CN103641209B - A kind of copper-containing wastewater combined electrolysis groove treatment process - Google Patents
A kind of copper-containing wastewater combined electrolysis groove treatment process Download PDFInfo
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Abstract
The invention discloses a kind of copper-containing wastewater combined electrolysis groove treatment process.Copper-containing wastewater is put into combined electrolysis groove and is carried out electrolysis treatment by the method, and extra electric field provides 26 ~ 30V volts DS after rectification, and react 25 ~ 35 minutes, strength of current is 0.85 ~ 1.05A; By often liter of copper-containing wastewater, add NaCl0.15 ~ 0.25g/L, controlling air water volume ratio is 2.5 ~ 3:1, uses air compressor machine air feed; Control electrolysis water outlet pH value to 8.5 ~ 10, the waste water after electrolysis treatment enters inclined-plate clarifying basin, precipitate 1 1.5 hours, supernatant liquor is discharged, and mud is sunken in pool bottom sludge groove; Copper removal Be very effective of the present invention, overall operation expense is low, and floor space is little, invests little, and pretreating effect is good, and the clearance of cupric ion is more than 99%.
Description
Technical field
The present invention relates to a kind of wastewater treatment, particularly relate to a kind of copper-containing wastewater combined electrolysis groove treatment process.
Background technology
Due to heavy metal ion not biodegradable, bioconcentration, as the key industry of heavy metal contamination, one of contaminated industry that the Yi Shi world today is the most serious, the governing problem of the heavy metal wastewater thereby produced has become the focus of field of Environment Protection concern.Cyanide wastewater can be divided into by contained pollutent, containing the heavy metal wastewater therebies such as zinc, nickel, copper, cadmium and lead, organic waste water, acidity and alkaline waste water etc. in waste water.
Major technique and the method for Treatment of Copper waste water mainly contain: (1) uses the reduction such as ferrous sulfate, sodium metabisulfite, S-WAT, sulfurous gas; (2) anionite-exchange resin is utilized to carry out ion-exchange; (3) electrochemical reduction; (4) evaporation is reclaimed; (5) absorption etc.But these methods also exist or process, and pollutant kind is single, complex process, investment cost are high, maybe needs to add excess chemical medicament, sludge quantity is large, and then produce the problem of secondary pollution, be difficult to reach emission standard.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, provide a kind of copper removal Be very effective, overall operation expense is low, and floor space is little, invests little copper-containing wastewater combined electrolysis groove treatment process.
Object of the present invention is achieved through the following technical solutions:
A kind of copper-containing wastewater combined electrolysis groove treatment process: copper-containing wastewater is put into combined electrolysis groove and carry out electrolysis treatment, extra electric field provides 26 ~ 30V volts DS after rectification, and react 25 ~ 35 minutes, strength of current is 0.85 ~ 1.05A; By often liter of copper-containing wastewater, add NaCl0.15 ~ 0.25g/L, controlling air water volume ratio ratio is 2.5 ~ 3:1, uses air compressor machine air feed; Control electrolysis water outlet pH value to 8.5 ~ 10, the waste water after electrolysis treatment enters inclined-plate clarifying basin, precipitate 1 ?1.5 hours, supernatant liquor is discharged, and mud is sunken in pool bottom sludge groove;
Described combined electrolysis groove becomes multiple electrolyzer unit by baffle for separating, the negative plate of each electrolyzer unit both sides and the opposing parallel setting of positive plate, the packing layer be made up of dissolving granule electrode and insulating particle electrode is provided with in electrolyzer unit, the volume ratio of dissolving granule electrode and insulating particle electrode is 1:1 ~ 2.5:1, dissolve granule electrode and insulating particle electrode account for electrolyzer unit cavity volume 40 ?50%, bottom of electrolytic tank is provided with aeration tube, and aeration tube bottom is provided with sludge sump;
Described dissolving granule electrode is that multiple diameter is less than 5mm, highly be less than the cylindrical particle of 1mm, by percentage to the quality, cylindrical particle is shaping by 83 ~ 87% iron powders, 3 ~ 13% activated carbon powders, 2 ~ 4% calcium lignin sulphonates, 1 ~ 2% copper powder, 1% zinc oxide and 0.3 ~ 0.5% Zirconium oxide sintering;
Described insulating particle electrode is that multiple diameter is less than 5mm, highly be less than the cylindrical particle of 1mm, by percentage to the quality, cylindrical particle is by 24 ~ 26% diatomite, 18 ~ 28% activated carbon powders, 36 ~ 56% clays, 3 ~ 8% calcium lignin sulphonates, 1 ~ 2% copper powder and 0.1 ~ 1% nickel oxide sinter molding.
