CN101549924A - Three-stage type electroplating waste water treatment method - Google Patents
Three-stage type electroplating waste water treatment method Download PDFInfo
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- CN101549924A CN101549924A CNA2008100602246A CN200810060224A CN101549924A CN 101549924 A CN101549924 A CN 101549924A CN A2008100602246 A CNA2008100602246 A CN A2008100602246A CN 200810060224 A CN200810060224 A CN 200810060224A CN 101549924 A CN101549924 A CN 101549924A
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Abstract
The invention belongs to the technical field of industrial waste water treatment, in particular to a three-stage type electroplating waste water treatment method. Aiming at overcoming the defects of high cost, no recycle of heavy metals, difficulty of treated waste water for reaching a standard and great difficulty of integrated waste water treatment of the prior electroplating waste water treatment method, the invention provides the three-stage type electroplating waste water treatment method which has less investment and low operation cost and can recycle various metals or alloy salts in the electroplating waste water and ensure that the treated waste water can reach the standard and become deionized water to be reused for electroplating. The method comprises the following steps: (1) using a chemical precipitation method to extract correlative metal salts and reusing the correlative metal salts for electroplating; (2) treating the electroplating integrated waste water to reach the standard; and (3) treating the standardized electroplating waste water into the deionized water by using an ion exchange device after being treated by a pretreatment device.
Description
Technical field
The invention belongs to the technical field of Industrial Wastewater Treatment, particularly a kind of three-stage type electroplating waste water treatment method.
Background technology
Up to now, electroplating wastewater is one of three major source of pollution in the world.The family surplus in the of 50,000 that has an appointment of producer is electroplated in the whole nation, and the electroplating wastewater annual emissions reaches more than 4,000,000,000 tons.Main harm is the severe toxicity effect of prussiate, the pollution of each heavy metal species in the electroplating wastewater.In recent years, the whole nation mainly is a requirement electroplating wastewater qualified discharge in the plating cleaner production activity of carrying out, in fact because existing plating method of wastewater treatment cost height, the enterprise of domestic Electroplate Factory energy stably reaching standard discharging is few in number, even if qualified discharge waste water, still contain heavy metal, still pollute the environment.
Mainly exist following weak point in the existing plating method of wastewater treatment:
1, cyanide wastewater processing cost height, the waste water difficulty after the processing is up to standard.Prussiate is strong complexing agent, plays an important role at electroplating industry, and under the complexing of strong complexing agent prussiate, heavy metal is difficult to precipitation, causes that heavy metal is difficult to up to standard in the waste water.The existing cyanide wastewater treatment process of generally using is alkaline hypochlorite oxidation method, and clorox itself can not the oxidation prussiate, resolve into Cl
2Ability oxidation prussiate, and this decomposition is very slow under alkaline condition, only under light or ultraviolet irradiation, clorox decomposes generation O, and single oxygen has very strong oxidation capacity, ability oxidation prussiate, this is difficult in suitability for industrialized production accomplish that this also is an oxidable prussiate in the alkaline clorox beaker under lab, and in suitability for industrialized production, be to adopt big jar of closed, this is the reason that is difficult to the oxidation prussiate.At present, handle 1 ton of cyanide wastewater and need change 1 many hours time, need the pH value of twice adjusting waste water in treating processes, the expense of processing is 15~20 yuan, and the cyanide wastewater after the processing still can not be up to standard.
2, heavy metal does not reclaim.The utilization ratio of heavy metal in plating be generally less than 50%, as: electrodeposited chromium has only 8%~13%, and electronickelling has only<and 45%; And heavy metal most is in electroplating wastewater, do not reclaim heavy metal, and make the whole or big portion of heavy metal in the electroplating wastewater become electroplating sludge, this is most at present common situation of electroplating producer to electroplating wastewater processing, this still not a kind of great wasting of resources also makes wastewater treatment more difficult.
Also have some to electroplate producer at present and reclaim heavy metal from electroplating wastewater, they generally are the heavy metals that adopts in the chemical precipitation method processing electroplating wastewater, make it precipitation; And the thorough sedimentary pH value of various metals is different, as: the pH value of nickel be>9.5, normally pH value is adjusted to 10~11; And the pH value of zinc is 9, when pH value 11, and the zinc dissolving, trivalent chromium also dissolves, and has caused and has attended to one thing and lose sight of another, and makes electroplating wastewater processing not up to standard.
