CN104071932B - A kind for the treatment of process of Cu-EDTA complexing waste water and electric flocculation plant - Google Patents
A kind for the treatment of process of Cu-EDTA complexing waste water and electric flocculation plant Download PDFInfo
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- CN104071932B CN104071932B CN201410347280.3A CN201410347280A CN104071932B CN 104071932 B CN104071932 B CN 104071932B CN 201410347280 A CN201410347280 A CN 201410347280A CN 104071932 B CN104071932 B CN 104071932B
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- 238000005189 flocculation Methods 0.000 title claims abstract description 83
- 239000002351 wastewater Substances 0.000 title claims abstract description 83
- 230000016615 flocculation Effects 0.000 title claims abstract description 82
- 230000000536 complexating effect Effects 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 227
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 109
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000004411 aluminium Substances 0.000 claims abstract description 105
- 229910052742 iron Inorganic materials 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 230000008859 change Effects 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 25
- 239000011780 sodium chloride Substances 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 19
- 230000005611 electricity Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000013043 chemical agent Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002594 sorbent Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 12
- 229910001431 copper ion Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000013049 sediment Substances 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229940001516 sodium nitrate Drugs 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910002707 Al–O–H Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DYGRBEQMHOCZMF-UHFFFAOYSA-K [OH-].[Na+].[Fe+2].[OH-].[OH-] Chemical compound [OH-].[Na+].[Fe+2].[OH-].[OH-] DYGRBEQMHOCZMF-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000002306 biochemical method Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a kind for the treatment of process of Cu-EDTA complexing waste water and electric flocculation plant, treatment process comprises the following steps: Cu-EDTA complexing waste water is put into reactive tank, and with aluminium electrode for anode, ferroelectric very negative electrode carries out electric flocculation reaction 30 ~ 50min; Then change the sense of current, with ferroelectric very anode, aluminium electrode is that negative electrode carries out electric flocculation reaction 30 ~ 50min, completes the process to Cu-EDTA complexing waste water.Electricity flocculation plant comprises power supply, rly., electrode, reactive tank, and electrode comprises aluminium electrode and iron electrode, and one end of aluminium electrode and described iron electrode is by rly. and power sources in series, and the other end of aluminium electrode and iron electrode is arranged in reactive tank.The present invention is processed Cu-EDTA complexing waste water by the synergy between aluminium electrode and iron electrode, without the need to adding chemical agent and sorbent material, has simple to operate, processing cost is low and cupric ion and COD clearance be high etc. advantage.
Description
Technical field
The present invention relates to field of environmental technology, particularly relate to a kind for the treatment of process of Cu-EDTA complexing waste water, also relate to the electric flocculation plant being applied to aforementioned processing methods.
Background technology
In the society of high speed information, the life of people be unable to do without the electronic product such as mobile phone, computer, and the production of these electronic products all be unable to do without printed circuit board (PCB) (PrintedCircuitBoard, PCB).Printed circuit board (PCB) is the basis of electronic industry, is that to connect for electronic component be main cross tie part.The important component part of nearly all electronic product all comprises printed circuit board (PCB), and printed circuit board (PCB) is widely used in the fields such as communication equipment, measurement and monitoring instrument instrument, household electronic apparatus, computer and components and parts.In order to improve the quality of product, the electroplating additive kind used in board production and quantity get more and more, and composition also becomes increasingly complex.Have in these additives and heavy metal ion (copper, nickel, the tin etc.) composition that coordination is stronger, as EDTA, ammonia, tartrate, cyanogen root, pyrophosphate salt and citric acid etc., they easily and heavy metal form more stable complex compound, have a strong impact on the removal of the heavy metal ion such as Cu in waste water.EDTA is a kind of organic complexing agent conventional in printed circuit board (PCB) electroless copper plating technique, and be made up of four carboxyls and two amino, cupric ion is surrounded by four carboxyls and two amino tightly, makes electrolytic solution in wider pH range, keep stable.Therefore, electroless copper plating technique often produces a large amount of Cu-EDTA complexing waste water.Cu-EDTA Stability of Metal Complexes is strong, is difficult to degraded, and LiZ.B research finds that the degradation time of Cu-EDTA in soil needs more than 15 years.Cu-EDTA complexing waste water, as mustn't go to effective process, will threaten the health of environment and the mankind.