For realizing the object of the invention further, preferably, described positive plate take titanium sheet as matrix, first through mechanical polishing acid corroding pretreatment, then prepares SnO by thermal decomposition method
2+ Sb
2o
3+ MnO
2active intermediate.Described negative plate is stainless steel plate.Described volts DS adopts TPR constant current constant voltage Power supply.Described control air water volume ratio ratio is 2.5 ~ 3:1 is adopt air compressor machine air feed.Described control electrolysis water outlet pH value regulates to 8.5 ~ 10 by adding alkali.
Copper-containing wastewater of the present invention enters combined electrolysis wastewater treatment equipment, compound light electrolysis wastewater treatment equipment passes through the efficient combination of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, by the direct electrochemistry redox of electrode, active substance ([H] and the Fe of electrode generation
2+, OH and H
2o
2deng) the high electric current spatiotemporal efficiency of indirectly redoxomorphism and three-diemsnional electrode, intensive treatment waste water.
The present invention carries out copper-containing wastewater combined electrolysis groove copper removal by compound electric solution, compound electric solution is the associating by three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, device inside is equipped with positive/negative plate electrode, is dissolved granule electrode and insulating particle electrode, wherein, dissolve particle and act as master with iron powder light electrolysis, insulating particle then plays against short-circuit effect, and pad electrode adopts titanium base SnO
2+ Sb
2o
3+ MnO
2coated electrode, as the anode of overpotential electrolysis, solves electrode and easily comes off, and electropotential is not high, and work-ing life is short, the problem of the easy adsorbed product in surface.The free radical of the nascent state produced in reaction process and coagulating agent, collection redox, flocculation adsorption, catalyzed oxidation, complexing and deposition etc. act as one, dissolve particle and dissolve the Fe produced
2+directly will with Cu
2+produce Cu (OH)
2with Fe (OH)
3co-precipitation, makes the copper in copper-containing wastewater remove rapidly.Do not need the chemical agent adding other more in the process, therefore this system cloud gray model is easy.By the direct electrochemistry redox of electrode, active substance ([H] and the Fe of electrode generation
2+, OH and H
2o
2deng) the high electric current spatiotemporal efficiency of indirectly redoxomorphism and three-diemsnional electrode, intensive treatment waste water copper removal efficiency.
Compared with the conventional method, tool has the following advantages in the present invention:
(1) copper-containing wastewater combined electrolysis groove copper removal of the present invention is by the combination of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, by the direct electrochemistry redox of electrode, active substance ([H] and the Fe of electrode generation
2+, OH and H
2o
2deng) the high electric current spatiotemporal efficiency of indirectly redoxomorphism and three-diemsnional electrode, strengthening copper removal efficiency, adopts three-diemsnional electrode or fluidized bed electrochemical reactor, the mass transfer specific surface area utilizing it higher, improves electrochemical reactor efficiency.
