CN101993158A - Method for treating stainless steel cold rolling pickling waste water - Google Patents
Method for treating stainless steel cold rolling pickling waste water Download PDFInfo
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- CN101993158A CN101993158A CN 200910101868 CN200910101868A CN101993158A CN 101993158 A CN101993158 A CN 101993158A CN 200910101868 CN200910101868 CN 200910101868 CN 200910101868 A CN200910101868 A CN 200910101868A CN 101993158 A CN101993158 A CN 101993158A
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Abstract
The invention discloses a method for treating stainless steel cold rolling pickling waste water, which adopts a lime milk pretreatment process and a waste water segmental treatment process and comprises the following steps of: firstly, performing lime milk pretreatment on the waste water to control the pH value between 5 and 6; secondly, adding liquid caustic soda to remove heavy metal ions in the waste water so as to form a metal oxide precipitate; and finally, treating fluorine ions, namely adding polyaluminium chloride and lime milk to remove the fluorine ions, and filtering and discharging the waste water after adjusting the pH. The treatment method has good using effect, the waste water reaches the required standard and is stable, the sludge quantity is small, and the cost is low.
Description
Technical field
The invention belongs to the technology for treating industrial waste water field, especially a kind of treatment process of stainless steel cold-rolling pickling wastewater.
Background technology
The acid-washing stainless steel line mainly produces two kinds of waste water, and the one, the chromyl neutral salt waste water that neutral salt electrolysis section produces, another kind are the acid waste water that nitration mixture pickling section produces.Have for these two kinds of wastewater treatment method at present:
1, traditional neutralisation:
General stainless steel plant adopts traditional lime neutralizing treatment method to handle pickling waste waters, and its advantage is a process stabilizing, and water conditioning is up to standard, and operation control is comparatively simple; But its shortcoming is also comparatively obvious:
(1) medicament expense is with higher, and certain stainless steel plant actual achievement in 2007 reaches 9.67 yuan/m
3
(2) mud of Chan Shenging is mixture, particularly contains fluorion, can not be as the raw material reuse of steel melting furnace;
(3) mud of Chan Shenging belongs to danger wastes, needs to handle by local Environmental Protection Agency fixed route, and processing costs is higher, and certain stainless steel plant actual achievement in 2007 is 8.58 yuan/m
3(local sludge disposal takes 300 yuan/ton)
2, mud divides the matter neutralisation:
This technology has applied for a patent and has obtained number of patent application in 2007, the patent No. is the treatment process of 200710067749.8 1 kinds of stainless steel acid cleaning waste waters, at present just in publicity.
The thinking of this technology be with liquid caustic soda (NaOH) replace lime as neutralizing agent, the heavy metal in the waste water is precipitated separately, and then adds the lime defluorination, make it to produce the mud of heavy metal sewage sludge and these two kinds of separate collections of fluorochemical mud, dehydration.Though this kind treatment process can significantly reduce sludge quantity (decrement reaches about 80%), also has weak point:
(1) (200～5000mg/L), there is fluctuation in the water outlet fluorinion concentration, needs reflow treatment when surpassing 10mg/L because of the water inlet fluorinion concentration changes greatly;
(2) medicament expense and mud take the still higher and traditional neutralizing treatment method of sum and are in same level.
Summary of the invention
Technical problem to be solved by this invention provides a kind of treatment process of stainless steel cold-rolling pickling wastewater of novel reduction process expense, can reduce the reagent consumption of pickling waste waters processing and the total expenses of sludge treatment, and can effectively remove fluorion.