3, the comprehensive wastewater intractability is big.Because heavy metal does not reclaim, cyanide wastewater is handled not thorough, contains contents of many kinds of heavy metal ion such as nickel, copper, trivalent chromium, zinc, tin in the electroplating integrated waste water, owing to contain the complexing agent that uses in the multiple plating, makes integrative electroplating waste be difficult to handle again.
Summary of the invention
The present invention is directed to existing plating method of wastewater treatment cost height, do not reclaim heavy metal, waste water difficulty after the processing is up to standard, the weak point that the comprehensive wastewater intractability is big, provide a kind of less investment, process cost low, can the various metal or alloy salt in the electroplating wastewater be reclaimed, reuse, the waste water after the processing not only can be up to standard, is back to galvanized a kind of three-stage type electroplating waste water treatment method and can become deionized water.
The technical solution used in the present invention is finished in the following way: a kind of three-stage type electroplating waste water treatment method, and it may further comprise the steps:
(1) one section: from various electroplating wastewaters, extract relevant metal-salt with chemical precipitation method as far as possible, and be back to plating:
1. reclaim nickel salt with chemical precipitation method from electronickelling waste water, and be back to the electronickelling groove, supernatant liquor flows into electroplating integrated wastewater disposal basin;
2. reclaim mantoquita with chemical precipitation method from the hydrosulphate copper plating wastewater, and be back to electro-coppering, supernatant liquor flows into electroplating integrated wastewater disposal basin;
3. reclaim chromic acid (sexavalent chrome) the chromic acid passivation waste water with chemical precipitation method and band porous ceramics jar electrolytic tank electrolysis method behind chromium-electroplating waste water and electro-galvanizing, and be back to electrodeposited chromium, secondary wastewater flows into electroplating integrated wastewater disposal basin;
4. reclaim zinc salt with chemical precipitation method from chloride galvanizing waste water, and be back to the electro-galvanizing groove, supernatant liquor flows into electroplating integrated wastewater disposal basin;
5. from other plated metal or alloy waste water, reclaim metal or alloy salt with chemical precipitation method, as: golden recovery, silver recovery, platinum recovery, plumbous recovery, tin recovery etc.
(2) two sections: electroplating integrated wastewater treatment is up to standard:
1. cyanide wastewater treatment process: add sulphuric acid soln in cyanide wastewater, making the waste water current potential is 100~130; Add oxygenant again, oxygenant adopts a kind of in potassium permanganate, perchloric acid, the Sodium Persulfate, and making the waste water current potential is more than 2000, reacts 15~30 minutes; Waste water flows into neutralization tank, neutralization precipitation;
2. electroplating integrated wastewater to reach standard is handled: it is 8~9 that electroplating integrated waste water is regulated pH value with lime white, stirring reaction 10~20 minutes; Add 5% sodium sulfide solution, added 5% sodium sulfide solution amount is by 0.8~1.2 liter of/ton waste water, stirring reaction 10~20 minutes; Add PAC flocculation agent 0.7~1.4Kg/ ton waste water in the waste water, stirring reaction 5~15 minutes adds 3 ‰ PAM700~1500ml/ ton waste water again, stir slightly and promptly stop natural subsidence, wastewater supernatant fluid qualified discharge, the precipitation press filtration, filtrate is returned into electroplating integrated wastewater disposal basin and is handled, and the precipitation pack is handled.
(3) three sections: wastewater treatment up to standard is become deionized water:
After electroplating wastewater up to standard was handled with pretreating device, the heavy metal that wherein contains, calcium, the equal content of magnesium were atomic, are processed into deionized water with ion exchange unit again, and this ionized water can be back to electroplates dosing or as water for cleaning.
In above-mentioned electroplating effluent treatment method, the instrument that is used for detecting the redox potential in the waste water is to use oxidation-reduction potentiometer, and this oxidation-reduction potentiometer can be used to indicate the current potential in the waste water; The instrument that is used for detecting the waste water pH value is a PH on-line Control instrument.
