CN104710051A - Processing technology for electroplating effluent of heavy metal - Google Patents
Processing technology for electroplating effluent of heavy metal Download PDFInfo
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- CN104710051A CN104710051A CN201510078237.6A CN201510078237A CN104710051A CN 104710051 A CN104710051 A CN 104710051A CN 201510078237 A CN201510078237 A CN 201510078237A CN 104710051 A CN104710051 A CN 104710051A
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Abstract
The invention discloses a processing technology for electroplating effluent of heavy metal. The processing technology comprises an iron-carbon micro electrolysis processing procedure and a sludge circulating and processing procedure, wherein the sludge circulating and processing procedure comprises an agitating tank, a sedimentation basin and an alkali tank which are successively and mutually connected to form sludge circulation; mixed effluent enters a micro electrolysis packed tower to be in contact with spherical iron-carbon composite materials for carrying out micro electrolytic reaction, and an iron-carbon micro electrolysis preprocessing procedure is completed; then, the sludge circulating and processing procedure is performed. The technology disclosed by the invention is simple, the electroplated effluent is not needed to be processed in a stream splitting manner, and all the electroplating effluent needs to be mixed into a stream to be processed. In the technology, except that the pH value is adjusted through acid and alkali, other medicaments are not needed to be added, so that the quantity of the produced sludge is substantially reduced by 50% or above as compared with that of a conventional precipitation method.
Description
Technical field
The present invention relates to heavy metal-containing electroplating effluent treatment process, belong to environment protection field of waste water treatment.
Background technology
Employ the poisonous and harmful chemical such as a large amount of strong acid, highly basic, complexing agent, CN, Cu, Cr, Cd, Ni, Zn in plating production process, often not only containing a heavy metal species in electroplating wastewater, mostly be two or more heavy metal ion.In addition, in order to improve the quality of plating piece, the electroplating additive kind used in Electroplating Production and quantity get more and more, composition also becomes increasingly complex, these additives contain the composition stronger with complex effect, as: tartrate, pyrophosphate salt, citric acid, ammonia and formaldehyde etc., discharge the waste water of a large amount of contaminate environment and harm humans health in electroplating process, Electroplating Operations is one of the current whole world three large contaminated industries.
Electroplating wastewater processing generally adopts traditional moderate water-cut stage.Usually electroplating wastewater is carried out share split process, i.e. chromate waste water, cyanide wastewater and acidic and alkaline waste water (copper nickel zinc waste water).Wherein, sexavalent chrome is under acid neutrality and alkaline condition, all do not produce precipitation, therefore need to be first under the acidic conditions of 2 ~ 3 in pH value by chromate waste water, add reductive agent (Sodium Pyrosulfite) and be reduced to trivalent chromium, adding alkali adjust ph is subsequently the removing of hydroxide three chromium precipitation, and chromate waste water is processed.Cyanide wastewater is the waste water that Electroplating Production toxic is larger, because cyanogen root has good complexing, surfactivity, activation, is thus widely used in Electroplating Production.The waste water that cyanide wastewater comprises cyanide electroplating, alkaline cyanide gold-plated, neutral and acid plating gold and silver, gunmetal etc. produce containing cyanogen electroplating work procedure, its principal pollutant are prussiate, complex state heavy metal ion etc.Cyanogen root and cupric ion or nickel ion can form stable complex compound, make to become difficulty by alkaline chemical precipitation cupric ion or nickel ion, affect the qualified discharge of copper, nickel.Cyanide wastewater generally adopts alkaline chlorination process process, namely in the basic conditions, adds the oxygenant such as clorox or chlorinated lime and is removed by cyanide oxidation.Become comprehensive wastewater after the waste water such as copper, nickel, zinc converge with chromate waste water and cyanide wastewater, by comprehensive wastewater by adjusted to ph, make the metal ion in comprehensive wastewater form oxyhydroxide and precipitate, thus reach removal heavy metal ions in wastewater.
The moderate water-cut stage that current electroplating wastewater processing factory extensively adopts has following shortcoming:
(1) because the optimal ph of different heavy metal formation oxyhydroxide is not quite similar, make, when processing containing various heavy waste water, to be difficult to take into account, to make mixture-metal after treatment, water quality is unstable, is difficult to qualified discharge.
(2) method of current share split process makes treatment process more complicated, and facility investment is comparatively large, adds that medicament kind is many and amount is large, the also large and complicated component of the sludge quantity produced.
(3) this method is difficult to solve current electroplating industry ubiquitous mixing problem, if namely have the waste water containing complex compound to be mixed in comprehensive wastewater, cupric ion or nickel ion (complex copper or complexing nickel) can be made to be difficult to qualified discharge.
