroxides such as Tang Weixue, poly-aluminium, FW complexing auxiliary agent etc. and fluorine,, the waste discharge fluorine content is up to state standards then with the polyacrylamide flocculation.The high-concentration fluorine-contained waste water effect that people such as Jiang Liqun handle North China aluminium processing factory by the method that adds lime, Tai-Ace S 150 and polyacrylamide is better.Dong Tie etc. are by adding slaked lime, calcium chloride processing Yuncheng, Shanxi aluminium processing factory fluoride waste.Fan Shengyan etc. are by the hexavalent chromium in the ferrite process processing painting workshop discharge waste water, and the waste water after the processing has reached national specified discharge standard.
Report about the reuse of aluminium section bar factory effluent is less, and does not all relate to the reuse that contains chromium and chemical oxygen demand COD waste water.
The paper report of Yang Xiaosong etc., adopt to regulate-in and coagulation-MS water purification element filters processing aluminium section bar factory effluent, handle back water quality and can reach the requirement of aluminium section bar production recycling water utilization, this research is used in the Henan three peaceful metal products company limiteds that produce 3000 tons of aluminium section bars per year.Be pointed out that the preceding fluorine content of wastewater treatment of using this technology is 0.26mg/l (far below fluorine content requirement in the drinking water sanitary standard), and does not see chromium and chemical oxygen demand COD content's index.
The paper report of Xu Xuan etc., the solution that normal temperature degreasing, alkaline etching, bright dipping, anodic oxidation and sealing of hole etc. are not satisfied production requirement is disposed to and neutralizes in the tempering tank, after adding sodium hydroxide (barium) and flocculation agent precipitation separation again, through ion exchange column, the recycle-water that obtains can return produces the groove repeated use.Be pointed out that, do not see each pollutant load in the processed waste water in this report, also do not relate to chromium and chemical oxygen demand COD content's index in full; In addition, this article was delivered in calendar year 2001, did not see related application so far.
In sum; present China; especially aluminium section bar industrial scale in Guangdong Province's is big; water resources takies with discharged waste water big; but the reuse of relevant waste water does not obtain mass-producing as yet uses, and presses for and carries out the aluminium section bar factory effluent reuse gordian technique research that this has widespread use value and social effect.
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of aluminium section bar is fluorine-containing in producing, the processing recovery method of the waste water of chromium ion.
For achieving the above object, technical scheme provided by the invention is:
According to the difference of pollutent waste water is divided three classes and shunts, to classify processing.
Above-mentioned waste water is divided three classes shunt, classify to handle specifically be meant: is principal pollutant that chromic chromate waste water, principal pollutant are the high fluorine-containing waste water of fluorine and chemical oxygen demand COD, the low fluoride waste that principal pollutant are aluminium, does three classes shunting processing.
Wherein principal pollutant are that the processing recovery method and the technological line of sexavalent chrome chromate waste water part are: make hexavalent chrome reduction to trivalent earlier, make trivalent chromium generate chromium hydroxide precipitation again, add PAM and make the chromium hydroxide precipitation flocculation, make the waste water recycling after the secondary treatment.
Wherein principal pollutant are that the processing recovery method and the technological line of the fluorine-containing high waste water part of fluorine and chemical oxygen demand COD are: drop into calcareous raw material, regulate pH value, make fluorion generate corresponding insolubles, coagulate, flocculate, precipitate through helping, fluorinion concentration is reduced to about 20ppm, the reuse of processed waste water part; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes wherein fluorine, chemical oxygen demand COD, subsequent portion reuse, part qualified discharge.
Wherein principal pollutant are that the method and the technological line of the low fluoride waste processing recovery partly of aluminium are: regulate pH value, coagulate, flocculate, precipitate through helping, aluminum ion is precipitated with the form of aluminium hydroxide, the most of reuse of processed waste water; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes chemical oxygen demand COD wherein, subsequently reuse.
In sum, the difference of the pH value of each the road waste water during the present invention produces according to aluminium section bar, contained ionic species etc. carries out the branch traffic classification to handle, and the waste water after the processing has reached national specified discharge standard.Simultaneously, realized the environmental protection production requirement that reduction of discharging and waste water reclamation utilize again.
Embodiment
Enforcement of the present invention is according to the difference of pollutent, aluminium section bar manufacturing enterprise (adopting fluorine-containing technology to do the surface handles) waste water is divided three classes, comprise that principal pollutant are that sexavalent chrome chromate waste water, principal pollutant are that high fluorine-containing waste water of fluorine and chemical oxygen demand COD and principal pollutant are the low fluoride waste of aluminium, do the classification shunting and handle.