The method that three-stage type electroplating waste water of the present invention is handled has following characteristics:
1, less investment, process cost are low, and the present invention only handles on the equipment at former waste water from plating plant has increased metal-salt recovery system, pre-processing device, and ion exchange method equipment is not changed the raw wastewater treatment facility;
2, to the various metal or alloy salt in the electroplating wastewater reclaim, reuse;
3, the present invention handles electroplating wastewater up to standard with ion exchange method becomes deionized water and is back to plating, and than reverse osmosis method reduced investment, process cost is low, and the deionized water cost of reuse is low, and can guarantee to electroplate the water quality requirement that makes water.
Embodiment
Below in conjunction with embodiment, a kind of three-stage type electroplating waste water treatment method of the present invention is described further.
A kind of treatment process of three-stage type electroplating waste water, it may further comprise the steps:
(1) one section: from various electroplating wastewaters, extract relevant metal-salt with chemical precipitation method as far as possible, and be back to plating:
1. reclaim nickel salt with chemical precipitation method from electronickelling waste water, and be back to the electronickelling groove, nickel content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
2. reclaim mantoquita with chemical precipitation method from the hydrosulphate copper plating wastewater, and be back to electro-coppering, copper content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
3. behind chromium-electroplating waste water and electro-galvanizing, reclaim chromic acid (sexavalent chrome) the chromic acid passivation waste water with chemical precipitation method and band porous ceramics jar electrolytic tank electrolysis method, and be back to electrodeposited chromium, contain sexavalent chrome in the secondary wastewater and total chrome is up to standard, flow into electroplating integrated wastewater disposal basin;
4. reclaim zinc salt with chemical precipitation method from chloride galvanizing waste water, and be back to the electro-galvanizing groove, zinc content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
5. from other plated metal or alloy waste water, reclaim metal or alloy salt with chemical precipitation method, as: golden recovery, silver recovery, platinum recovery, plumbous recovery, tin recovery etc.
(2) two sections: electroplating integrated wastewater treatment is up to standard:
1. cyanide wastewater treatment process: add sulphuric acid soln in cyanide wastewater, making the waste water current potential is 100~130; Add oxygenant again, oxygenant adopts a kind of in potassium permanganate, perchloric acid, the Sodium Persulfate, and making the waste water current potential is more than 2000, reacts 15~30 minutes; Waste water flows into neutralization tank, neutralization precipitation;
2. electroplating integrated wastewater to reach standard is handled: electroplating integrated waste water injects electroplating integrated wastewater disposal basin, and wherein electroplating integrated waste water comprises secondary wastewater, pickling waste waters, alkali cleaning waste water, other electroplating wastewater after secondary wastewater, the cyanide wastewater after various metal-salts reclaim handled; It is 8~9 that electroplating integrated waste water is regulated pH value with lime white, stirring reaction 15 minutes; Add 5% sodium sulfide solution, added 5% sodium sulfide solution amount is by 1 liter of/ton waste water, stirring reaction 15 minutes; Add PAC flocculation agent 1Kg/ ton waste water in the waste water, stirring reaction 10 minutes adds 3 ‰ PAM1000ml/ ton waste water again, stir slightly and promptly stop natural subsidence, wastewater supernatant fluid qualified discharge, the precipitation press filtration, filtrate is returned into electroplating integrated wastewater disposal basin and is handled, and the precipitation pack is handled.
(3) three sections: wastewater treatment up to standard is become deionized water:
After electroplating wastewater up to standard was handled with pretreating device, the heavy metal that wherein contains, calcium, the equal content of magnesium were atomic, are processed into deionized water with ion exchange unit again.
