CN105174562A - Method for electric flocculation treatment of heavy metal wastewater - Google Patents
Method for electric flocculation treatment of heavy metal wastewater Download PDFInfo
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Abstract
The invention provides a method for electric flocculation treatment of heavy metal wastewater. The method comprises the following steps: firstly, performing electrocoagulation, wherein metal ions (such as iron ions or zinc ions) generated by electrolysis are combined with a sulfide to form a coagulation source, the generated sulfide and heavy metal ions are subjected to displacement reaction to deposit other heavy metal ions at the same time, and moreover, hydrolysis can generate a large amount of multi-hydroxyl compounds which are subjected to enrichment effects of reaction, adsorption and chelating with low-concentration heavy metal ions; secondly, adjusting the pH value, and adding the sulfides which can achieve a synergistic action with electric flocculation to remove heavy metals; and finally, aerating for a period of time, and filtering to drain off water. The method provided by the invention can ensure that the content of the heavy metals in effluent is lower and can meet discharge standards; and meanwhile, the method is high in treatment efficiency and is pollution-free, and the used equipment is simple, occupies a small floor area and is convenient to operate.
Description
Technical field
The invention belongs to sewage treatment area, relate to a kind of method of electric flocculation treatment heavy metal wastewater thereby, particularly relate to a kind of method of electric flocculation treatment low concentration heavy metal water.
Background technology
Heavy metal wastewater thereby refers to the trade effluent containing heavy metal ion such as chromium, cadmium, nickel and lead.Mechanical industry, mine smelting industry and part chemical enterprise can produce heavy metal wastewater thereby in process of production, the concentration <50mg/L of this kind of waste water heavy metal ion after various preliminary treatment, but the heavy metal wastewater thereby of this lower concentration reaches discharging standards not yet, if directly discharge can cause water pollution, and by soil, water and air, particularly by food chain, directly serious harm is caused to human health.Therefore, one of problem demanding prompt solution in environment protection has been become to the purifying treatment containing low concentration heavy metal water.
The treatment process of current heavy metal wastewater thereby mainly contains chemical precipitation, chemical flocculation, electrolytic reduction, membrane separation process and chemisorption etc., and various treatment process all has its respective relative merits.Planting as first three subject matter that treatment process exists is that the serious and effective processing rate of secondary pollution is low etc., and the problem such as membrane separation process exists that film easily pollutes, cost is high and membrane lifetime is short, chemisorption exists that adsorption rate is low, sorbent material is expensive and the difficulties such as difficult life.Any single treatment process all can not meet the requirement of present heavy metal discharge of wastewater, therefore adopts technique coupling technique to become the important development direction of heavy metal waste water treatment process.
In recent years in heavy metal containing wastewater treatment field, the application of electrochemistry flocculation technique is more and more extensive, this contains the multiple reactions such as electrolytic reduction, electrofloatation and adsorption-flocculation due to electrocoagulation process and respectively reacts synergy, thus can fast and process heavy metal wastewater thereby efficiently, simple to operate, or seldom can not produce secondary pollution etc.; But single electrocoagulation technology is bad to low-concentration heavy metal treatment effect, and current consumption is large, costly and treatment effect is not obvious.Sulfide precipitation removal heavy metal effect is fine, and heavy metal concentration can be dropped to below 0.05mg/L, but the easy contaminate environment of sulfide, the less not free settling of metal sulfide grain of generation.
Patent CN104261526A discloses a kind for the treatment of process of heavy metal wastewater thereby, and this treatment process adopts the method heavy metal adding separately sulfide to process, but sulfide excessive after do not process, be easy to contaminate environment.Patent CN103288185A discloses a kind of method utilizing outer circulation electric flocculation technique process heavy metal wastewater thereby, and after the electric flocculation treatment heavy metal of employing, in water outlet, heavy metal concentration is still 20 ~ 30mg/L separately, bad to low-concentration heavy metal treatment effect.Patent CN102001779A discloses a kind of electricity flocculation-active carbon adsorption that utilizes to process the method for heavy metal-containing electroplating effluent, in order to adsorb the low-concentration heavy metal after electricity flocculation, the process employs follow-up charcoal absorption, after absorption, gac needs regeneration, make this technological operation comparatively complicated and level of automation is low, gac link improves a ton cost of water treatment to a certain extent simultaneously.CN103193343A discloses a kind of method utilizing electricity flocculation-ion exchange method to carry out advanced treatment chromate waste water, after electricity flocculation, the heavy metal of lower concentration adopts the method for ion-exchange to reduce its concentration further, although heavy metal reaches emission standard, but ion exchange resin easily pollutes, need desorption and regeneration, add technical process, complicated operation.