At present, modal Cu-EDTA complexing waste water treatment process mainly chemical precipitation method and biological process.Chemical precipitation method process, because waste water stability is quite high, need use more coagulating agent, produce a large amount of heavy metal sewage sludges, not only really cannot deal with problems, also increase cost.Biochemical method, necessary first contact break, is separated cupric ion with EDTA, and EDTA needs itself just can utilize biological treatment for bioerodible.So chemical precipitation method and the treatment effect of biological process to Cu-EDTA complexing waste water all undesirable.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided a kind of simple to operate, non-secondary pollution, processing cost are lower and the method for cupric ion and the high process Cu-EDTA complexing waste water of COD clearance, also provide a kind of electric flocculation plant being applied to aforementioned processing methods.
For solving the problems of the technologies described above, the invention provides a kind for the treatment of process of Cu-EDTA complexing waste water, comprise the following steps: regulated by described Cu-EDTA complexing waste water pH for acid, then with the aluminium electrode of electric flocculation plant for anode, the ferroelectric very negative electrode of electric flocculation plant carries out electric flocculation reaction 30 ~ 50min in Cu-EDTA complexing waste water; Then change the sense of current, with ferroelectric very anode, aluminium electrode is that negative electrode carries out electric flocculation reaction 30 ~ 50min, completes the process to Cu-EDTA complexing waste water.
Further, before Cu-EDTA complexing waste water is put into reactive tank, first pre-treatment is carried out to Cu-EDTA complexing waste water: be 3.00 ~ 3.02 by described Cu-EDTA complexing waste water salt acid for adjusting pH.
Further, the sodium chloride solution of the electrolytic solution that electric flocculation plant adopts to be concentration be 0.5 ~ 1g/L.
Further, electric flocculation reaction adopts DC power supply, and constant current density is 6.66 ~ 11.1mA/cm
2.
Further, in described electric flocculation reaction process, pass into air, aeration rate is 0.35 ~ 1L/min.
Aforementioned electric flocculation plant can be arbitrary electric flocculation plant comprising aluminium electrode and iron electrode, in order to reach better effect, present invention also offers a kind of electric flocculation plant of the treatment process for aforementioned Cu-EDTA complexing waste water, specifically comprise power supply, rly., electrode, reactive tank; Electrode comprises aluminium electrode and iron electrode, and one end of aluminium electrode and iron electrode is by rly. and power sources in series, and the other end of aluminium electrode and iron electrode is arranged in reactive tank;
Further, aluminium electrode comprises the first aluminium electrode and the second aluminium electrode, and iron electrode comprises the first iron electrode and the second iron electrode; Second aluminium electrode is arranged between the first iron electrode and the second iron electrode, is connected in parallel on one end of described rly. with the first aluminium electrode; First iron electrode is arranged at the other end being parallel to rly. between the first aluminium electrode and the second aluminium electrode with the second iron electrode.
Further, the first aluminium electrode and the spacing between the first iron electrode, the spacing between the first iron electrode and the second aluminium electrode, the spacing between the second aluminium electrode and the second iron electrode are all identical, and preferred spacing is 10 ~ 16mm.
Further, described electric flocculation plant also comprises mixing groove, peristaltic pump, and mixing groove is juxtaposed on reactive tank side, is realized the exchange of Cu-EDTA complexing waste water between described reactive tank and described mixing groove by described peristaltic pump.In electric flocculation reaction process, peristaltic pump is continuous firing, by the exchange of Cu-EDTA complexing waste water in mixing groove and reactive tank, makes the waste water sampling detection from mixing groove more representative.
Further, described mixing trench bottom is provided with magnetic stirring apparatus; Described electric flocculation plant also comprises the pneumatic pump for passing into air in reactive tank, is provided with the under meter for detecting air flow quantity between described reactive tank and described pneumatic pump.