(2) compound electric solution of the present invention has that device structure is simple, applied widely, treatment effect is good;
(3) because without the need to adding chemical agent, sludge quantity is little, and power consumption greatly reduces compared with electrolysis, and therefore copper-containing wastewater combined electrolysis groove treatment process working cost of the present invention is cheap;
(4) because of employing is combined electrolysis slot device, and operating parameter can adjust with change of water quality, and combined electrolysis groove has the packing layer of insulating particle electrode simultaneously, can play shock absorption to waste water that is a large amount of and high density; Therefore copper-containing wastewater combined electrolysis groove treatment process of the present invention can bear the impact of big yield and high-concentration waste water;
(5) copper-containing wastewater combined electrolysis groove treatment process convenient operating maintenance of the present invention and easily and the advantage such as other method of wastewater treatment couplings.
(6) the present invention adds diatomite in insulated electrode, and diatomite can adsorb Cr
3+, Pb
2+, Cd
2+, Cu
2+, contribute to the removal of Cu in waste water ion.
Accompanying drawing explanation
Fig. 1 is combined electrolysis groove structural representation of the present invention.
Shown in figure: 1 aeration tube; 2 insulating particle electrodes; 3 dissolve granule electrode; 4 positive plates; 5 negative plates; 6 dividing plates; 7 electrolyzer units; 8 support air distribution plate; 9 sludge sumps.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated, but the scope of protection of present invention is not limited to the scope of embodiment statement.
As shown in Figure 1, combined electrolysis groove of the present invention is separated into multiple electrolyzer unit 7 by dividing plate 6, the negative plate 5 of each electrolyzer unit both sides and the opposing parallel setting of positive plate 4, is provided with and dissolves granule electrode 3 and insulating particle electrode 2 in electrolyzer unit 7; The volume ratio of dissolving granule electrode 3 and insulating particle electrode 2 is 1:1 ~ 2:1; Dissolving granule electrode 3 and insulating particle electrode 2 form packing layer; Bottom of electrolytic tank is provided with aeration tube 1, and aeration tube 1 bottom is provided with sludge sump 9; Aeration tube 1 is positioned at and supports below air distribution plate 8, and by supporting air distribution plate 8 evenly gas distribution, aeration tube 1 is connected with air compressor machine.Negative plate 5 is connected with TPR constant current constant voltage power supply with positive plate 4.Inclined-plate clarifying basin is conventional equipment, be connected with last electrolyzer unit 7, is used for precipitate and separate.
Embodiment 1
With the copper-containing wastewater of the inventive method concentration for the treatment of 126.4mg/L.The water quality situation of this copper-containing wastewater is as follows: Cu126.4mg/L, COD
cr185mg/L, SS67mg/L, pH4.8.Correlative study shows, as the beneficial element that life is necessary, the toxicity of copper own is less, but after human body sucks excessive copper, will stimulate digestion system, causing stomachache vomiting, excessively for a long time causes liver cirrhosis.Copper is also comparatively large to unicellular lower eukaryote and farm crop toxicity, and reaching 0.1 ~ 0.2mg/L to fish can be lethal; To farm crop, copper is heavy metal poisoning soprano, and it is fixed on root with the form of ion, affects nutrition absorption function, makes farm crop occur disease.Further, the SS contained in waste water and other metal ions also can cause larger harm to environment.
In the present embodiment, reactor is divided into four electrolyzer units by dividing plate by combined electrolysis groove 7 inside, current are advanced in plug-flow mode in reactor, ensure waste liquid and in granule electrode, have sufficient contact, battery lead plate is equipped with in reactor both sides, adopt TPR constant current constant voltage power supply supply current/voltage, negative plate 5 and the opposing parallel setting of positive plate 4, device internal main will comprise the packing layer dissolving granule electrode 3 and insulating particle electrode 2, dividing plate 6, support air distribution plate 8, aeration tube 1, the parts such as sludge sump 9, extra electric field provides the volts DS of the 26V after rectification, strength of current is 0.85A, NaCl dosage is 0.15g/L, gas-water ratio is 2.5:1, use air compressor machine air feed, reactor bottom arranges micro-hole aerator, react after 25 minutes.(volume ratio of dissolving granule electrode 3 and insulating particle electrode 2 is 1.5:1, and the two accounts for 50% of electrolyzer unit cavity volume together, and electrolyzer unit cavity volume refers to the volume in whole space between negative plate 5 and positive plate 4 in electrolyzer unit.