In sum, in order to carry out low cost, technique to low concentration heavy metal water simply and process efficiently, in order to promote the application of electrochemistry flocculation technique in heavy metal wastewater thereby industry, be necessary to improve traditional electrochemistry flocculation technique again, to reduce process energy consumption and cost.
Summary of the invention
For the secondary pollution existed in low concentration heavy metal water in prior art (concentration of heavy metal ion is 0.1 ~ 20mg/L) treatment process, cost is high, technical process is loaded down with trivial details, complicated operation, independent electric flocculation technique treatment effect are undesirable and cause out the problems such as water pollutions owing to adding other materials in treating processes, the invention provides a kind of method of electric flocculation treatment low concentration heavy metal water.First the method carries out electrocoagulation step, and the metal ion (as iron ion or zine ion) that electrolysis produces is combined with sulfide and forms cohesion source; Meanwhile, sulfide and the heavy metal ion generation replacement(metathesis)reaction of generation precipitate other heavy metal ion, and the heavy metal ion that hydrolysis can produce a large amount of polyols and lower concentration reacts, adsorbs and the inrichment such as chelating; Then adjust ph, then add sulfide, the sulfide added also can to flocculate the removal heavy metal that acts synergistically with electricity; Last period of aeration, filters draining.Present method can make water outlet heavy metal content lower, meets qualified discharge standard; Present method processing efficiency is high, pollution-free simultaneously, and the equipment of use is simple, and floor space is little and easy to operate.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of method of electric flocculation treatment heavy metal wastewater thereby, said method comprising the steps of: added by heavy metal wastewater thereby in electric flocculation reactor, carry out electric flocculation reaction 10 ~ 60min; Regulate pH again, add sulfide, then carry out Air Exposure, filter water outlet.
Wherein, the electric flocculation reaction time can be 10min, 14min, 18min, 22min, 26min, 30min, 34min, 40min, 45min, 50min, 55min or 60min etc.
With ferroelectric very example, in electric flocculation process, electrolytic ferrous ion is combined with sulfide and forms cohesion source, and meanwhile, Iron sulfuret and the heavy metal ion generation replacement(metathesis)reaction of generation precipitate other heavy metal ion; Further, in electrochemical process, high reactivity adsorption group can be produced, this group can adsorb, the impurity such as colloidal solid, suspended substance and heavy metal ion in chelating water, form larger batting-unit structure and separate out from water.
Adopt zinc electrode, or adopt the combination of iron electrode and aluminium electrode, or when adopting the combination of zinc electrode and aluminium electrode, its electric flocculation process principle with adopt iron electrode similar, repeat no more herein.
In the present invention, the pH regulating heavy metal wastewater thereby is 7.0 ~ 11.0, such as 7.0,8.0,9.0,10.0 or 11.0 etc., be preferably 7.0 ~ 10.0.
In the present invention, described sulfide is the combination of any one or at least two kinds in sodium sulphite, potassium sulphide, Sodium sulfhydrate, calcium polysulfide, zinc sulphide or Iron sulfuret, described combination typical case but limiting examples have: the combination of sodium sulphite and potassium sulphide, the combination of potassium sulphide and Sodium sulfhydrate, the combination of Sodium sulfhydrate and calcium polysulfide, the combination of sodium sulphite, potassium sulphide and Sodium sulfhydrate, the combination of sodium sulphite, potassium sulphide, Sodium sulfhydrate and calcium polysulfide, the combination etc. of Sodium sulfhydrate, calcium polysulfide, zinc sulphide and Iron sulfuret.
In the present invention, in electric flocculation treatment process, adopt direct supply or action of low-voltage pulse Energy control electrode.
In the present invention, the voltage of direct supply or action of low-voltage pulse Energy control often pair of electrode is adopted to be 0 ~ 50V and not comprise 0V in electricity flocculation treatment process, such as 1V, 2V, 6V, 10V, 14V, 18V, 20V, 22V, 26V, 30V, 34V, 40V, 45V or 50V etc., be preferably 0 ~ 30V and do not comprise 0V.