(1) chromate waste water is handled
At first be to carry out wastewater collection, regulate pH value, waste water after collecting is carried out hexavalent chrome reduction to tervalent chemical reaction, make trivalent chromium generate chromium hydroxide precipitation, add PAM again and make the chromium hydroxide precipitation flocculation, obtain Calcium Fluoride (Fluorspan) precipitation, carry out again that mud concentrates, press filtration, remake the waste water recycling after the secondary treatment.Technical process as shown in Figure 1.
(2) high fluoride waste is handled
Drop into calcareous raw material, regulate pH value, make fluorion generate corresponding insolubles, coagulate, flocculate, precipitate, fluorinion concentration is reduced to about 20ppm, the reuse of processed waste water part through helping; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes wherein fluorine, chemical oxygen demand COD, subsequent portion reuse, part qualified discharge.
(3) low fluoride waste is handled
Regulate pH value, coagulate, flocculate, precipitate, make the form precipitation of aluminum ion, the most of reuse of processed waste water with aluminium hydroxide through helping; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes chemical oxygen demand COD wherein, subsequently reuse.
The above-mentioned technology of comprehensive use makes aluminium section bar water of productive use amount by 25m
3/ ton is reduced to 8m
3Below/the ton.
Claims (5)
1, a kind of wastewater treatment recovery method of fluorine-containing, chromium ion, its principal character is exactly: according to the difference of pollutent waste water is divided three classes and shunts, classify processing.
2, the wastewater treatment recovery method of a kind of fluorine-containing, chromium ion according to claim 1, it is characterized in that: waste water is divided into: principal pollutant are that chromic chromate waste water, principal pollutant are the high fluorine-containing waste water of fluorine and chemical oxygen demand COD, the low fluoride waste that principal pollutant are aluminium, do the shunting of three classes and handle.
3, according to the wastewater treatment recovery method of described a kind of fluorine-containing, the chromium ion of right 2, it is characterized in that: wherein principal pollutant are that the processing recovery method and the technological line of sexavalent chrome chromate waste water part are: make hexavalent chrome reduction to trivalent earlier, make trivalent chromium generate chromium hydroxide precipitation again, add PAM and make the chromium hydroxide precipitation flocculation, make the waste water recycling after the secondary treatment.
4, according to the wastewater treatment recovery method of described a kind of fluorine-containing, the chromium ion of right 2, it is characterized in that: wherein principal pollutant are that the processing recovery method and the technological line of the fluorine-containing high waste water part of fluorine and chemical oxygen demand COD are: drop into calcareous raw material, regulate pH value, make fluorion generate corresponding insolubles, coagulate, flocculate, precipitate through helping, fluorinion concentration is reduced to about 20ppm, the reuse of processed waste water part; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes wherein fluorine, chemical oxygen demand COD, subsequent portion reuse, part qualified discharge.
5, according to the wastewater treatment recovery method of described a kind of fluorine-containing, the chromium ion of right 2, it is characterized in that: wherein principal pollutant are that the method and the technological line of the low fluoride waste processing recovery partly of aluminium are: regulate pH value, coagulate, flocculate, precipitate through helping, make the form precipitation of aluminum ion, the most of reuse of processed waste water with aluminium hydroxide; Another part waste water carries out secondary treatment so that modified activated carbon and modified zeolite are compound, further removes chemical oxygen demand COD wherein, subsequently reuse.
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| CNA2008100285462A CN101293717A (en) | 2008-06-05 | 2008-06-05 | Method for processing and recycling wastewater containing fluorine, chromium ion |
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| CNA2008100285462A CN101293717A (en) | 2008-06-05 | 2008-06-05 | Method for processing and recycling wastewater containing fluorine, chromium ion |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126798A (en) * | 2011-01-17 | 2011-07-20 | 无锡德宝水务投资有限公司 | Method for reclaiming fluorine-containing and ammonia nitrogen-containing waste water in electronic industry |