Innovative point of the present invention is:
The present invention adopts ferro-aluminum electrode coupling electricity flocculence to process to Cu-EDTA complexing waste water, after add Cu-EDTA complexing waste water in reactive tank, electric flocculation reaction occurs:
Anode: Al (s)-3e
-=Al (aq)
3+(1)
Al(aq)
3++3H
2O＝Al(OH)
3+3H
+(2)
4OH
--4e
-＝2H
2O+O
2(g)(3)
2H
2O-4e
-＝4H
++O
2(g)(4)
2Cl
--2e
-＝Cl
2(g)(5)
Cl
2(g)+H
2O＝HOCl+H
++Cl
-(6)
Negative electrode: 2H
3o
++ 2e
-=2H
2o+H
2(g) (acid solution) (7)
2H
2o+2e
-=2OH
-+ H
2(g) (alkaline solution) (8)
2H
2O+O
2+4e
-＝4OH
-(9)
Cu
2++2OH
-＝Cu(OH)
2(10)
Cu
2++2e
-＝Cu(11)
From the foregoing, Al hydrolysis in anode, and existed by following form: gel polymerisation state, monokaryon state and multinuclear state.Wherein gel polymerisation state aluminium mainly plays the flocculation sediment effect of oxyhydroxide, monokaryon state aluminium and multinuclear state aluminium can combine with the anionic sites of organic molecule, in and electric charge, strengthen the contact of organic molecule and gel polymerisation state aluminium, and then promote flocculation sediment effect, reach the object of organics removal; So the removal mechanisms at work of EDTA mainly: the oxyhydroxide flocculation sediment effect under alkaline condition and monokaryon state aluminium/iron and multinuclear state aluminium/iron charge neutralization.Secondly, Cu-EDTA complexing waste water regulates pH to be 3.0 ~ 3.02 by the present invention, and hypochlorous acid oxidization effect just can remove the organism in waste water equally in acid condition.On the other hand, in the treating processes of electricity flocculation, the cupric ion in Cu-EDTA complexing waste water obtains electronics, forms copper simple substance on iron cathode surface.
Because Cu-EDTA complex compound is more stable, now the removal effect of cupric ion and organic molecule is still not obvious, in order to improve removal efficiency further, rly. is used to change the sense of current, make aluminium electrode become negative electrode, iron electrode becomes anode, and electric flocculation reaction occurs in reactive tank:
Anode: Fe-3e
-=Fe
3+(12)
Fe(s)-2e
-＝Fe(aq)
2+(13)
Fe(aq)
2++2H
2O＝Fe(OH)
2+2H
2O(14)
Fe(OH)
2+HOCl＝Fe(OH)
3+Cl
-(15)
Fe
2+-e
-＝Fe
3+(16)
Fe
3++3H
2O＝Fe(OH)
3+3H
+(17)
Negative electrode: Fe (OH)
3+ OH
-=[Fe (OH)
4]
-(18)
[Fe (OH)
4]
-+ 2OH
-=[Fe (OH)
6]
3-(strong base solution) (19)
Al (s)+4OH
-=[Al (OH)
4]
-+ 3e
-(strong base solution) (20)
2H
3o
++ 2e
-=2H
2o+H
2(g) (acid solution) (21)
2H
2o+2e
-=2OH
-+ H
2(g) (alkaline solution) (22)
2H
2O+O
2+4e
-＝4OH
-(23)
Cu
2++2OH
-＝Cu(OH)
2(24)
The chemically stable constant of Cu-EDTA, Al-EDTA and Fe (III)-EDTA is respectively 10
18.8, 10
16.3with 10
25.1, because the chemical stability of Fe (III) is better than Cu-EDTA, mean that iron (III) that iron anode produces can replace the copper in Cu-EDTA; Iron anode betatopic simultaneously, electrode surface absorbing copper simple substance, is removed copper by galvanic deposit; Moreover along with the carrying out of reaction, the pH value of solution rises gradually, copper is removed with the form of copper hydroxide precipitation, or polluted by copper coprecipitation occurs on sodium hydroxide iron/aluminium flco surface and removes.So the impact of the removal of cupric ion mainly three aspects: the flocculation sediment effect of the metathesis of iron (III), galvanic deposit effect and oxyhydroxide.
The beneficial effect of the present inventor is:
(1) the invention provides a kind of method for removing Cu-EDTA complexing waste water, carrying out under mildly acidic conditions, reaction conditions is gentle, and high to organic mineralization rate, simple to operate, level of automation is high.
(2) the present invention realizes the removal of Cu-EDTA complexing waste water by electric flocculence, without the need to adding chemical agent and additional sorbent material, can not produce secondary pollution, has environmental protection and the low double benefit of cost.