In the present invention, the current density in electric flocculation treatment process on battery lead plate is 5 ~ 20mA/cm
2, 5mA/cm
2, 9mA/cm
2, 13mA/cm
2, 15mA/cm
2, 17mA/cm
2or 20mA/cm
2deng, be preferably 6 ~ 15mA/cm
2.
Preferably, in electric flocculation treatment process, interelectrode distance is 20 ~ 60mm, such as 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm, 55mm or 60mm etc., is preferably 20 ~ 40mm.
In the present invention, in electric flocculation treatment process, the electric flocculation reaction time is 15 ~ 60min.
Preferably, the time of described Air Exposure is 3 ~ 20min, such as 3min, 8min, 10min, 13min, 15min, 17min or 20min etc.Adopt the method for aeration by excessive S
2-and Fe
2+oxidation, not only can prevent sulphide staining, the Fe of generation
3+can also and S
2-there is redox reaction and remove excessive sulphur, simultaneously Fe
3+generate Fe (OH)
3, it has flocculating effect well, contributes to the pollutent removed further in water.
In the present invention, in electric flocculation treatment process, electrode is iron electrode and/or zinc electrode, and namely in electric flocculation treatment process, electrode all adopts iron electrode or electrode all to adopt zinc electrode, or electrode adopts the combination of iron electrode and zinc electrode.
Preferably, in electric flocculation treatment process, electrode also can be the combination of iron electrode and aluminium electrode.
Preferably, in electric flocculation treatment process, electrode also can be the combination of zinc electrode and aluminium electrode.
In the present invention, in described heavy metal wastewater thereby, the concentration of heavy metal ion is 0.1 ~ 20mg/L, such as 0.1mg/L, 1mg/L, 3mg/L, 5mg/L, 7mg/L, 10mg/L, 13mg/L, 15mg/L, 17mg/L or 20mg/L etc.
Wherein, described heavy metal refer to proportion be greater than 5 metal (density is greater than 4.5g/cm in general
3metal).
Preferably, described sulfide is (1.5 ~ 5) by the mol ratio of sulfonium ion and divalence heavy metal cation: 1 adds, such as 1.5:1,2:1,2.5:1,3:1,3.5:1,4:1,4.5:1 or 5:1 etc., is preferably 3:1.
In the present invention, filtration medium in described filtration is the combination of any one or at least two kinds in hard coal, quartz sand, gac, coke or porous ceramics, described combination typical case but limiting examples have: the combination of hard coal and quartz sand, the combination of quartz sand and gac, the combination of gac and coke, the combination of coke and porous ceramics, the combination of hard coal, quartz sand and gac, the combination of quartz sand, gac, coke and porous ceramics, the combination etc. of hard coal, quartz sand, gac, coke and porous ceramics.
Now with ferroelectric very example, mechanism of the present invention is described:
For Fe anode, the Fe that electrolysis produces
2+with S
2-reaction generates molecule FeS, and then heavy metal ion is (with M
2+example) there is with FeS the heavy metal sulfide (MS) that replacement(metathesis)reaction generates more indissoluble, with this fixing heavy metal ion, and S
2-also can directly and M
2+reaction generates heavy metal sulfide (MS, solubility product is very little, can generate rapidly) hard to tolerate, precipitates drive new particulate matter precipitation with the FeS generated; Fe simultaneously
2+can oxidized generation Fe
3+, Fe
3+rapidly with hydrated ion Fe (H in water
2o)
6 3+form exist, subsequently very soon hydrolysis lose H
+, form a series of mononuclear complex, as Fe (H
2o)
5oH
2+, Fe (H
2o)
4(OH)
2+with Fe (H
2o)
3(OH)
3deng.
Because montmorillonite increases, remain a large amount of lone-pair electron, hydroxyl coordination ability unsaturation, therefore montmorillonite can be polymerized to hydroxyl bridge crosslinking structure gradually with another iron ion, form two hydroxyl bond bridges, thus slowly aggregate into the multinuclear polymer network polymer [Fe of rich surface hydroxyl by the complex compound of monokaryon iron
m(H
2o)
x(OH)
n]
(3m-n), and finally change into unbodied [Fe (OH)
3]
nflocculation agent.