With material component mass percent, wherein dissolve granule electrode raw material by 84% iron powder, 8% activated carbon powder, 5% calcium lignin sulphonate, 1% copper powder, 1% zinc oxide, 1% zirconium white composition, is squeezed into the post strip that diameter is 5mm after raw material mixes, cut into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
With material component mass percent, insulating particle electrode material by 24% diatomite, 20.8% activated carbon powder, 50% clay, 4% calcium lignin sulphonate, 1% copper powder, 0.2% nickel oxide composition, is squeezed into the post strip that diameter is 5mm after raw material mixes, cut into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
Positive plate 4 for matrix, uses emery cloth, 300 with thick 0.8mm, the size titanium sheet that is 80mm × 10mm successively
#after liquid honing, in 0.1mol/L oxalic acid solution, boil 2h, put into 0.1mol/L oxalic acid solution and preserve stand-by, through pre-treatment such as mechanical polishing acid etchings; Preparation middle layer masking liquid: first by SnCl
45H
2o, SbCl
38:1 mixing in mass ratio, then be dissolved in hydrochloric acid and propyl carbinol (1:1) solution by 1:10, make middle layer masking liquid.Pre-treatment titanium sheet is cleaned, dries, coat prepared intermediate layer solution, put into 120 DEG C of baking ovens and react 15min, then proceed to thermolysis 10min in the retort furnace of 500 DEG C, 5 times repeatedly, be extended down to 1.0h for the last time, be i.e. obtained middle layer; Continue coating on the intermediate layer and be added with saturated Mn (NO
3)
2propyl carbinol water (1:1) solution, put into the retort furnace thermolysis 10min proceeding to 475 DEG C after 100 DEG C of baking ovens react 10min, 10 times repeatedly, be extended down to 1.0h for the last time, be i.e. obtained SnO
2+ Sb
2o
3+ MnO
2middle layer; Wherein Mn, O, Sn, Sb mass ratio is 48.8%, 26.1%, 14.7%, 10.4%.Finally the back side rubber seal being shaped with the titanium sheet in middle layer is lived, be contained on electrolyzer, carry out one-side electroplating, increase the good combination of coating and matrix, improve electropotential, the problem of the easy adsorbed product in surface.Negative plate 5 is stainless steel plate.
The process of copper-containing wastewater combined electrolysis groove, comprises the steps:
(1) waste water enters combined electrolysis wastewater treatment equipment, extra electric field provides and form 26V volts DS after rectification, adopt TPR constant current constant voltage power supply supply current/voltage, react 25 minutes, strength of current is 0.85A, NaCl dosage is that 0.15g/L is (under 26V volts DS, can generation current intensity be 0.85A, required interpolation 0.15g/LNaCl).With air compressor machine by aeration tube 1 air feed, gas-water ratio is 2.5:1.(ratio of dissolving between granule electrode 3 and insulating particle electrode 2 is 1.5:1, the two ratio accounting for combined electrolysis groove 7 electrolyzer unit space is together 1:1 by the free radical of the nascent state produced in the association response process of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech and coagulating agent, collection redox, flocculation adsorption, catalyzed oxidation, complexing and deposition etc. act as one, dissolve particle and dissolve the Fe produced
2+directly and Cu
2+rear generation Cu (OH)
2with Fe (OH)
3co-precipitation, makes the copper in copper-containing wastewater remove rapidly.