The present invention solves the problems of the technologies described above the technical scheme of being taked to be: a kind of treatment process of stainless steel cold-rolling pickling wastewater, described stainless steel cold-rolling pickling wastewater comprises the acid waste water of chromyl neutral salt waste water, sulfuric acid electrolysis wastewater and the generation of nitration mixture pickling section that neutral salt electrolysis section produces, it is characterized in that comprising following processing step:
1) the nitration mixture pickling waste waters enters the acid waste water equalizing tank and regulates water quality; The nitration mixture pickling waste waters tentatively neutralizes at pretreatment tank earlier, by adding milk of lime pH value is controlled at 5～6, can reduce the injected volume of later process liquid caustic soda like this, and wherein the calcium ion of Jia Ruing reacts generation Calcium Fluoride (Fluorspan) at neutralizing well and fluorochemical;
2) neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater enter the neutral salt wastewater equalization pond and regulate water quality; Neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater enter one-level reducing bath, second-stage reduction groove successively, make the hexavalent chrome reduction in the waste water become trivalent chromium by adding reductive agent;
3) behind the nitration mixture pickling waste waters and neutral salt electrolysis wastewater or the mixing of sulfuric acid electrolysis wastewater through preliminary treatment, enter one-level neutralizing well, secondary neutralizing well successively, by adding liquid caustic soda pH value is controlled at 9.0～9.5, makes heavy metal ion such as iron in the waste water, chromium, nickel, manganese generate Fe (OH) respectively
3, Cr (OH)
3, Ni (OH)
2And Mn (OH)
4Precipitation;
4) enter the reaction settling pond and separate, heavy metal sewage sludge is sent into the plate-and-frame filter press press filtration after sludge thickener concentrates, and waste water enters fluorochemical treatment process section;
5) waste water is removed fluorion by adding hydrochloric acid, polymerize aluminum chloride (PAC) and milk of lime in the fluorine reaction tank, add hydrochloric acid control pH value in 8～9 scope, calcium ion in the milk of lime and fluorion generate the Calcium Fluoride (Fluorspan) precipitation, polymerize aluminum chloride is a kind of inorganic polymer coagulant, can promote to flocculate into piece and rapid subsidence, the dosage of polymerize aluminum chloride is for handling 0.2～0.4% of the water yield;
6) enter inclined-plate clarifying basin and separate, fluorochemical mud reclaims send into the plate-and-frame filter press press filtration after sludge thickener concentrates after;
7) waste water is adjusted to neutrality through PH after sand-bed filter discharges after filtering through final neutralizing well.
Described reductive agent is hydrochloric acid, sodium bisulfite, and the add-on of reductive agent is by pH value and current potential ORP control, and pH value is 2.5～3, and current potential ORP is that 280～320mv can add by volume pump;
Described liquid caustic soda is a sodium hydroxide;
Used neutralization reagent was hydrochloric acid or sodium hydroxide during described final neutralizing well PH regulated;
Compared with prior art, the present invention has taked milk of lime pretreatment technology and waste water staging treating technology, and its advantage is:
(1) milk of lime by pretreatment section adds and plays the consumption that reduces liquid caustic soda in the neutralizing well, makes in the waste water that enters the defluorinating process section fluorinion concentration stable, and waste water is absolutely up to standard, has avoided reflow treatment;
(2) mud decrement effect highly significant;
(3) medicament expense reduces, and sludge quantity reduces, and total processing costs reduces greatly than traditional neutralizing treatment method.
Description of drawings
Fig. 1 is a kind of stainless steel cold-rolling pickling wastewater processing technological flow figure.
Embodiment
Below in conjunction with embodiment the present invention is done and to describe in further detail.
A kind of treatment process of stainless steel cold-rolling pickling wastewater is characterized in that comprising successively following processing step:
1) the nitration mixture pickling waste waters is entered the acid waste water equalizing tank and regulate water quality, enter pretreatment tank then and tentatively neutralize, pH value is controlled at 5～6 by adding milk of lime;
2) neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater are entered neutral salt wastewater equalization pond adjusting water quality, enter one-level reducing bath, second-stage reduction groove then successively, make the hexavalent chrome reduction in the waste water become trivalent chromium by adding reductive agent;
Reductive agent is hydrochloric acid, sodium bisulfite, and the add-on of reductive agent is by pH value and current potential ORP control, and pH value is 2.5～3, and current potential ORP is 280～320mv;
3) the nitration mixture pickling waste waters of process preliminary treatment and neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater enter one-level neutralizing well, secondary neutralizing well successively, by adding liquid caustic soda pH value is controlled at 9.0～9.5, makes heavy metal ion such as iron in the waste water, chromium, nickel, manganese generate Fe (OH) respectively
3, Cr (OH)
3, Ni (OH)
2And Mn (OH)
4Etc. precipitation; Liquid caustic soda adopts sodium hydroxide;
4) enter the reaction settling pond and separate, heavy metal sewage sludge reclaims send the plate-and-frame filter press press filtration after sludge thickener concentrates after, and waste water enters fluorochemical treatment process section;
5) the clarification waste liquid after will separating is put into the fluorine reaction tank, removes fluorion by adding hydrochloric acid, polymerize aluminum chloride and milk of lime, and the control pH value is in 8～9 scope, and the dosage of polymerize aluminum chloride makes to generate CaF for handling 0.2～0.4% of the water yield
2Precipitation; Milk of lime and fluorion reaction, so its addition is monitored the water inlet of fluorine reaction tank, inclined-plate clarifying basin water outlet by online fluorion detector, set the opening time that lime adds pneumavalve according to these two values
6) enter inclined-plate clarifying basin and separate, fluorochemical mud reclaims send the plate-and-frame filter press press filtration after sludge thickener concentrates after;
7) waste water discharges after sand-bed filter filters after final neutralizing well is adjusted to neutrality with hydrochloric acid or sodium hydroxide with PH.By method of wastewater treatment of the present invention the 1# waste water processing station neutralization station that adopts traditional technology is transformed, the waste water quality after the processing is up to standard stable and sludge quantity is few, and processing cost reduces.