(3) the present invention adopts the electric flocculation plant of ferro-aluminum electrode, aluminium electrode and the effect of iron electrode in Cu-EDTA complexing waste water are given full play to, synergy is utilized to realize the removal of EDTA and Cu, wherein the clearance of Cu can reach more than 99.7%, the clearance of COD can reach more than 80%, apparently higher than prior art, copper simple substance can also be recycled to a certain extent.
Accompanying drawing explanation
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the electric flocculation plant structure iron for the treatment of Cu-EDTA complexing waste water of embodiment 1.
Fig. 2 be embodiment 1 for the treatment of electrode structural chart in the electric flocculation plant of Cu-EDTA complexing waste water.
Fig. 3 is Cu and the COD clearance graphic representation that different initial pH is corresponding.
Fig. 4 is in electric flocculation reaction process, the solution Zeta potential value change curve that different initial pH is corresponding.
Fig. 5 is in electric flocculation reaction process, the solution ph change curve that different initial pH is corresponding.
Fig. 6 is Cu and the COD clearance graphic representation that different sodium chloride concentration is corresponding.
Fig. 7 is the electric flocculate precipitate FTIR spectrum figure of embodiment 2.
Fig. 8 is the electric flocculate precipitate of embodiment 2 and the electron-microscope scanning figure of iron electrode and energy spectrum analysis figure.
Marginal data:
In the accompanying drawings, 1, power supply; 2, rly.; 3, electrode; 31, aluminium electrode; 311, the first aluminium electrode; 312, the second aluminium electrode; 32, iron electrode; 321, the first iron electrode; 322, the second iron electrode; 4, reactive tank; 5, groove is mixed; 6, peristaltic pump; 7, magnetic stirring apparatus; 8, pneumatic pump; 9, under meter.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
Embodiment 1
See Fig. 1: a kind of electric flocculation plant comprises power supply 1, rly. 2, electrode 3, reactive tank 4, mixing groove 5, peristaltic pump 6, pneumatic pump 8, one end of electrode 3 is connected with power supply 1 by rly. 2, the other end of electrode 3 is arranged in reactive tank 4, and mixing groove 5 is juxtaposed on reactive tank 4 side.Reactive tank 4 and mixing groove 5 built with Cu-EDTA complexing waste water, by the exchange of Cu-EDTA complexing waste water between peristaltic pump 6 realization response groove 4 and mixing groove 5.Preferably, the bottom of mixing groove 5 is provided with magnetic stirring apparatus 7, realizes the quick mixing of Cu-EDTA complexing waste water.
Pneumatic pump 8 is arranged at outside reactive tank 4, passes into air by blast main bottom reactive tank 4.Preferably, being provided with the under meter 9 for detecting air flow quantity between reactive tank 4 and pneumatic pump 8, facilitating the control of aeration rate in electric flocculation reaction process.
Simultaneously with reference to Fig. 2: further, former electrodes 3 comprises aluminium electrode 31 and iron electrode 32, and the positive pole of power supply 1 is held with the A1 of rly. 2 and is connected, and the negative pole of power supply 1 is held with the A2 of rly. 2 and is connected, aluminium electrode 31 is held with the B1 of rly. and is connected, and iron electrode 32 is held with the B2 of rly. and is connected.
As the preferred implementation of the present embodiment, aluminium electrode 31 also comprises the first aluminium electrode 311 and the second aluminium electrode 312; Iron electrode 32 also comprises the first iron electrode 321 and the second iron electrode 322, second aluminium electrode 312 is arranged between the first iron electrode 321 and the second iron electrode 322, and the B1 being connected in parallel on rly. with the first aluminium electrode 311 holds; First iron electrode 321 is arranged at the B2 being parallel to rly. between the first aluminium electrode 311 and the second aluminium electrode 312 with the second iron electrode 322 and holds.First aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 spacing is between any two adjustable.
When electric flocculation plant is started working, the A1 end of rly. is held with B1 and is connected, A2 end is held with B2 and is connected, electric current flows out from the positive pole of power supply 1, and successively through A1 end, B1 holds, flow to the first aluminium electrode 311 and the second aluminium electrode 312, and flow out from the first iron electrode 321 and the second iron electrode 322, through B2 end, A2 end gets back to power cathode.In this process, the first aluminium electrode 311 and the second aluminium electrode 312 are anode, and the first iron electrode 321 and the second iron electrode 322 are negative electrode.