Experiment proves, has more than tens kinds of unit price iron core negatively charged ion and multiple multivalent iron core negatively charged ion.These hydroxo complexes can react with heavy metal, adsorb and the effect such as cohesion, thus enrichment is carried out to the heavy metal in waste water, according to negative positive and negative positive form constantly in conjunction with heavy metal, form the macromole with colloidal structure, these colloids are coacervating large particle coagulation under the effect of the precipitation generated (as FeS and MS etc.), then can remove colloid and suspended particle completely by filtration, reach the object of complete removal heavy metal; Simultaneously, the swimming in the electric field of charged pollutent, its Partial charge is neutralized by electrode and impels its de-steady coagulation, realize good solid-liquid separation effect, and last aeration phase can remove the sulfide of excessive solubility completely, each concentration of heavy metal ion in its water outlet can be made to be down to below 0.05mg/L, and sulfide content, lower than 0.1mg/L, reaches discharging standards.
With ferroelectric very example, principal reaction formula involved in the present invention is as follows:
Anode: Fe (s)-2e
-=Fe
2+(aq)
Negative electrode: M
2+(metal ion)+2e
-=M
2H
2O+O
2+4e
-＝4OH
-
Enrichment, flocculation and precipitin reaction:
Fe
2++S
2-＝FeS
FeS+M
2+＝MS+Fe
2+
Fe
2++2H
2O＝Fe(OH)
2+2H
+
4Fe(OH)
2+O
2+2H
2O＝4Fe(OH)
3
mFe
3+(aq)+xH
2O+nOH
-→[Fe
m(H
2O)
x(OH)
n]
3m-n
[Fe
m(H
2o)
x(OH)
n]
3m-n+ yM
z+→ { [Fe
m(H
2o)
x(OH)
n]
3m-nm
y]
3m-n+yx(colloid)
2S
2-+O
2+2H
2O＝2S+4OH
-
S
2-+Fe
3+＝S+Fe
2+
Adopt zinc electrode, or adopt the combination of iron electrode and aluminium electrode, or when adopting the combination of zinc electrode and aluminium electrode, its reaction mechanism with adopt iron electrode similar, repeat no more herein.
Compared with prior art, the present invention has following beneficial effect:
(1) the electrochemistry flocculation in the present invention in electric flocculation reaction, air supporting and flocculation sediment and chemical precipitation technique all concentrate in a reactor and complete, and equipment is simple, saves fixed investment and floor space.
(2) what in the present invention, electrode pad adopted is iron zinc electrode plate, contributes to flocculation sediment, and what adopt is the voltage of periodic reverse, and two-plate can use simultaneously, can prevent electrode passivation.
(3) the present invention utilizes electric flocculation technique to operate in conjunction with aeration the heavy metal ion removed in heavy metal wastewater thereby again with the sulfide synergy added, the heavy metal wastewater thereby of heavy metal concentration very low (heavy metal concentration is 0.01 ~ 10mg/L) can be processed, processing efficiency is high, in water outlet, the concentration (concentration as nickel, lead, cadmium and cupric ion) of each heavy metal ion is all low to moderate 0.05mg/L, sulfide content, lower than 0.1mg/L, reaches discharging standards.
(4) electric flocculation technique and the sulfide synergy that adds in the present invention, not only can reduce current consumption but also can reduce the consumption of chemical agent, running cost is lower, and pollution-free.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
The present invention utilizes electric flocculation technique to operate in conjunction with aeration the heavy metal ion removed in heavy metal wastewater thereby again with the sulfide synergy added, and makes heavy metal ion content in water outlet lower, meets qualified discharge standard.
Embodiment 1:
Method of the present invention is adopted to process cupric heavy metal wastewater thereby, wherein Cu
2+concentration be 20mg/L.
First electric flocculation reaction 30min is carried out, then the pH of heavy metal wastewater thereby is regulated to be 7, be that 5:1 adds sodium sulphite by the mol ratio of sulfonium ion and divalence heavy metal cation, wherein, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode in electricity flocculation reaction is 30V, and the current density on battery lead plate is 10mA/cm
2, interelectrode distance is 20mm.Then carry out filtration after Air Exposure 4min and obtain water outlet.
After electricity flocculation reaction completes, measure the Cu in water outlet
2+concentration be 0.005mg/L, sulfide content, lower than 0.1mg/L, meets qualified discharge standard.
Embodiment 2:
Method of the present invention is adopted to process containing cadmium heavy metal wastewater thereby, wherein Cd
2+concentration be 10mg/L.