1, the processed waste water water conditioning is up to standard:
Under the quantity-produced situation, through 23 times sampling analysis, the indicator ion that all water outlets detect is all up to standard, and far below the emission standard of stipulating.
2, compare with original technology, use waste water treatment process total cost of the present invention to reduce greatly, the wastewater treatment total expenses has comprised sludge disposal expense and reagent consumption expense.
2.1 reagent consumption expense
The hexavalent chrome reduction processing section is not changed in new, old technology, and the consumption of sodium bisulfite can not change, and therefore following medicament expense will be deducted sodium bisulfite with comparative data, lime, hydrochloric acid, liquid caustic soda, PAM and PAC is compared.
Ton water medicament expense is as follows with the data of (not comprising sodium bisulfite):
PAM promptly is a polyacrylamide, is a kind of organic floculant, is used to react settling pond and inclined-plate clarifying basin, helps the mud-water separation process.
2.2 sludge quantity is relatively:
Illustrate:
Therefore (1) less because of the plate-and-frame filter press ability of former oily(waste)water treatment station, fluorochemical mud fails to transport outward after whole press filtrations, and the mud cake amount of coming out according to press filtration and this type of sludge quantity of mud conservative estimation in the sludge sump are 5 tons.
In January, (2) 2008 is longer because of the 3AP scheduled outage time, handles actual achievements relatively with 2007 years, this month waste water acidity lighter; Therefore consider 1# waste water that neutralization station is handled mainly from 1,2AP, acidity is lighter, with the novel process sludge quantity and January piece of data relatively have certain representativeness.
2.3 cost for wastewater treatment: (comprising the sodium bisulfite expense)
After adopting the treatment process of stainless steel cold-rolling pickling wastewater of the present invention that 1# waste water processing station neutralization station is transformed, waste water quality is up to standard stable, and sludge quantity reduces 70%, and the total processing costs of waste water reduces by 54.3% than traditional neutralizing treatment method.
Claims (4)
1. the treatment process of a stainless steel cold-rolling pickling wastewater is characterized in that comprising successively following processing step:
1) the nitration mixture pickling waste waters is entered the acid waste water equalizing tank and regulate water quality, enter pretreatment tank then and tentatively neutralize, pH value is controlled at 5～6 by adding milk of lime;
2) neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater are entered neutral salt wastewater equalization pond adjusting water quality, enter one-level reducing bath, second-stage reduction groove then successively, make the hexavalent chrome reduction in the waste water become trivalent chromium by adding reductive agent;
3) the nitration mixture pickling waste waters of process preliminary treatment and neutral salt electrolysis wastewater or sulfuric acid electrolysis wastewater enter one-level neutralizing well, secondary neutralizing well successively, by adding liquid caustic soda pH value is controlled at 9.0～9.5, makes heavy metal ion such as iron in the waste water, chromium, nickel, manganese generate Fe (OH) respectively
3, Cr (OH)
3, Ni (OH)
2And Mn (OH)
4Precipitation;
4) go into to react settling pond and separate, heavy metal sewage sludge reclaims send the plate-and-frame filter press press filtration after sludge thickener concentrates after, and waste water enters fluorochemical treatment process section;
5) the clarification waste liquid after separating is put into the fluorine reaction tank, removes fluorion by adding hydrochloric acid, polymerize aluminum chloride and milk of lime, and the control pH value is in 8～9 scope, and the dosage of polymerize aluminum chloride makes to generate CaF for handling 0.2～0.4% of the water yield
2Precipitation;
6) enter inclined-plate clarifying basin and separate, fluorochemical mud reclaims send the plate-and-frame filter press press filtration after sludge thickener concentrates after;
7) waste water discharges after sand-bed filter filters after final neutralizing well PH is adjusted to neutrality.