To sum up, need a kind of dosage badly little, add species few, and can by the art treatment of various heavy electroplating wastewater comprehensive treating process, meet the convenient and swift and effective processing demands of electroplating wastewater.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides a kind of without share split process, except adding soda acid adjust ph, do not add other any medicaments, significantly reduce sludge quantity, significantly reduce the heavy metal-containing electroplating effluent treatment process of working cost.
Technical scheme: for achieving the above object, technical scheme of the present invention is as follows:
A kind of heavy metal-containing electroplating effluent treatment process, comprises the following steps:
1) wastewater collection: in electroplated heavy metals wastewater collection to collecting tank after mixing, forms composite waste, the heavy metal concentration≤350mg/L in described composite waste;
2) iron-carbon micro-electrolysis pretreatment process: described composite waste enters in described micro-electrolysis stuffing tower, the bottom of described micro-electrolysis stuffing tower is provided with air intlet, pass into air aeration at the bottom of tower and play the effect of stirring, aeration rate is 5L/min, described composite waste contacts with the spherical iron carbon composite in described micro-electrolysis stuffing tower and carries out micro-electrolysis reaction, " contact break " reaction is carried out to the organic complex in composite waste, and the heavy metal ion in composite waste is reduced, meanwhile, iron carbon composite dissociation generates Fe
2+;
3) sludge circulation treatment operation: the composite waste after the process of iron-carbon micro-electrolysis pretreatment process enters in steel basin, and from the alkali lye mix and blend in alkali groove, described alkali lye is for containing alkali mud, and form mixing mud, reaction generates patina;
Mixing mud in described steel basin enters in described settling tank, and after carrying out solid-liquid separation, supernatant liquor qualified discharge, the backflow residual sludge reflux of bottom, to described alkali groove, adds alkali and regulates pH, then enter reuse in steel basin.
Further, in the present invention, step 1) in, the pH value of described composite waste is less than 5.
Further, in the present invention, step 2) in, after iron carbon composite micro-electrolysis reaction, the redox potential entering the described composite waste of sludge circulation treatment operation is 100mV ~ 400mV.
Further, in the present invention, step 3) in, in the backflow residual sludge reflux bottom described settling tank to described alkali groove, add alkali and regulate pH to 8.5 ~ 13.
Further, in the present invention, step 3) in, when in described steel basin, the solids concn of mixing mud is 500mg/L ~ 4000mg/L, the excess sludge bottom described settling tank is discharged.
Further, in the present invention, the reflux ratio of described backflow excess sludge is 20% ~ 50%.
Beneficial effect: compare with conventional electroplating waste processing process, the present invention has following outstanding advantage and unusual effect:
1) technique is simple, and electroplating wastewater, without the need to share split process, only need blend together one and process.
2) this technique is except with except acid-alkali accommodation pH value, without the need to adding other medicaments, makes the sludge quantity produced significantly reduce more than 50% relative to conventional precipitation method.
3) by iron-carbon micro-electrolysis operation, the effect of " contact break " can be played, destroy the complex compound such as prussiate, tartrate, EDTA, pyrophosphate salt, citric acid, ammonia common in electroplating wastewater.Be conducive to the qualified discharge of cupric ion and nickel ion.
4) mud in sludge circulation treatment operation contains a large amount of patinas, has extremely strong reductibility, reducible sexavalent chrome, by recycling of reductibility mud, and can the next Fe to iron-carbon micro-electrolysis operation of efficiency utilization
2+.
Accompanying drawing explanation
Accompanying drawing 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Be a kind of heavy metal-containing electroplating effluent treatment process as shown in Figure 1, the device that this technique relates to comprises iron-carbon micro-electrolysis treatment unit and sludge circulation treatment device successively; Iron-carbon micro-electrolysis treatment unit comprises micro-electrolysis stuffing tower 1, and be filled with a large amount of spherical iron carbon composite in micro-electrolysis stuffing tower 1, the bottom of micro-electrolysis stuffing tower 1 is provided with air intlet; Sludge circulation treatment device comprises steel basin 2, settling tank 3 and alkali groove 4, and steel basin 2, settling tank 3 and alkali groove 4 are interconnected successively, forms sludge circulation; Micro-electrolysis stuffing tower 1 is connected with steel basin 2.
Based on described heavy metal-containing electroplating effluent treatment process, comprise the following steps:
1) wastewater collection: in the electroplated heavy metals wastewater collections to collecting tank such as the chromate waste water that Electroplate Factory produces, cyanide wastewater and acidic and alkaline waste water (copper nickel zinc waste water) after mixing, form composite waste, heavy metal concentration≤the 350mg/L such as chromium, nickel, copper in composite waste, the pH value of composite waste controls be less than 5.Same collecting tank collected by multiple electroplating wastewater, need not share split process again.