First electric flocculation reaction 30min is carried out, then the pH of heavy metal wastewater thereby is regulated to be 8, be that 4:1 adds potassium sulphide by the mol ratio of sulfonium ion and divalence heavy metal cation, wherein, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode in electricity flocculation reaction is 20V, and the current density on battery lead plate is 8mA/cm
2, interelectrode distance is 30mm.Then carry out filtration after Air Exposure 4min and obtain water outlet.
After electricity flocculation reaction completes, measure the Cd in water outlet
2+concentration be 0.015mg/L, sulfide content, lower than 0.1mg/L, meets qualified discharge standard.
Embodiment 3:
Method of the present invention is adopted to process nickeliferous heavy metal wastewater thereby, wherein Ni
2+concentration be 5mg/L.
First carrying out electric flocculation reaction 30min, then regulate the pH of heavy metal wastewater thereby to be 8, is that 3:1 adds Sodium sulfhydrate by the mol ratio of sulfonium ion and divalence heavy metal cation; Wherein, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode in electric flocculation reaction is 20V, and the current density on battery lead plate is 20mA/cm
2, interelectrode distance is 20mm.Then carry out filtration after Air Exposure 4min and obtain water outlet.
After electricity flocculation reaction completes, measure the Ni in water outlet
2+concentration be 0.02mg/L, sulfide content, lower than 0.1mg/L, meets qualified discharge standard.
Embodiment 4:
Method of the present invention is adopted to process leaded heavy metal wastewater thereby, wherein Pb
2+concentration be 1mg/L.
First electric flocculation reaction 40min is carried out, then the pH of heavy metal wastewater thereby is regulated to be 9, be the mixture that 2:1 adds sodium sulphite and potassium sulphide by the mol ratio of sulfonium ion and divalence heavy metal cation, wherein, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode in electricity flocculation reaction is 20V, and the current density on battery lead plate is 10mA/cm
2, interelectrode distance is 20mm.Then carry out filtration after Air Exposure 3min and obtain water outlet.
After electricity flocculation reaction completes, measure the Pb in water outlet
2+concentration be 0.003mg/L, sulfide content, lower than 0.1mg/L, meets qualified discharge standard.
Embodiment 5:
Method heavy metal waste water of the present invention is adopted to process, wherein Cu
2+, Cd
2+, Ni
2+and Pb
2+concentration be 5mg/L.
First carrying out electric flocculation reaction 60min, then regulate the pH of heavy metal wastewater thereby to be 8, is that 3:1 adds sodium sulphite by the mol ratio of sulfonium ion and divalence heavy metal cation; Wherein, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode in electric flocculation reaction is 20V, and the current density on battery lead plate is 5mA/cm
2, interelectrode distance is 20mm, then carries out filtration after Air Exposure 4min and obtains water outlet.
After electricity flocculation reaction completes, measure Cu in water outlet
2+, Cd
2+, Ni
2+and Pb
2+concentration be respectively 0.005mg/L, 0.01mg/L, 0.01mg/L and 0.004mg/L, sulfide content, lower than 0.1mg/L, meets qualified discharge standard.
Embodiment 6:
Method of the present invention is adopted to process cupric heavy metal wastewater thereby, wherein Cu
2+concentration be 0.1mg/L.
Except electric flocculation reaction 15min, then the pH of heavy metal wastewater thereby is regulated to be 10, be that 1.5:1 adds sodium sulphite by the mol ratio of sulfonium ion and divalence heavy metal cation, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode is 50V, and the current density on battery lead plate is 6mA/cm
2, interelectrode distance is 40mm, and outside Air Exposure 15min, other steps are all in the same manner as in Example 1.
After electricity flocculation reaction completes, measure the Cu in water outlet
2+concentration be 0.005mg/L, sulfide content, lower than 0.01mg/L, meets qualified discharge standard.
Embodiment 7:
Method of the present invention is adopted to process nickeliferous heavy metal wastewater thereby, wherein Ni
2+concentration be 10mg/L.
Except electric flocculation reaction 10min, then regulate the pH of heavy metal wastewater thereby to be 11, the voltage adopting direct supply or action of low-voltage pulse Energy control electrode to control often pair of electrode is 36V, and the current density on battery lead plate is 15mA/cm
2, interelectrode distance is outside 60mm, and outside Air Exposure 20min, other steps are all in the same manner as in Example 1.