| CN102126799A (en) * | 2011-01-17 | 2011-07-20 | 无锡德宝水务投资有限公司 | Method for treating fluorine-containing and ammonia nitrogen-containing waste water in electronic industry |
| CN101823799B (en) * | 2009-03-06 | 2012-08-15 | 昆山工研院华科生物高分子材料研究所有限公司 | Method for treating acidic fluorine-containing waste water |
| CN102795722A (en) * | 2012-08-15 | 2012-11-28 | 张宏智 | Method for treating waste water generated from surface treatment of aluminum products |
| CN102863093A (en) * | 2011-07-07 | 2013-01-09 | 山东博丰利众化工有限公司 | Aluminum fluoride production sewage processing device |
| CN103058413A (en) * | 2012-12-30 | 2013-04-24 | 江苏梅兰化工有限公司 | Fluorine-containing industrial wastewater treatment technology |
| CN103819028A (en) * | 2014-03-20 | 2014-05-28 | 湖州巨力铝型材有限公司 | Aluminum profile modification wastewater treatment method |
| CN104230053A (en) * | 2014-09-12 | 2014-12-24 | 四川龙蟒钛业股份有限公司 | Method for neutralizing and treating waste water in sulfur-phosphorus-titanium industry chain |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN105540801A (en) * | 2016-01-28 | 2016-05-04 | 上海华虹宏力半导体制造有限公司 | Fluoride-containing wastewater treatment system and method |
| CN106348489A (en) * | 2016-08-31 | 2017-01-25 | 安徽枫慧金属股份有限公司 | Method for treating surface treatment pollutant of aluminum plastic panel |
| CN107459179A (en) * | 2017-09-29 | 2017-12-12 | 安徽凤杰金属资源有限公司 | The processing method of caused waste water in a kind of aluminum products processing |
| CN107698065A (en) * | 2017-11-14 | 2018-02-16 | 蚌埠市嘉实机电设备制造有限公司 | Caused dirty water purification method in a kind of production to aluminum products |
| CN110790433A (en) * | 2019-12-01 | 2020-02-14 | 柏威达(南京)环境科技有限公司 | Treatment process of industrial aluminum production wastewater |
| CN113087040A (en) * | 2021-04-20 | 2021-07-09 | 山西国际电力技术咨询有限公司 | Novel defluorinating agent and fluorine-containing waste liquid treatment process |
-
2008
- 2008-06-05 CN CNA2008100285462A patent/CN101293717A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101823799B (en) * | 2009-03-06 | 2012-08-15 | 昆山工研院华科生物高分子材料研究所有限公司 | Method for treating acidic fluorine-containing waste water |
| CN102126799A (en) * | 2011-01-17 | 2011-07-20 | 无锡德宝水务投资有限公司 | Method for treating fluorine-containing and ammonia nitrogen-containing waste water in electronic industry |
| CN102126798A (en) * | 2011-01-17 | 2011-07-20 | 无锡德宝水务投资有限公司 | Method for reclaiming fluorine-containing and ammonia nitrogen-containing waste water in electronic industry |
| CN102863093A (en) * | 2011-07-07 | 2013-01-09 | 山东博丰利众化工有限公司 | Aluminum fluoride production sewage processing device |
| CN102795722B (en) * | 2012-08-15 | 2014-06-25 | 张宏智 | Method for treating waste water generated from surface treatment of aluminum products |
| CN102795722A (en) * | 2012-08-15 | 2012-11-28 | 张宏智 | Method for treating waste water generated from surface treatment of aluminum products |
| CN103058413A (en) * | 2012-12-30 | 2013-04-24 | 江苏梅兰化工有限公司 | Fluorine-containing industrial wastewater treatment technology |
| CN103819028B (en) * | 2014-03-20 | 2015-04-08 | 湖州巨力铝型材有限公司 | Aluminum profile modification wastewater treatment method |
| CN103819028A (en) * | 2014-03-20 | 2014-05-28 | 湖州巨力铝型材有限公司 | Aluminum profile modification wastewater treatment method |
| CN104230053B (en) * | 2014-09-12 | 2016-08-24 | 四川龙蟒钛业股份有限公司 | Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain |
| CN104230053A (en) * | 2014-09-12 | 2014-12-24 | 四川龙蟒钛业股份有限公司 | Method for neutralizing and treating waste water in sulfur-phosphorus-titanium industry chain |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN104445717B (en) * | 2014-11-13 | 2016-04-27 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process |
| CN105540801B (en) * | 2016-01-28 | 2018-12-11 | 上海华虹宏力半导体制造有限公司 | Fluorine-contained wastewater treatment system and method |
| CN105540801A (en) * | 2016-01-28 | 2016-05-04 | 上海华虹宏力半导体制造有限公司 | Fluoride-containing wastewater treatment system and method |
| CN106348489A (en) * | 2016-08-31 | 2017-01-25 | 安徽枫慧金属股份有限公司 | Method for treating surface treatment pollutant of aluminum plastic panel |
| CN107459179A (en) * | 2017-09-29 | 2017-12-12 | 安徽凤杰金属资源有限公司 | The processing method of caused waste water in a kind of aluminum products processing |
| CN107459179B (en) * | 2017-09-29 | 2020-10-09 | 安徽凤杰金属资源有限公司 | Treatment method of wastewater generated in aluminum product processing |
| CN107698065A (en) * | 2017-11-14 | 2018-02-16 | 蚌埠市嘉实机电设备制造有限公司 | Caused dirty water purification method in a kind of production to aluminum products |
| CN110790433A (en) * | 2019-12-01 | 2020-02-14 | 柏威达(南京)环境科技有限公司 | Treatment process of industrial aluminum production wastewater |
| CN113087040A (en) * | 2021-04-20 | 2021-07-09 | 山西国际电力技术咨询有限公司 | Novel defluorinating agent and fluorine-containing waste liquid treatment process |
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Open date: 20081029 |