When needing the current methods changing electric flocculation plant, the A1 of rly. 2 end is held with B2 and is connected, A2 end is held with B1 and is connected, electric current flows out from the positive pole of power supply, and successively through A1 end, B2 holds, flow in the first iron electrode 321 and the second iron electrode 322, and flow out from the first aluminium electrode 311 and the second aluminium electrode 312, through B1 end, A2 end gets back to power cathode.In this process, the first iron electrode 321 and the second iron electrode 322 are anode, and the first aluminium electrode 311 and the second aluminium electrode 312 are negative electrode.
Embodiment 2
A kind of method adopting ferro-aluminum electrode coupling electricity flocculence process Cu-EDTA complexing waste water:
1) Cu-EDTA complexing waste water, wherein content of copper ion is 50mg/L, COD levels is 200mg/L, is 3.01 with salt acid for adjusting pH value;
2) adopt preferred electric flocculation plant in embodiment 1, regulate the spacing in the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 between two adjacent electrodes to be 15mm.Take concentration as the sodium chloride solution of 0.75g/L be electrolytic solution, electrolytic solution is put into the reactive tank 4 of aforementioned electric flocculation plant, then in reactive tank 4, add the Cu-EDTA complexing waste water of 2.5L step (1), make Cu-EDTA complexing waste water and electrolytic solution mixing obtain mixing solutions, the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 all immerses in mixing solutions.Then be that 0.7L/min passes into air in reactive tank 4 with aeration rate.Opening power 1, adopt DC power supply, adjustment constant current density is 8.89mA/cm
2.The A1 of rly. 2 end is held be connected with the positive pole of power supply 1, the B1 of rly. 2 respectively, and A2 end is held be connected with the negative pole of power supply 1, the B2 of rly. 2 respectively.After power supply is connected, the first aluminium electrode 311 and the second aluminium electrode 312 are anode, and the first iron electrode 321 and the second iron electrode 322 are negative electrode, and with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 40min;
3) after question response completes, the A1 of rly. 2 end is held with B2 and is connected, A2 end is held with B1 and is connected, first aluminium electrode 311 and the second aluminium electrode 312 become negative electrode, first iron electrode 321 and the second iron electrode 322 become anode, with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 40min;
4) reacted, left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 0.1mg/L, and clearance is 99.8%, COD levels is 33.8mg/L, and clearance is 83.1%.
Embodiment 3
1) get Cu-EDTA complexing waste water, wherein content of copper ion is 50mg/L, COD levels is 200mg/L, is 3.00 with salt acid for adjusting pH value;
2) adopt preferred electric flocculation plant in embodiment 1, regulate the spacing in the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 between two adjacent electrodes to be 10mm.Take concentration as the sodium chloride solution of 0.5g/L be electrolytic solution, electrolytic solution is put into the reactive tank 4 of aforementioned electric flocculation plant, then in reactive tank 4, add the Cu-EDTA complexing waste water of 2.5L step (1), make Cu-EDTA complexing waste water and electrolytic solution mixing obtain mixing solutions, the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 all immerses in mixing solutions.Then be that 0.35L/min passes into air in reactive tank 4 with aeration rate.Opening power 1, adopt DC power supply, adjustment constant current density is 6.66mA/cm
2.The A1 of rly. 2 end is held be connected with the positive pole of power supply 1, the B1 of rly. 2 respectively, and A2 end is held be connected with the negative pole of power supply 1, the B2 of rly. 2 respectively.After power supply is connected, the first aluminium electrode 311 and the second aluminium electrode 312 are anode, and the first iron electrode 321 and the second iron electrode 322 are negative electrode, and with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 30min;
3) after question response completes, the A1 of rly. 2 end is held with B2 and is connected, A2 end is held with B1 and is connected, the first aluminium electrode 311 and the second aluminium electrode 312 is made to become negative electrode, first iron electrode 321 and the second iron electrode 322 become anode, with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 30min;
4) reacted, left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 0.15mg/L, and clearance is 99.7%, COD levels is 38.6mg/L, and clearance is 80.7%.