2. the treatment process of a kind of stainless steel cold-rolling pickling wastewater according to claim 1, it is characterized in that described reductive agent is hydrochloric acid, sodium bisulfite, the add-on of reductive agent is by pH value and current potential ORP control, and pH value is 2.5～3, and current potential ORP is 280～320mv.
3. the treatment process of a kind of stainless steel cold-rolling pickling wastewater according to claim 1 is characterized in that described liquid caustic soda is a sodium hydroxide.
4. the treatment process of a kind of stainless steel cold-rolling pickling wastewater according to claim 1 is characterized in that used neutralization reagent is hydrochloric acid or sodium hydroxide in the described final neutralizing well PH adjusting.
Priority Applications (1)
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|---|---|---|---|
| CN 200910101868 CN101993158A (en) | 2009-08-28 | 2009-08-28 | Method for treating stainless steel cold rolling pickling waste water |
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|---|---|---|---|
| CN 200910101868 CN101993158A (en) | 2009-08-28 | 2009-08-28 | Method for treating stainless steel cold rolling pickling waste water |
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| CN101993158A true CN101993158A (en) | 2011-03-30 |
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Cited By (27)
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| CN102295372A (en) * | 2011-05-18 | 2011-12-28 | 山东恒邦冶炼股份有限公司 | Method for treating acidic smelting waste water containing high arsenic and heavy metal ions |
| CN102351348A (en) * | 2011-09-06 | 2012-02-15 | 中冶南方工程技术有限公司 | Anti-scaling treatment method for stainless steel acid waste water subsequent treatment |
| CN102583815A (en) * | 2012-01-28 | 2012-07-18 | 马鞍山市桓泰环保设备有限公司 | Method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with potassium dichromate method |
| CN102836583A (en) * | 2012-09-05 | 2012-12-26 | 江苏永钢集团有限公司 | Device for prolonging service life of oil-containing filter cloth of continuous casting plate frame |
| CN102992512A (en) * | 2012-10-15 | 2013-03-27 | 天津市亿博制钢有限公司 | Treatment method of industrial wastewater |
| CN103449631A (en) * | 2013-09-02 | 2013-12-18 | 苏州富奇诺水治理设备有限公司 | Treatment method of iron and steel pickling waste water |
| CN103484888A (en) * | 2012-06-14 | 2014-01-01 | 兰州大学 | Treatment method for chromium-containing sodium sulfate waste solution and sulfuric acid acid-washing waste solution in stainless steel production |
| CN103922516A (en) * | 2014-05-07 | 2014-07-16 | 苏州皇森机电科技有限公司 | Stainless steel pickling wastewater treatment device |
| CN104310652A (en) * | 2014-10-28 | 2015-01-28 | 温玉友 | Stainless steel cold-rolled acidic wastewater treatment device and method |
| CN105859005A (en) * | 2016-05-10 | 2016-08-17 | 宝钢工程技术集团有限公司 | Method and system for treating stainless steel cold-rolling and pickling waste acid |
| CN105923840A (en) * | 2016-06-20 | 2016-09-07 | 宁波宝新不锈钢有限公司 | Technology for treating stainless steel nitrate-free pickling waste water |
| CN105948312A (en) * | 2016-05-23 | 2016-09-21 | 武汉工程大学 | Technical method for CPE wastewater treatment |
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| CN106830167A (en) * | 2017-02-27 | 2017-06-13 | 沈阳化工大学 | A kind of method of fluorine ion in selective removal stainless steel acid cleaning waste water |
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| CN108928953A (en) * | 2018-06-29 | 2018-12-04 | 中国科学院过程工程研究所 | A kind of method of stainless steel acid cleaning waste water recycling |