(2) inclined-plate clarifying basin precipitation: the water outlet that step (1) obtains is added alkali adjust ph to 8.5 ~ 10, enter inclined-plate clarifying basin (process conventional equipment), after waste water enters combined electrolysis wastewater treatment equipment, flowed into by pipeline and enter inclined-plate clarifying basin, supernatant liquor is discharged, and mud is sunken in the sludge sump of pool bottom sludge groove 9 inclined-plate clarifying basin.
(3) water outlet that step (2) obtains being added mass concentration is that 10% dilute sulphuric acid carries out pH value and pulls back to 9.0, realizes qualified discharge.
Treatment effect is analyzed:
When the starting point concentration of copper-containing wastewater is Cu126.4mg/L, COD
cr185mg/L, SS67mg/L, pH4.8, when electrolysis time is 25min, strength of current be 0.85A, NaCl dosage is 0.15g/L.Adopt aas determination copper ion concentration, measuring the water outlet Cu concentration after electrolysis treatment is 0.29mg/L, COD
cr34mg/L, SS12mg/L (GB/T7473 ?1987GB/T11914 ?1989GB/T11901 ?1989), the clearance of cupric ion ((initial Nong Du ?the aqueous concentration)/starting point concentration that is 99.8%).After process, water outlet is lower than discharging standards 1.0mg/L.Working cost: 1.35 yuan/m
3(processing the electric cost needed for copper-containing wastewater of unit volume, cost of drugs and consumption of electrode cost sum)
In this example, compound electric solution is the associating by three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, device inside is equipped with positive/negative plate electrode, is dissolved granule electrode and insulating particle electrode, wherein, dissolve particle and act as master with iron powder light electrolysis, insulating particle then plays against short-circuit effect, and adds zirconium white, plays the effect of stabilized electrodes.Three-diemsnional electrode greatly increases the contact area between electrode and waste water, and the efficiency of electrolytic pole board process waste water is improved greatly.The employing titanium base SnO that electrode is breakthrough
2+ Sb
2o
3+ MnO
2coated electrode, as the anodizing copper-containing wastewater of overpotential electrolysis, solves electrode and easily comes off, and electropotential is not high, and work-ing life is short, the problem of the easy adsorbed product in surface.Significantly diatomite is added unlike in insulating particle electrode with patent 200710026285.6, because it has excellent chemical stability, not with electrolytic solution generation chemical reaction, not easily corroded by infiltration, and obviously increase with other component bonding strength of insulating particle, mechanical property improves greatly.The free radical of the nascent state produced in reaction process and coagulating agent, collection redox, flocculation adsorption, catalyzed oxidation, complexing and deposition etc. act as one, dissolve particle and dissolve the Fe produced
2+with Cu
2+reaction produces Cu (OH)
2with Fe (OH)
3co-precipitation, makes the copper in copper-containing wastewater remove rapidly.Do not need the chemical agent adding other more in the process, therefore this system cloud gray model is easy.By the direct electrochemistry redox of electrode, active substance ([H] and the Fe of electrode generation
2+, OH and H
2o
2deng) the high electric current spatiotemporal efficiency of indirectly redoxomorphism and three-diemsnional electrode, intensive treatment waste water copper removal efficiency.
Embodiment 2
With the inventive method Treatment of Copper waste water: Cu247.3mg/L, COD
cr284mg/L, SS135mg/L, pH7.3.
(1) waste water enters combined electrolysis wastewater treatment equipment, and compound light electrolysis wastewater treatment equipment is by the efficient combination of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech.Wherein, reactor is divided into four rooms by dividing plate by combined electrolysis groove 7 inside, current are advanced in plug-flow mode in reactor, ensure waste liquid and in granule electrode, have sufficient contact, battery lead plate is equipped with in reactor both sides, adopt TPR constant current constant voltage power supply supply current/voltage, negative plate 5 and the opposing parallel setting of positive plate 4, device internal main will comprise the packing layer dissolving granule electrode 3 and insulating particle electrode 2, dividing plate 6, support air distribution plate 8, aeration tube 1, the parts such as sludge sump 9, extra electric field provides the volts DS of the 28V after rectification, react after 30 minutes, extra electric field provides the volts DS of the 30V after rectification, strength of current is 0.95A, NaCl dosage is 0.20g/L, gas-water ratio is 2.8:1, use air compressor machine air feed, reactor bottom arranges micro-hole aerator, react 30 minutes.