2) iron-carbon micro-electrolysis pretreatment process: described composite waste enters in described micro-electrolysis stuffing tower 1, pass into air aeration at the bottom of tower and play the effect of stirring, aeration rate is 5L/min, composite waste contacts with spherical iron carbon composite and carries out micro-electrolysis reaction, " contact break " reaction is carried out to the organic complex in composite waste, and the heavy metal ion in composite waste is reduced, meanwhile, iron carbon composite dissociation generates Fe
2+; After iron carbon composite micro-electrolysis reaction, the redox potential entering the composite waste of sludge circulation treatment operation is 100mV ~ 400mV.Wherein, spherical iron carbon composite is purchased from Jiangsu ATK Environmental Engineering Design & Research Institute Co., Ltd..
This pretreatment process mainly contains the effect of three aspects in the method: (a) carries out " contact break " reaction to the organic complex in composite waste, is conducive to adding alkali subsequently and makes heavy metal ion generate precipitate and separate; B heavy metal ion in composite waste can be reduced by () iron carbon composite, as sexavalent chrome the most common can be reduced to trivalent chromium, adding alkali subsequently can generate precipitate and separate by trivalent chromium; C () iron carbon composite dissociation can go out a large amount of Fe
2+, rear section Fe is contacted with air
2+fe can be oxidized to
3+, the iron ion that dissociation goes out also can be used as the source of iron of next process.
3) sludge circulation treatment operation: the composite waste after the process of iron-carbon micro-electrolysis pretreatment process enters in steel basin 2, with from the alkali lye mix and blend in alkali groove 4, alkali lye is for containing alkali mud, form mixing mud, reaction generates a kind of based on Fe (II) and Fe (III) cationic layered hydroxide, i.e. patina;
If wherein part Fe (II) is oxidized, hydroxide layer will be changed into positively charged by electric neutrality, negatively charged ion can insert immediately, it is made to become electric neutrality, therefore patina has extremely strong sorptive power, can reduce anion concentration, as chromate, nitrate radical, selenate radical etc.; Patina, by Adsorption of Heavy Metal Ions, is changed into precipitation removing; In addition, due to the absorption of ferrous ion in patina, OH
-supply electric charge, makes ferrous ion have stronger reductibility, can be directly zeroth order by reducing metal ions.
Mixing mud in steel basin 2 enters in settling tank 3, after carrying out solid-liquid separation, and supernatant liquor qualified discharge, the backflow residual sludge reflux of bottom, in alkali groove 4, adds alkali and regulates pH to 8.5 ~ 13, then enter reuse in steel basin 2, so move in circles, can continuously process electroplated heavy metals waste water, recycle mud, extend mud mud age, this technique is except with except acid-alkali accommodation pH value, without the need to adding other medicaments, sludge quantity significantly reduces, and running cost significantly reduces.Steel basin 2 and alkali groove 4 are configured with agitator respectively, are conveniently uniformly mixed.
When in steel basin 2, the solids concn of mixing mud is 500mg/L ~ 4000mg/L, the excess sludge bottom settling tank 3 is discharged, and makes filter cake after filtration, pending.Wherein, the reflux ratio of backflow excess sludge is 20%-50%.
In the treatment process of indegradable industrial effluent, Fe-C Micro Electrolysis Method is a kind of effective method, the action principle of the method is: iron filings and carbon granule are immersed in slant acidity waste water, utilize the galvanic interaction mechanism in electrochemistry, the metal Fe (anode) of low potential and the carbon material (negative electrode) of noble potential form countless microbattery in water; Under acid aerobic condition, redox reaction occurs, can make the effects such as organism generation chain rupture and open loop, its reaction process is as follows:
Anode: Fe-2e → Fe
2+
Negative electrode: 2H
++ 2e → 2 [H] → H
2
O
2+4H
++4e→H
2O
O
2+H
2O+4e→4OH
-
Patina is based on Fe
2+and Fe
3+hydroxide mixture, the general formula of patina can be expressed as:
Wherein X=0.9 ~ 4.2, A: negatively charged ion (SO
4 2-, Cl
-, CO
3 2-), y: middle water molecule number (2 ~ 4);
If the negatively charged ion of Intercalation reaction is SO
4 2-, then its chemical formula can be written as:
Patina is between Fe (OH)
2with Fe
3o
4between a kind of metastable condition, it not only has extremely strong reducing power, but also has unique laminate structure, and interlayer spacings can also embed corresponding negatively charged ion.By the reducing power of patina, can be used for U (VI), NO
3 -, Cr (VI), Se (VI) plasma reduces, in addition, and can also to CCl
4carry out dechlorination process; The unique laminate structure had by patina and higher specific surface area, can adsorb a large amount of heavy metal ion.