Claims (3)
1, a kind of three-stage type electroplating waste water treatment method is characterized in that this three-stage type electroplating waste water treatment method, may further comprise the steps:
(1) one section: from various electroplating wastewaters, extract relevant metal-salt with chemical precipitation method as far as possible, and be back to plating:
1. reclaim nickel salt with chemical precipitation method from electronickelling waste water, and be back to the electronickelling groove, supernatant liquor flows into the comprehensive wastewater pond;
2. reclaim mantoquita with chemical precipitation method from the hydrosulphate copper plating wastewater, and be back to electro-coppering, supernatant liquor flows into electroplating integrated wastewater disposal basin;
3. reclaim chromic acid (sexavalent chrome) the chromic acid passivation waste water with chemical precipitation method and band porous ceramics jar electrolytic tank electrolysis method behind chromium-electroplating waste water and electro-galvanizing, and be back to electrodeposited chromium, secondary wastewater flows into the comprehensive wastewater pond;
4. reclaim zinc salt with chemical precipitation method from chloride galvanizing waste water, and be back to the electro-galvanizing groove, supernatant liquor flows into electroplating integrated wastewater disposal basin;
5. from other plated metal or alloy waste water, reclaim metal or alloy salt with chemical precipitation method, as: golden recovery, silver recovery, platinum recovery, plumbous recovery, tin recovery etc.;
(2) two sections: electroplating integrated wastewater treatment is up to standard:
1. cyanide wastewater treatment process: add sulphuric acid soln in cyanide wastewater, making the waste water current potential is 100~130; Add oxygenant again, oxygenant adopts a kind of in potassium permanganate, perchloric acid, the Sodium Persulfate, and making the waste water current potential is more than 2000, reacts 15~30 minutes; Waste water flows into neutralization tank, neutralization precipitation;
2. electroplating integrated wastewater to reach standard is handled: it is 8~9 that electroplating integrated waste water is regulated pH value with lime white, stirring reaction 10~20 minutes; Add 5% sodium sulfide solution, added 5% sodium sulfide solution amount is by 0.8~1.2 liter of/ton waste water, stirring reaction 10~20 minutes; Add PAC flocculation agent 0.7~1.4Kg/ ton waste water in the waste water, stirring reaction 5~15 minutes adds 3 ‰ PAM700~1500ml/ ton waste water again, stir slightly and promptly stop natural subsidence, wastewater supernatant fluid qualified discharge, the precipitation press filtration, filtrate is returned into the comprehensive wastewater pond and is handled, and the precipitation pack is handled;
(3) three sections: wastewater treatment up to standard is become deionized water:
Electroplating wastewater up to standard is processed into deionized water with ion exchange unit after handling with pretreating device again.
2, three-stage type electroplating waste water treatment method according to claim 1, the instrument that it is characterized in that being used for detecting the redox potential in the waste water is to use oxidation-reduction potentiometer; The instrument that is used for detecting the waste water pH value is a PH on-line Control instrument.
3, three-stage type electroplating waste water treatment method according to claim 1 and 2 is characterized in that three-stage type electroplating waste water treatment method may further comprise the steps:
(1) one section: from various electroplating wastewaters, extract relevant metal-salt with chemical precipitation method as far as possible, and be back to plating:
1. reclaim nickel salt with chemical precipitation method from electronickelling waste water, and be back to the electronickelling groove, nickel content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
2. reclaim mantoquita with chemical precipitation method from the hydrosulphate copper plating wastewater, and be back to electro-coppering, copper content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
3. behind chromium-electroplating waste water and electro-galvanizing, reclaim chromic acid (sexavalent chrome) the chromic acid passivation waste water with chemical precipitation method and band porous ceramics jar electrolytic tank electrolysis method, and be back to electrodeposited chromium, contain sexavalent chrome in the secondary wastewater and total chrome is up to standard, flow into electroplating integrated wastewater disposal basin;
4. reclaim zinc salt with chemical precipitation method from chloride galvanizing waste water, and be back to the electro-galvanizing groove, zinc content<0.5mg/l in the secondary wastewater, supernatant liquor flow into electroplating integrated wastewater disposal basin;
5. from other plated metal or alloy waste water, reclaim metal or alloy salt with chemical precipitation method, as: golden recovery, silver recovery, platinum recovery, plumbous recovery, tin recovery etc.
(2) two sections: electroplating integrated wastewater treatment is up to standard:
1. cyanide wastewater treatment process: add sulphuric acid soln in cyanide wastewater, making the waste water current potential is 100~130; Add oxygenant again, oxygenant adopts a kind of in potassium permanganate, perchloric acid, the Sodium Persulfate, and making the waste water current potential is more than 2000, reacts 15~30 minutes; Waste water flows into neutralization tank, neutralization precipitation;
2. electroplating integrated wastewater to reach standard is handled: electroplating integrated waste water injects electroplating integrated wastewater disposal basin, and wherein electroplating integrated waste water comprises secondary wastewater, pickling waste waters, alkali cleaning waste water, other electroplating wastewater after secondary wastewater, the cyanide wastewater after various metal-salts reclaim handled; It is 8~9 that electroplating integrated waste water is regulated pH value with lime white, stirring reaction 15 minutes; Add 5% sodium sulfide solution, added 5% sodium sulfide solution amount is by 1 liter of/ton waste water, stirring reaction 15 minutes; Add PAC flocculation agent 1Kg/ ton waste water in the waste water, stirring reaction 10 minutes adds 3 ‰ PAM1000ml/ ton waste water again, stir slightly and promptly stop natural subsidence, wastewater supernatant fluid qualified discharge, the precipitation press filtration, filtrate is returned into electroplating integrated wastewater disposal basin and is handled, and the precipitation pack is handled.