Filler is by dissolving granule electrode 3 and insulating particle electrode 2 (volume ratio 1:1) electrode forms, dissolving granule electrode 3 and insulating particle electrode 2 account for 45% of electrolyzer unit cavity volume, by percentage to the quality, dissolve granule electrode by 85% iron powder, 8.7% activated carbon powder, 4% calcium lignin sulphonate, 1% copper powder, 1% zinc oxide, 0.3% zirconium white, is squeezed into the post strip that diameter is 5mm, cut into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
By percentage to the quality, insulating particle electrode by 23.8% activated carbon powder, the diatomite of 25%, 45% clay, 5% calcium lignin sulphonate, 1% copper powder, 0.2% nickel oxide, is squeezed into the post strip that diameter is 5mm, cut into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
Positive plate 4 take titanium sheet as matrix, first through pre-treatment such as mechanical polishing acid etchings, then prepares active intermediate SnO by thermal decomposition method
2+ Sb
2o
3+ MnO
2, increase the good combination of coating and matrix, improve electropotential, the problem of the easy adsorbed product in surface.Negative plate 5 is stainless steel plate.
(2) described combined electrolysis groove is utilized to carry out copper removal, extra electric field provides the volts DS of the 28V after rectification, adopt TPR constant current constant voltage power supply supply current/voltage, react 30 minutes, strength of current is 0.95A, NaCl dosage is 0.20g/L, gas-water ratio is 2.8:1, uses air compressor machine air feed.Dissolving granule electrode 3 with the volume ratio of noble electrode 2 is 1:1, and by the associating of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, device inside is equipped with positive/negative plate electrode, is dissolved granule electrode and insulating particle electrode.The free radical of the nascent state produced in reaction process and coagulating agent, collection redox, flocculation adsorption, catalyzed oxidation, complexing and deposition etc. act as one, dissolve particle and dissolve the Fe produced
2+direct Cu reaction produces Cu (OH)
2with Fe (OH)
3co-precipitation, makes the copper in copper-containing wastewater remove rapidly.Dissolve granule electrode 3 and defining of insulating particle electrode 2 consumption please supplement, electrolytic process and dissolve granule electrode 3 and insulating particle electrode 2 and how to act on these contents to waste water and will describe and will supplement
(3) inclined-plate clarifying basin precipitation: the water outlet that step (2) obtains is added alkali adjust ph to 8.5 ~ 10, enters inclined-plate clarifying basin, supernatant liquor is discharged, and mud is sunken in pool bottom sludge groove.
(4) water outlet that step (3) obtains is added 10% dilute sulphuric acid to carry out pH value and pull back to 9.0, realize qualified discharge.
Treatment effect is analyzed:
With the inventive method Treatment of Copper waste water.Its Cu247.3mg/L, CODCr284mg/L, SS135mg/L, pH7.3.
When treated for 30min, strength of current be 0.95A, NaCl dosage be 0.20g/L time, Cr
6+clearance be 99.8%, water outlet Cu concentration reaches 0.44mg/L, COD
cr65mg/L, SS24mg/L, working cost: 2.05 yuan/m
3, after process, copper water outlet is lower than discharging standards 0.5mg/L.
Embodiment 3
With the inventive method Treatment of Copper waste water.Its Cu112.3mg/L, COD
cr194mg/L, SS52mg/L, pH5.6.