Embodiment 1
The indices analytical results of each stock waste water water outlet after mixed composite waste (former water) with present invention process process of certain Electroplate Factory discharge is in table 1.
Analysis Results of Water Quality before and after the process of table 1. present invention process
As shown in Figure 1, the present invention includes the treatment process of two series connection: iron-carbon micro-electrolysis pretreatment process and sludge circulation treatment operation.Iron-carbon micro-electrolysis pretreatment process mainly comprises the micro-electrolysis stuffing tower 1 that is filled a large amount of spherical iron carbon composite, and the bottom of micro-electrolysis stuffing tower 1 passes into air and carries out aeration, and aeration rate is 5L/min.Sludge circulation treatment operation forms primarily of a steel basin 2, settling tank 3 and an alkali groove 4.
The various waste water of Electroplate Factory's discharge are after mixing, pH value is that 1.12 composite wastes introduce micro-electrolysis stuffing tower 1 by pump, heavy metal concentration≤the 350mg/L such as chromium, nickel, copper in composite waste, pass into air aeration at the bottom of tower and play the effect of stirring, react to redox potential (Ag/AgCl electrode) lower than 400mV time, waste water can be introduced in sludge circulation treatment operation.
Sludge circulation treatment operation is entered by the heavy metal wastewater thereby after iron-carbon micro-electrolysis process, the precipitation of hydroxide generating composition metal in steel basin 2 is entered together with the alkali lye (mass concentration 20%) from alkali groove 4, control the pH value 8.5 ~ 8.8 in steel basin 2, mixing mud in steel basin 2 is after settling tank 3 solid-liquid separation, supernatant liquor meets plating pollutant emission standard (GB 21900-2008) and carries out draining, the backflow excess sludge of bottom then reenters alkali groove 4, add alkali by about the pH regulator to 9.0 of mixing mud, again enter steel basin 2 and carry out contact reacts with the heavy metal wastewater thereby after the process of iron-carbon micro-electrolysis operation.Reaction terminate after, the mixing mud in steel basin 2 after settling tank 3 solid-liquid separation, supernatant liquor qualified discharge, after bottom backflow excess sludge then adds alkali by alkali groove 4 again, enter steel basin 2 reuse, so move in circles, continuously can process heavy metal wastewater thereby.When the solids concn of mixing mud in steel basin 2 is more than 3500mg/L, in follow-up settling tank 3, needs the precipitation taking part away namely to discharge excess sludge, make filter cake after filtration, pending.Wherein, the reflux ratio of backflow excess sludge is 50%.
Embodiment 2
Be a kind of heavy metal-containing electroplating effluent treatment process as shown in Figure 1, the device that this technique relates to comprises iron-carbon micro-electrolysis treatment unit and sludge circulation treatment device successively; Iron-carbon micro-electrolysis treatment unit comprises micro-electrolysis stuffing tower 1, is filled with a large amount of spherical iron carbon composite in micro-electrolysis stuffing tower 1, and the bottom of micro-electrolysis stuffing tower 1 passes into air and carries out aeration; Sludge circulation treatment device comprises steel basin 2, settling tank 3 and alkali groove 4, and steel basin 2, settling tank 3 and alkali groove 4 are interconnected successively, forms sludge circulation; Micro-electrolysis stuffing tower 1 is connected with steel basin 2.
A kind of heavy metal-containing electroplating effluent treatment process, comprises the following steps:
1) wastewater collection: in the electroplated heavy metals wastewater collections to collecting tank such as the chromate waste water that Electroplate Factory produces, cyanide wastewater and acidic and alkaline waste water (copper nickel zinc waste water) after mixing, form composite waste, heavy metal concentration≤the 350mg/L such as chromium, nickel, copper in composite waste, the pH value of composite waste controls be less than 4.Same collecting tank collected by multiple electroplating wastewater, need not share split process again.
2) iron-carbon micro-electrolysis pretreatment process: composite waste enters in micro-electrolysis stuffing tower 1, the bottom of packing tower passes into air and carries out aeration and play stirring action, aeration rate is 5L/min, composite waste contacts with spherical iron carbon composite and carries out micro-electrolysis reaction, " contact break " reaction is carried out to the organic complex in composite waste, and the heavy metal ion in composite waste is reduced, meanwhile, iron carbon composite dissociation generates Fe
2+; After iron carbon composite micro-electrolysis reaction, the redox potential entering the composite waste of sludge circulation treatment operation is 100mV ~ 400mV.