| CN109609962A (en) * | 2018-12-29 | 2019-04-12 | 佛山市诚德新材料有限公司 | A kind of acid washing method of stainless steel band |
| CN110182991A (en) * | 2019-05-24 | 2019-08-30 | 江苏甬金金属科技有限公司 | A kind of method that the neutral salt Sewage treatment that pickling of metal generates utilizes |
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| CN102351348A (en) * | 2011-09-06 | 2012-02-15 | 中冶南方工程技术有限公司 | Anti-scaling treatment method for stainless steel acid waste water subsequent treatment |
| CN102351348B (en) * | 2011-09-06 | 2013-07-17 | 中冶南方工程技术有限公司 | Anti-scaling treatment method for stainless steel acid waste water subsequent treatment |
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| CN103484888A (en) * | 2012-06-14 | 2014-01-01 | 兰州大学 | Treatment method for chromium-containing sodium sulfate waste solution and sulfuric acid acid-washing waste solution in stainless steel production |
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| CN104310652A (en) * | 2014-10-28 | 2015-01-28 | 温玉友 | Stainless steel cold-rolled acidic wastewater treatment device and method |
| CN104310652B (en) * | 2014-10-28 | 2017-01-04 | 温玉友 | Stainless-steel cold-rolling process for treating acidic waste water |
| CN105859005A (en) * | 2016-05-10 | 2016-08-17 | 宝钢工程技术集团有限公司 | Method and system for treating stainless steel cold-rolling and pickling waste acid |
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| CN105948313A (en) * | 2016-05-25 | 2016-09-21 | 秦华达 | Mixed treatment process for stainless steel pickling wastewater and washing wastewater |
| CN105923840A (en) * | 2016-06-20 | 2016-09-07 | 宁波宝新不锈钢有限公司 | Technology for treating stainless steel nitrate-free pickling waste water |
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| CN106865677A (en) * | 2017-02-27 | 2017-06-20 | 沈阳化工大学 | The method that fluorine ion in stainless steel acid cleaning waste water is removed with magnalium hydrotalcite |
| CN106830167A (en) * | 2017-02-27 | 2017-06-13 | 沈阳化工大学 | A kind of method of fluorine ion in selective removal stainless steel acid cleaning waste water |
| WO2018166503A1 (en) * | 2017-03-15 | 2018-09-20 | 福建欣宇卫浴科技股份有限公司 | Stainless steel pickling wastewater treatment system |
| CN108585157A (en) * | 2018-04-23 | 2018-09-28 | 天津大学 | A method of removing coal converts fluorine in wastewater compound |
| CN110451676A (en) * | 2018-05-07 | 2019-11-15 | 惠州市鸿宇泰科技有限公司 | A kind of processing method of acidic industrial effluent |
| CN108793592A (en) * | 2018-06-07 | 2018-11-13 | 四川旭昊德环保设备有限公司 | A kind of Industrial sewage treatment system |
| CN108793592B (en) * | 2018-06-07 | 2021-10-22 | 四川纯阳润森节能环保有限公司 | Industrial sewage treatment system |
| CN108928953A (en) * | 2018-06-29 | 2018-12-04 | 中国科学院过程工程研究所 | A kind of method of stainless steel acid cleaning waste water recycling |
| CN109609962A (en) * | 2018-12-29 | 2019-04-12 | 佛山市诚德新材料有限公司 | A kind of acid washing method of stainless steel band |
| CN110182991A (en) * | 2019-05-24 | 2019-08-30 | 江苏甬金金属科技有限公司 | A kind of method that the neutral salt Sewage treatment that pickling of metal generates utilizes |
| CN112499815A (en) * | 2020-11-25 | 2021-03-16 | 山东宏旺实业有限公司 | Stainless steel cold rolling sludge recovery treatment method |
| CN114455776A (en) * | 2021-12-21 | 2022-05-10 | 中煤科工集团杭州研究院有限公司 | Stainless steel pickling wastewater treatment method based on biological denitrification |
| CN114455776B (en) * | 2021-12-21 | 2022-12-06 | 中煤科工集团杭州研究院有限公司 | Stainless steel pickling wastewater treatment method based on biological denitrification |
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Application publication date: 20110330 |