(1) waste water enters combined electrolysis wastewater treatment equipment, and compound light electrolysis wastewater treatment equipment is by the efficient combination of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech.Wherein, reactor is divided into four rooms by dividing plate by combined electrolysis groove 7 inside, current are advanced in plug-flow mode in reactor, ensure waste liquid and in granule electrode, have sufficient contact, battery lead plate is equipped with in reactor both sides, adopt TPR constant current constant voltage power supply supply current/voltage, negative plate 5 and the opposing parallel setting of positive plate 4, device internal main will comprise the packing layer dissolving granule electrode 3 and insulating particle electrode 2, dividing plate 6, support air distribution plate 8, aeration tube 1, the parts such as sludge sump 9, extra electric field provides the volts DS of the 30V after rectification, react after 35 minutes, extra electric field provides the volts DS of the 30V after rectification, strength of current is 1.05A, NaCl dosage is 0.25g/L, gas-water ratio is 3:1, use air compressor machine air feed, reactor bottom arranges micro-hole aerator, react after 35 minutes.
Filler is by dissolving granule electrode 3 and insulating particle electrode 2 (volume ratio 2:1) electrode forms, dissolving granule electrode 3 and insulating particle electrode 2 account for 40% of electrolyzer unit cavity volume, by percentage to the quality, dissolve granule electrode by 86% iron powder, 7.7% activated carbon powder, 4% calcium lignin sulphonate, 1% copper powder, 1% zinc oxide, 0.3% zirconium white, is squeezed into the post strip that diameter is 5mm, cut into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
Insulating particle electrode is by 19.8% activated carbon powder, the diatomite of 26%, 48% clay, 5% calcium lignin sulphonate, 1% copper powder, 0.2% nickel oxide, be squeezed into the post strip that diameter is 5mm, cutting into is highly the column of 1mm, sintering 2 hours under 480 DEG C of conditions with anoxic, formation diameter is 5mm, is highly the column of 1mm.
Positive plate 4 take titanium sheet as matrix, first through pre-treatment such as mechanical polishing acid etchings, then prepares active intermediate SnO by thermal decomposition method
2+ Sb
2o
3+ MnO
2, increase the good combination of coating and matrix, improve electropotential, the problem of the easy adsorbed product in surface.Negative plate 5 is stainless steel plate.
(2) described combined electrolysis groove is utilized to carry out copper removal, extra electric field provides the volts DS of the 30V after rectification, adopts TPR constant current constant voltage power supply supply current/voltage, reacts 35 minutes, strength of current is 1.05A, NaCl dosage is 0.25g/L, gas-water ratio is 3:1, uses air compressor machine air feed.Dissolving granule electrode 3 with the volume ratio of noble electrode 2 is 2:1, and by the associating of three-diemsnional electrode, catalytic oxidation and micro electrolysis tech, device inside is equipped with positive/negative plate electrode, is dissolved granule electrode and insulating particle electrode.The free radical of the nascent state produced in reaction process and coagulating agent, collection redox, flocculation adsorption, catalyzed oxidation, complexing and deposition etc. act as one, dissolve the Fe that particle produces
2+directly and Cu
2+reaction produces Cu (OH)
2with Fe (OH)
3co-precipitation, makes the copper in copper-containing wastewater remove rapidly.
(3) inclined-plate clarifying basin precipitation: the water outlet that step (2) obtains is added alkali adjust ph to 8.5 ~ 10, enters inclined-plate clarifying basin, supernatant liquor is discharged, and mud is sunken in pool bottom sludge groove.
(4) water outlet that step (3) obtains is added 10% dilute sulphuric acid to carry out pH value and pull back to 9.0, realize qualified discharge.
Treatment effect is analyzed: when treated for 35min, strength of current be 1.05A, NaCl dosage be 0.25g/L time, water outlet Cu concentration reaches 0.52mg/L, COD
cr62mg/L, SS24mg/L, working cost: 1.42 yuan/m
3, after process, water outlet Cu is lower than discharging standards 1.0mg/L.