Embodiment 4
1) get Cu-EDTA complexing waste water, wherein content of copper ion is 50mg/L, COD levels is 200mg/L, is 3.02 with salt acid for adjusting pH value;
2) adopt preferred electric flocculation plant in embodiment 1, regulate the spacing in the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 between two adjacent electrodes to be 16mm.Take concentration as the sodium chloride solution of 1g/L be electrolytic solution, electrolytic solution is put into the reactive tank 4 of aforementioned electric flocculation plant, then in reactive tank 4, add the Cu-EDTA complexing waste water of 2.5L step (1), make Cu-EDTA complexing waste water and electrolytic solution mixing obtain mixing solutions, the first aluminium electrode 311, first iron electrode 321, second aluminium electrode 312, second iron electrode 322 all immerses in mixing solutions.Then be that 1L/min passes into air in reactive tank 4 with aeration rate.Opening power 1, adopt DC power supply, adjustment constant current density is 11.1mA/cm
2.The A1 of rly. 2 end is held be connected with the positive pole of power supply 1, the B1 of rly. 2 respectively, A2 end is held be connected with the negative pole of power supply 1, the B2 of rly. 2 respectively, the first aluminium electrode 311 and the second aluminium electrode 312 is made to be anode, first iron electrode 321 and the second iron electrode 322 are negative electrode, with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 50min;
3) after question response completes, the A1 of rly. 2 end is held with B2 and is connected, A2 end is held with B1 and is connected, the first aluminium electrode 311 and the second aluminium electrode 312 is made to be negative electrode, first iron electrode 321 and the second iron electrode 322 are anode, and make the first aluminium electrode 311 and the second aluminium electrode 312 be negative electrode, the first iron electrode 321 and the second iron electrode 322 are anode, with the Cu-EDTA complexing waste water in reactive tank 4, sodium chloride solution, electric flocculation reaction occurs, the electric flocculation reaction time is 50min;
4) reacted, left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 0.1mg/L, and clearance is 99.8%, COD levels is 31.6mg/L, and clearance is 84.2%.
Comparative example 1
Four electrodes of electrode 3 are aluminium electrode, and all the other treatment condition are identical with embodiment 2.
After having processed, after being left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 21.9mg/L, and clearance is 56.2%, COD levels is 88.4mg/L, and clearance is 55.8%.
Comparative example 2
Four electrodes of electrode 3 are iron electrode, and all the other treatment condition are identical with embodiment 2.
After having processed, after being left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 0.05mg/L, and clearance is 99.9%, COD levels is 96.6mg/L, and clearance is 51.7%.
Comparative example 3
First aluminium electrode 311 in electrode 3 is replaced to iron electrode, and the second iron electrode 322 is replaced to aluminium electrode, and all the other treatment condition are identical with embodiment 2.
After having processed, after being left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 0.35mg/L, and clearance is 99.3%, COD levels is 72.8mg/L, and clearance is 63.6%.
Comparative example 4
First aluminium electrode 311 and the second aluminium electrode 312 in electrode 3 are all replaced to iron electrode, and the first iron electrode 321 and the second iron electrode 322 are all replaced to aluminium electrode, and all the other treatment condition are identical with embodiment 2.
After having processed, after being left standstill by Cu-EDTA complexing waste water, detecting content of copper ion in Cu-EDTA complexing wastewater supernatant fluid is 1.25mg/L, and clearance is 97.5%, COD levels is 76.2mg/L, and clearance is 61.9%.
Comparative example 5
1) get Cu-EDTA complexing waste water, wherein content of copper ion is 640mg/L, COD levels is 2560mg/L, is 3 with salt acid for adjusting pH value;
2) adopt electric flocculation plant to process Cu-EDTA complexing waste water, the treatment time is 30min, and electric flocculation plant is with the titanium net electrode of 1 ferroelectric very anode, 1 platinum plating for negative electrode, and electrolytic solution is sodium chloride solution.
After having processed, after being left standstill by Cu-EDTA complexing waste water, the clearance detecting cupric ion in Cu-EDTA complexing wastewater supernatant fluid is 51%, the clearance of COD is 10%.
The investigation that initial ph value affects electric flocculation reaction:
Regulate the initial ph value of Cu-EDTA complexing waste water to be respectively 1,3,5,7,9,11 respectively with the hydrochloric acid of 1mol/L and sodium hydroxide solution, then adopt the method for embodiment 2 to process Cu-EDTA complexing waste water.