After electricity flocculation reaction completes, measure the Ni in water outlet
2+concentration be 0.042mg/L, sulfide content, lower than 0.05mg/L, meets qualified discharge standard.
Comparative example 1:
Cupric heavy metal wastewater thereby is processed, wherein Cu
2+concentration be 20mg/L.
Except not adding except sulfide, other steps are all in the same manner as in Example 1, after electric flocculation reaction completes, measure the Cu in water
2+concentration is 2.5mg/L.
Comparative example 2:
Cupric heavy metal wastewater thereby is processed, wherein Cu
2+concentration be 20mg/L.
Except not carrying out except electric flocculation treatment, other steps are all in the same manner as in Example 1, after reaction terminates, measure the Cu in water
2+concentration is 0.15mg/L, sulfide concentration 0.50mg/L.
Comparative example 3:
Cupric heavy metal wastewater thereby is processed, wherein Cu
2+concentration be 20mg/L.
Except not carrying out except Air Exposure, other steps are all in the same manner as in Example 1, after reaction terminates, measure the Cu in water
2+concentration is 0.14mg/L, and sulfide concentration is 0.46mg/L.
Comparative example 4:
Electricity flocculation is only adopted to process cupric heavy metal wastewater thereby, wherein Cu
2+concentration be 20mg/L, in electric flocculation treatment process, each technical qualification are all in the same manner as in Example 1, after reaction terminates, measure the Cu in water
2+concentration is 2.3mg/L.
Comparative example 5:
Only add sulfide to process cupric heavy metal wastewater thereby, wherein Cu
2+concentration be 20mg/L, the consumption of sulfide is in the same manner as in Example 1, after reaction terminates, measures the Cu in water
2+concentration is 1.2mg/L, and sulfide concentration is 0.58mg/L.
The result of integrated embodiment 1-7 and comparative example 1-5 can be found out, the present invention utilizes electric flocculation technique to operate in conjunction with aeration the heavy metal ion removed in heavy metal wastewater thereby again with the sulfide synergy added, the heavy metal wastewater thereby of heavy metal concentration very low (heavy metal concentration is 0.01 ~ 10mg/L) can be processed, processing efficiency is high, in water outlet, the concentration (concentration as nickel, lead, cadmium and cupric ion) of each heavy metal ion is all low to moderate 0.05mg/L, sulfide content, lower than 0.1mg/L, reaches discharging standards; What in the present invention, electrode pad adopted is iron zinc electrode plate, contributes to flocculation sediment, and what adopt is the voltage of periodic reverse, and two-plate can use simultaneously, can prevent electrode passivation; Electrochemistry flocculation in the present invention in electric flocculation reaction, air supporting and flocculation sediment and chemical precipitation technique all concentrate in a reactor and complete, and equipment is simple, saves fixed investment and floor space; Meanwhile, electric flocculation technique and the sulfide synergy added, not only can reduce current consumption but also can reduce the consumption of chemical agent, running cost is lower, and pollution-free.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a method for electric flocculation treatment heavy metal wastewater thereby, is characterized in that, said method comprising the steps of: added by heavy metal wastewater thereby in electric flocculation reactor, carries out electric flocculation reaction 10 ~ 60min; Adjust ph again, adds sulfide, then carries out Air Exposure, filters water outlet.
2. method according to claim 1, is characterized in that, the pH regulating heavy metal wastewater thereby is 7.0 ~ 11.0, is preferably 7.0 ~ 10.0.
3. method according to claim 1 and 2, is characterized in that, described sulfide is the combination of any one or at least two kinds in sodium sulphite, potassium sulphide, Sodium sulfhydrate, calcium polysulfide, zinc sulphide or Iron sulfuret etc.
4. the method according to any one of claim 1-3, is characterized in that, adopts direct supply or action of low-voltage pulse Energy control electrode in electric flocculation treatment process.
5. the method according to any one of claim 1-4, is characterized in that, adopts the voltage of direct supply or action of low-voltage pulse Energy control often pair of electrode be 0 ~ 50V and do not comprise 0V in electric flocculation treatment process, is preferably 0 ~ 30V and does not comprise 0V.