Claims (6)
1. a copper-containing wastewater combined electrolysis groove treatment process, it is characterized in that: cupric board wastewater is put into combined electrolysis groove and carries out electrolysis treatment, extra electric field provides 26 ~ 30V volts DS after rectification, and react 25 ~ 35 minutes, strength of current is 0.85 ~ 1.05A; By often liter of copper-containing wastewater, add NaCl0.15 ~ 0.25g/L, controlling air water volume ratio is 2.5 ~ 3:1; Control electrolysis water outlet pH value to 8.5 ~ 10, the waste water after electrolysis treatment enters inclined-plate clarifying basin, precipitate 1 ?1.5 hours, supernatant liquor is discharged, and mud is sunken in pool bottom sludge groove;
Described combined electrolysis groove becomes multiple electrolyzer unit by baffle for separating, the negative plate of each electrolyzer unit both sides and the opposing parallel setting of positive plate, the packing layer be made up of dissolving granule electrode and insulating particle electrode is provided with in electrolyzer unit, the volume ratio of dissolving granule electrode and insulating particle electrode is 1:1 ~ 2.5:1, dissolve granule electrode and insulating particle electrode account for electrolyzer unit cavity volume 40 ?50%, bottom of electrolytic tank is provided with aeration tube, and aeration tube bottom is provided with sludge sump;
Described dissolving granule electrode is that multiple diameter is less than 5mm, highly be less than the cylindrical particle of 1mm, by percentage to the quality, cylindrical particle is shaping by 83 ~ 87% iron powders, 3 ~ 13% activated carbon powders, 2 ~ 4% calcium lignin sulphonates, 1 ~ 2% copper powder, 1% zinc oxide and 0.3 ~ 0.5% Zirconium oxide sintering, and each component sum is 100%;
Described insulating particle electrode is that multiple diameter is less than 5mm, highly be less than the cylindrical particle of 1mm, by percentage to the quality, cylindrical particle is by 24 ~ 26% diatomite, 18 ~ 28% activated carbon powders, 36 ~ 56% clays, 3 ~ 8% calcium lignin sulphonates, 1 ~ 2% copper powder and 0.1 ~ 1% nickel oxide sinter molding, and each component sum is 100%.
2. copper-containing wastewater combined electrolysis groove treatment process according to claim 1, is characterized in that: described positive plate take titanium sheet as matrix, first through mechanical polishing acid corroding pretreatment, then prepares SnO by thermal decomposition method
2+ Sb
2o
3+ MnO
2active intermediate.
3. copper-containing wastewater combined electrolysis groove treatment process according to claim 1, is characterized in that: described negative plate is stainless steel plate.
4. copper-containing wastewater combined electrolysis groove treatment process according to claim 1, is characterized in that: described volts DS adopts TPR constant current constant voltage Power supply.
5. copper-containing wastewater combined electrolysis groove treatment process according to claim 1, is characterized in that: described control air water volume ratio is 2.5 ~ 3:1 is adopt air compressor machine air feed.
6. copper-containing wastewater combined electrolysis groove treatment process according to claim 1, is characterized in that: described control electrolysis water outlet pH value regulates to 8.5 ~ 10 by adding alkali.
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| CN101172688A (en) * | 2007-09-28 | 2008-05-07 | 浙江工商大学 | Method for removing heavy metal in electroplating waste |
| CN102070230A (en) * | 2010-12-10 | 2011-05-25 | 华中师范大学 | Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof |
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| CN101028944A (en) * | 2007-01-12 | 2007-09-05 | 华南理工大学 | Composite electrolytic bath and method for electrolyzing and decoloring pulp-making effluent |
| CN101172688A (en) * | 2007-09-28 | 2008-05-07 | 浙江工商大学 | Method for removing heavy metal in electroplating waste |
| CN102070230A (en) * | 2010-12-10 | 2011-05-25 | 华中师范大学 | Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof |
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