As can be known from Fig. 3, when the initial ph value of Cu-EDTA complexing waste water is 3, COD treatment effect is better, this is because when initial pH is 3, in reactor 4, the aluminium/iron of precipitation is maximum, and the flocculation sediment effect of aluminium/iron hydroxide makes COD clearance higher.
As can be known from Fig. 4, when initial ph value is 1, the Zeta potential in reaction process in system be always on the occasion of, when initial pH is 3 and 5, along with the prolongation in reaction times, Zeta potential is gradually by just becoming negative, when initial pH is greater than 7, Zeta potential is negative value always, reaction 80min after, initial ph value be 3 system Zeta potential be-14.9mV, closest to 0, molecule or dispersed particle tend to condensation or cohesion, and facilitate COD flocculation sediment, COD clearance is higher.
As can be known from Fig. 5: when initial ph value is 3 to 11, before exchanging electrode (i.e. 40min before reaction), in reaction process, pH value trends towards 9, and after exchanging electrode (i.e. 40min after reaction), pH value slowly raises.We find in experimentation, and when initial ph value is 1, in electric flocculation process, pH change is very little, and the aluminium in solution is with Al
3+form exists, and the iron in solution is with Fe
2+, Fe
3+form exists, and does not almost have flocculation sediment effect, is unfavorable for the removal of COD and Cu.Do not precipitate generation in experimentation, but the clearance of Cu reaches 63.1%, found by the energy spectrum analysis of aluminium/iron electrode, remove Cu and be attracted in iron electrode, removed by galvanic deposit effect.
Sodium chloride concentration is investigated the impact of electric flocculation reaction:
Prepare respectively sodium chloride concentration be respectively 0,0.5,1,1.5, the electrolytic solution of 2.5g/L, when sodium chloride concentration is 0g/L, add the electroconductibility that SODIUMNITRATE maintains electrolytic solution.The method of embodiment 2 is adopted to proceed electric flocculation reaction.Different sodium-chlor experimental result as shown in Figure 6.As can be known from Fig. 6: when sodium chloride concentration is 0, when sodium nitrate concentration is 1g/L, the clearance of COD and Cu is all undesirable, and when sodium chloride concentration is 0.5g/L, the clearance that the clearance of COD reaches 78.7%, Cu reaches 99.9%.This is because under acidic conditions, chlorion effectively can destroy the zone of oxidation of electrode surface, and at the Surface Creation chlorine of aluminum anode and hypochlorous acid.Hypochlorous acid is the extremely strong oxygenant of a kind of oxidisability, can carry out contact break to Cu-EDTA, and then oxidation EDTA.When the concentration of sodium-chlor is more than 1g/L, COD clearance declines along with the increase of sodium chloride concentration, and its reason is excessive chlorion and Al (OH)
3/ Fe (OH)
4react, finally dissolve by excessive chlorion, be again released from the pollutent of flocculation sediment, cause COD clearance to decline.
FTIR spectrum investigation is carried out to the electric flocculate precipitate in embodiment 2:
Step 4 by embodiment 2) in Cu-EDTA complexing waste water filtering, get precipitation dry, the throw out of oven dry is carried out FTIR spectrum scanning, and scanning result is as shown in Figure 7.In Fig. 7: wave number is 3443cm
-1and 1609cm
-1absorption peak connected that-OH stretching vibration and H-O-H flexural vibration produce respectively by hydrogen bond, wave number 1400 represents-COOH stretching vibration; Wave number 1090 represents N-H stretching vibration, and 926 is charateristic avsorption bands that Al-O-H vibrates, and 552 is magnetite (Fe
3o
4, Fe
3-XO
4) charateristic avsorption band.
As can be known from Fig. 7: the oxide compound that electric flocculate precipitate mainly contains aluminium and iron is formed, and has adsorbed a small amount of carboxyl class itrogenous organic substance, proves that the flocculation sediment effect of oxyhydroxide is the main removal mechanisms at work of EDTA.
Electron-microscope scanning and energy spectrum analysis are carried out to the electric flocculate precipitate of embodiment 2 and iron electrode:
By embodiment 2 step 4) in Cu-EDTA complexing waste water filtering, get precipitation to dry, the throw out of oven dry is carried out electron-microscope scanning and energy spectrum analysis, sedimentary electron-microscope scanning and EDAX results are as shown in (a) in Fig. 8: part Cu is attached to sedimentary surface, is removed by flocculation sediment.