3) sludge circulation treatment operation: the composite waste after the process of iron-carbon micro-electrolysis pretreatment process enters in steel basin 2, and from the alkali lye mix and blend in alkali groove 4, alkali lye is for containing alkali mud, and form mixing mud, reaction generates patina;
As the mixing mud in steel basin 2 enters in settling tank 3, after carrying out solid-liquid separation, supernatant liquor qualified discharge, the backflow residual sludge reflux of bottom, in alkali groove 4, adds alkali and regulates pH to 12, then enter reuse in steel basin 2, so move in circles, can continuously process electroplated heavy metals waste water, recycle mud, extend mud mud age, this technique is except with except acid-alkali accommodation pH value, without the need to adding other medicaments, sludge quantity significantly reduces, and running cost significantly reduces.Steel basin 2 and alkali groove 4 are configured with agitator respectively, are conveniently uniformly mixed.
When in steel basin 2, the solids concn of mixing mud reaches 2000mg/L, the excess sludge bottom settling tank 3 is discharged, and makes filter cake after filtration, pending.Wherein, the reflux ratio of described backflow excess sludge is 35%.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a heavy metal-containing electroplating effluent treatment process, is characterized in that: comprise the following steps:
1) wastewater collection: in electroplated heavy metals wastewater collection to collecting tank after mixing, forms composite waste, the heavy metal concentration≤350mg/L in described composite waste;
2) iron-carbon micro-electrolysis pretreatment process: described composite waste enters in described micro-electrolysis stuffing tower (1), the bottom of described micro-electrolysis stuffing tower (1) is provided with air intlet, pass into air aeration at the bottom of tower and play the effect of stirring, aeration rate is 5L/min, described composite waste contacts with the spherical iron carbon composite in described micro-electrolysis stuffing tower (1) and carries out micro-electrolysis reaction, contact break reaction is carried out to the organic complex in composite waste, and the heavy metal ion in composite waste is reduced, meanwhile, iron carbon composite dissociation generates Fe
2+;
3) sludge circulation treatment operation: the composite waste after the process of iron-carbon micro-electrolysis pretreatment process enters in steel basin (2), with from the alkali lye mix and blend in alkali groove (4), described alkali lye, for containing alkali mud, forms mixing mud, and reaction generates patina;
Mixing mud in described steel basin (2) enters in settling tank (3), after carrying out solid-liquid separation, supernatant liquor qualified discharge, the backflow residual sludge reflux of bottom is to described alkali groove (4), add alkali and regulate pH, then enter reuse in steel basin (2).
2. heavy metal-containing electroplating effluent treatment process according to claim 1, is characterized in that: step 1) in, the pH value of described composite waste is less than 5.
3. heavy metal-containing electroplating effluent treatment process according to claim 1, it is characterized in that: step 2) in, after spherical iron carbon composite micro-electrolysis reaction, the redox potential entering the described composite waste of sludge circulation treatment operation is 100mV ~ 400mV.
4. heavy metal-containing electroplating effluent treatment process according to claim 1, is characterized in that: step 3) in, the backflow residual sludge reflux of described settling tank (3) bottom, to described alkali groove (4), adds alkali and regulates pH to 8.5 ~ 13.
5. heavy metal-containing electroplating effluent treatment process according to claim 1, it is characterized in that: step 3) in, when in described steel basin (2), the solids concn of mixing mud is 500mg/L ~ 4000mg/L, the excess sludge of described settling tank (3) bottom is discharged.
6. heavy metal-containing electroplating effluent treatment process according to claim 5, is characterized in that: the reflux ratio of described backflow excess sludge is 20% ~ 50%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105948336A (en) * | 2016-07-04 | 2016-09-21 | 北方工程设计研究院有限公司 | Treatment process of electroplating wastewater containing cyanogen and chromium |
| CN108218059A (en) * | 2018-03-13 | 2018-06-29 | 江苏艾特克环境工程有限公司 | One kind is used for electroplating waste processing equipment |
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| CN102101733A (en) * | 2011-01-12 | 2011-06-22 | 中国科学院生态环境研究中心 | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology |
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| CN1926071A (en) * | 2004-04-26 | 2007-03-07 | 三菱麻铁里亚尔株式会社 | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
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| CN105948336A (en) * | 2016-07-04 | 2016-09-21 | 北方工程设计研究院有限公司 | Treatment process of electroplating wastewater containing cyanogen and chromium |
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Application publication date: 20150617 |