6. the method according to any one of claim 1-5, is characterized in that, the current density in electric flocculation treatment process on battery lead plate is 5 ~ 20mA/cm
2, be preferably 6 ~ 15mA/cm
2;
Preferably, in electric flocculation treatment process, interelectrode distance is 20 ~ 60mm, is preferably 20 ~ 40mm.
7. the method according to any one of claim 1-6, is characterized in that, in electric flocculation treatment process, the electric flocculation reaction time is 15 ~ 60min;
Preferably, the time of described Air Exposure is 3 ~ 20min.
8. the method according to any one of claim 1-7, is characterized in that, in electric flocculation treatment process, electrode is iron electrode and/or zinc electrode;
Preferably, in electric flocculation treatment process, electrode also can be the combination of iron electrode and aluminium electrode;
Preferably, in electric flocculation treatment process, electrode also can be the combination of zinc electrode and aluminium electrode.
9. the method according to any one of claim 1-8, is characterized in that, in described heavy metal wastewater thereby, the concentration of heavy metal ion is 0.1 ~ 20mg/L;
Preferably, described sulfide is (1.5 ~ 5) by the mol ratio of sulfonium ion and divalence heavy metal cation: 1 adds, and is preferably 3:1.
10. the method according to any one of claim 1-9, is characterized in that, the filtration medium in described filtration is the combination of any one or at least two kinds in hard coal, quartz sand, gac, coke or porous ceramics.
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| CN106517543A (en) * | 2016-11-27 | 2017-03-22 | 杭州水处理技术研究开发中心有限公司 | Device for removing heavy metals in hard waste water |
| CN106630036A (en) * | 2016-12-28 | 2017-05-10 | 清华大学 | Low-energy-consumption electric flocculation device for removing heavy metals in water body |
| CN107337261A (en) * | 2017-08-22 | 2017-11-10 | 嘉兴合益环境工程有限公司 | A kind of method that processing calcium-magnesium-containing ion waste water is co-precipitated by ferrite |
| CN107640859A (en) * | 2017-08-21 | 2018-01-30 | 苏州美源达环保科技股份有限公司 | The comprehensive treatment equipment and technique of high concentration COD waste browning liquid |
| CN108395025A (en) * | 2018-05-10 | 2018-08-14 | 长沙矿冶研究院有限责任公司 | A kind of the electric flocculation deep treatment method and electric flocculation device of waste water containing thallium |
| CN110668619A (en) * | 2019-11-01 | 2020-01-10 | 桂润环境科技股份有限公司 | Lead-zinc industrial mineral processing wastewater treatment device and treatment method |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN116282118A (en) * | 2022-12-28 | 2023-06-23 | 广西国盛稀土新材料有限公司 | Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater |
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| CN106517543A (en) * | 2016-11-27 | 2017-03-22 | 杭州水处理技术研究开发中心有限公司 | Device for removing heavy metals in hard waste water |
| CN106630036A (en) * | 2016-12-28 | 2017-05-10 | 清华大学 | Low-energy-consumption electric flocculation device for removing heavy metals in water body |
| CN106630036B (en) * | 2016-12-28 | 2019-11-22 | 清华大学 | A kind of device of the electric flocculation removal Heavy Metals in Waters of low energy consumption |
| CN107640859A (en) * | 2017-08-21 | 2018-01-30 | 苏州美源达环保科技股份有限公司 | The comprehensive treatment equipment and technique of high concentration COD waste browning liquid |
| CN107337261A (en) * | 2017-08-22 | 2017-11-10 | 嘉兴合益环境工程有限公司 | A kind of method that processing calcium-magnesium-containing ion waste water is co-precipitated by ferrite |
| CN108395025A (en) * | 2018-05-10 | 2018-08-14 | 长沙矿冶研究院有限责任公司 | A kind of the electric flocculation deep treatment method and electric flocculation device of waste water containing thallium |
| CN108395025B (en) * | 2018-05-10 | 2024-03-22 | 长沙矿冶研究院有限责任公司 | Electric flocculation advanced treatment method and electric flocculation device for thallium-containing wastewater |
| CN110668619A (en) * | 2019-11-01 | 2020-01-10 | 桂润环境科技股份有限公司 | Lead-zinc industrial mineral processing wastewater treatment device and treatment method |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN111960602B (en) * | 2020-08-04 | 2022-11-22 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN116282118A (en) * | 2022-12-28 | 2023-06-23 | 广西国盛稀土新材料有限公司 | Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater |
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