The electron-microscope scanning of iron electrode and EDAX results are as shown in (b) in Fig. 8: part Cu is adsorbed on iron electrode surface, is removed by galvanic deposit.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from spirit of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (9)
1. the treatment process of a Cu-EDTA complexing waste water, it is characterized in that, electric flocculation plant is adopted to process Cu-EDTA complexing waste water, described treatment step is: regulated by described Cu-EDTA complexing waste water pH for acid, then with the aluminium electrode of described electric flocculation plant for anode, the ferroelectric very negative electrode of described electric flocculation plant carries out electric flocculation reaction 30 ~ 50min in Cu-EDTA complexing waste water; Then change the sense of current, with ferroelectric very anode, aluminium electrode is that negative electrode carries out electric flocculation reaction 30 ~ 50min, completes the process to Cu-EDTA complexing waste water;
Described Cu-EDTA complexing waste water is 3.00 ~ 3.02 by salt acid for adjusting pH.
2. treatment process according to claim 1, is characterized in that, the sodium chloride solution of the electrolytic solution that described electric flocculation plant adopts to be concentration be 0.5 ~ 1g/L.
3. treatment process according to claim 1, is characterized in that, adopt DC power supply in described electric flocculation reaction process, constant current density is 6.66 ~ 11.1mA/cm
2.
4. treatment process according to claim 1, is characterized in that, in described electric flocculation reaction process, pass into air, aeration rate is 0.35 ~ 1L/min.
5. the electric flocculation plant for treatment process according to any one of Claims 1-4, it is characterized in that, described electric flocculation plant comprises power supply (1), rly. (2), electrode (3), reactive tank (4), described electrode (3) comprises aluminium electrode (31) and iron electrode (32), connected with power supply (1) by rly. (2) in one end of described aluminium electrode (31) and described iron electrode (32), described aluminium electrode (31) is arranged in described reactive tank (4) with the other end of described iron electrode (32).
6. electric flocculation plant according to claim 5, is characterized in that, described aluminium electrode (31) comprises the first aluminium electrode (311) and the second aluminium electrode (312), and described iron electrode (32) comprises the first iron electrode (321) and the second iron electrode (322); Described second aluminium electrode (312) is arranged between described first iron electrode (321) and the second iron electrode (322), is connected in parallel on one end of described rly. with described first aluminium electrode (311); Described first iron electrode (321) is arranged between the first aluminium electrode (311) and the second aluminium electrode (312), is parallel to the other end of described rly. with described second iron electrode (322).
7. electric flocculation plant according to claim 6, it is characterized in that, the spacing between described first aluminium electrode (311) and described first iron electrode (321), the spacing between described first iron electrode (321) and described second aluminium electrode (312), the spacing between described second aluminium electrode (312) and described second iron electrode (322) are 10 ~ 16mm.
8. the electric flocculation plant according to any one of claim 5 to 7, it is characterized in that, described electric flocculation plant also comprises mixing groove (5), peristaltic pump (6), described mixing groove (5) is juxtaposed on described reactive tank (4) side, is realized the exchange of Cu-EDTA complexing waste water between described reactive tank (4) and described mixing groove (5) by described peristaltic pump (6).
9. electric flocculation plant according to claim 8, is characterized in that, described mixing groove (5) bottom is provided with magnetic stirring apparatus (7); Described electric flocculation plant also comprises the pneumatic pump (8) for passing into air in reactive tank (4), is provided with the under meter (9) for detecting air flow quantity between described reactive tank (4) and described pneumatic pump (8).
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| CN108529797B (en) * | 2018-04-17 | 2020-10-20 | 南京大学 | Treatment method of Cu-EDTA heavy metal complexing wastewater |
| CN110835190A (en) * | 2019-11-21 | 2020-02-25 | 武汉科技大学 | Wastewater treatment system and method for degrading Cu-EDTA by electric flocculation coupling ultraviolet light |
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| CN202849130U (en) * | 2012-10-26 | 2013-04-03 | 成都飞创科技有限公司 | Electric flocculation wastewater treatment device |
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| CN202849130U (en) * | 2012-10-26 | 2013-04-03 | 成都飞创科技有限公司 | Electric flocculation wastewater treatment device |
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