(3) three sections: wastewater treatment up to standard is become deionized water:
Electroplating wastewater up to standard is processed into deionized water with ion exchange unit after handling with pretreating device again.
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Cited By (13)
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CN101817608A (en) * | 2010-04-02 | 2010-09-01 | 厦门百仕洁环保科技有限公司 | Two-stage treatment method for heavy metal wastewater |
CN101717134B (en) * | 2009-12-04 | 2011-05-18 | 浙江师范大学 | Method for treating zinc-containing electroplating wastewater and recovering zinc by electrolysis |
CN102115282A (en) * | 2011-01-20 | 2011-07-06 | 中南民族大学 | Method for recycling copper smelting wastewater |
CN102284464A (en) * | 2010-12-28 | 2011-12-21 | 陈启松 | Harmless disposal method for stainless steel acid washing residues |
CN102452743A (en) * | 2010-10-25 | 2012-05-16 | 上海丰信环保科技有限公司 | Method for treating complex-containing nickel plating wastewater |
CN102557299A (en) * | 2012-01-11 | 2012-07-11 | 浙江海拓环境技术有限公司 | Recovery method of copper-nickel heavy metals in electroplated mixed-flow waste water |
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CN105565553A (en) * | 2015-12-22 | 2016-05-11 | 解艳超 | Zero-emission purifying and recycling system of cyanide-containing heavy metal wastewater |
CN107758903A (en) * | 2016-08-16 | 2018-03-06 | 江苏恩飞特环保工程有限公司 | A kind of processing method of chemical nickel plating waste solution |
CN108911229A (en) * | 2018-06-02 | 2018-11-30 | 南通盛州电子科技有限公司 | A kind of cupro-nickel electroplating effluent recovery of circulatory system and recovery method |
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CN101717134B (en) * | 2009-12-04 | 2011-05-18 | 浙江师范大学 | Method for treating zinc-containing electroplating wastewater and recovering zinc by electrolysis |
CN101817608A (en) * | 2010-04-02 | 2010-09-01 | 厦门百仕洁环保科技有限公司 | Two-stage treatment method for heavy metal wastewater |
CN102452743A (en) * | 2010-10-25 | 2012-05-16 | 上海丰信环保科技有限公司 | Method for treating complex-containing nickel plating wastewater |
CN102284464A (en) * | 2010-12-28 | 2011-12-21 | 陈启松 | Harmless disposal method for stainless steel acid washing residues |
CN102115282A (en) * | 2011-01-20 | 2011-07-06 | 中南民族大学 | Method for recycling copper smelting wastewater |
CN102557299B (en) * | 2012-01-11 | 2013-06-12 | 浙江海拓环境技术有限公司 | Recovery method of copper-nickel heavy metals in electroplated mixed-flow waste water |
CN102557299A (en) * | 2012-01-11 | 2012-07-11 | 浙江海拓环境技术有限公司 | Recovery method of copper-nickel heavy metals in electroplated mixed-flow waste water |
CN103011360A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Treatment method for industrial wastewater generated by copper wet-process smelting |
CN105565553A (en) * | 2015-12-22 | 2016-05-11 | 解艳超 | Zero-emission purifying and recycling system of cyanide-containing heavy metal wastewater |
CN107758903A (en) * | 2016-08-16 | 2018-03-06 | 江苏恩飞特环保工程有限公司 | A kind of processing method of chemical nickel plating waste solution |
CN108911229A (en) * | 2018-06-02 | 2018-11-30 | 南通盛州电子科技有限公司 | A kind of cupro-nickel electroplating effluent recovery of circulatory system and recovery method |
CN111170530A (en) * | 2018-11-13 | 2020-05-19 | 上海朗蔚环保科技有限公司 | Electroplating wastewater treatment system |
CN111606519A (en) * | 2020-06-09 | 2020-09-01 | 闫娟 | Advanced treatment method for electroplating wastewater |
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