CN111410374A - System and method for treating nickel-containing electroplating wastewater - Google Patents
System and method for treating nickel-containing electroplating wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 121
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 46
- 238000009713 electroplating Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 67
- 230000003647 oxidation Effects 0.000 claims abstract description 56
- 238000006065 biodegradation reaction Methods 0.000 claims abstract description 41
- 239000010802 sludge Substances 0.000 claims abstract description 41
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 26
- 239000011550 stock solution Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- 238000004062 sedimentation Methods 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229920002521 macromolecule Polymers 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 238000005189 flocculation Methods 0.000 claims description 15
- 230000016615 flocculation Effects 0.000 claims description 15
- 230000020477 pH reduction Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 238000005273 aeration Methods 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 244000005700 microbiome Species 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 5
- 229910001447 ferric ion Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910017112 Fe—C Inorganic materials 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000006378 damage Effects 0.000 claims description 2
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
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- 241000894006 Bacteria Species 0.000 description 5
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000003513 alkali Substances 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
- 230000000694 effects Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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Abstract
A system and a method for treating nickel-containing electroplating wastewater adopt a physical-chemical-biological three-stage integrated one-dragon flow line treatment mode. The wastewater treatment system consists of a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system. Which can effectively remove nickel ions and organic pollutants in the nickel-containing wastewater. After wastewater is sequentially treated by four treatment modules, namely a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system, the indexes of pollutants in effluent can reach the discharge limit value standard shown in table 3 of GB21900-2008 'discharge Standard for electroplating pollutants'. Compared with a single Fenton advanced oxidation treatment technology, the treatment process has high treatment efficiency and small sludge production, has strong impact load resistance and high system stability compared with the traditional activated sludge treatment technology, and is suitable for the advanced treatment of electroplating comprehensive wastewater.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a system and a method for treating nickel-containing electroplating wastewater.
Background
The electroplating industry is an important component of the industry in China and is also a high-pollution industry. The nickel-containing wastewater generated by the electroplating industry has complex components, contains a large amount of heavy metal nickel ions, organic matters (such as organic acid and the like) which are difficult to degrade, has the problems of low BOD/COD ratio and poor biodegradability, and COD (BOD is biological oxygen demand, which refers to the amount of dissolved oxygen consumed in the biochemical reaction process performed by microorganisms for decomposing the biodegradable organic matters in water under certain conditions; COD is chemical oxygen demand, which is the amount of reducing substances needing to be oxidized in a water sample measured by a chemical method; and the BOD/COD ratio reflects the biodegradation capacity of the wastewater).
Along with the release of GB21900-2008 'discharge Standard of electroplating pollutants', the treatment problem of electroplating wastewater is concerned by people in the industry, especially the discharge requirement of electroplating wastewater on nickel is stricter, wherein the total nickel required by the standard 3 in the above national standard is less than or equal to 0.1 mg/L.
Disclosure of Invention
The invention aims to solve the technical problem of providing a system and a method for treating nickel-containing electroplating wastewater, which adopt a physical-chemical-biological three-stage integrated one-stage assembly line treatment mode to ensure that each pollutant index of treated effluent can reach the discharge limit value standard shown in GB21900-2008 'electroplating pollutant discharge standard' table 3.
In order to solve the technical problems, the invention adopts the technical scheme that:
the system for treating nickel-containing electroplating wastewater comprises a wastewater collecting pool for storing stock solution of nickel-containing wastewater and a wastewater treatment system, and is characterized in that: the wastewater treatment system consists of a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system, wherein,
the three-dimensional electrolytic reaction system is used for carrying out three-dimensional electrolytic reaction on the wastewater stock solution under an acidic condition, and breaking chains of organic macromolecules in the wastewater stock solution to decompose the organic macromolecules so as to break the complex nickel into free-state positive divalent free nickel;
the deep oxidation system is used for carrying out structural destruction and oxidative decomposition on organic matters which are difficult to degrade in the wastewater treated by the three-dimensional electrolytic reaction system so as to enable free-state nickel ions in the wastewater to generate precipitable granular Ni (OH)2；
The biodegradation system adopts microorganisms to hydrolyze insoluble organic matters into soluble organic matters and converts macromolecular substances which are difficult to biodegrade into micromolecular substances which are easy to biodegrade;
and the biochemical effluent purification system is used for collecting the effluent treated by the biodegradation system, filtering out fine suspended matters and colloidal particles in the effluent and discharging the standard-reaching wastewater into a municipal drainage pipe network.
The three-dimensional electrolytic reaction system consists of a primary pH adjusting tank and a three-dimensional electrolytic reaction tank, wherein,
the primary pH adjusting tank is used for adjusting the pH value of the wastewater stock solution pumped into the primary pH adjusting tank from the wastewater collecting tank to be beneficial to the pH adjusting tank to be capable of generating hydroxyl radicals in the three-dimensional electrolytic reaction tank under the acidic condition, and the wastewater stock solution is pumped into the three-dimensional electrolytic reaction tank through stirring uniformly;
the three-dimensional electrolytic reaction tank consists of an electrolytic tank, a cathode plate, an anode plate, a particle electrode and an aeration device, wherein the cathode plate and the anode plate are parallel to the flowing direction of a wastewater stock solution, the particle electrode is filled between the cathode plate and the anode plate, the aeration device is arranged at the bottom of the three-dimensional electrolytic reaction tank, and the hydraulic retention time of wastewater in the three-dimensional electrolytic reaction tank is 1-2 hours.
The deep oxidation system consists of a Fenton oxidation system and a solid-liquid separation sedimentation tank, wherein,
the Fenton oxidation system consists of four treatment tanks which are arranged in parallel, wherein the four treatment tanks are respectively a secondary pH adjusting tank (2.0-4.0), a Fenton oxidation tank, a precipitation reaction tank (7.0-8.0) and a flocculation tank which are connected in series, the wastewater treated by the previous treatment tank is conveyed to the next treatment tank in an overflow mode, and the hydraulic retention time of the wastewater in each treatment tank is 1 hour;
the waste water treated by the Fenton oxidation system is sent into the sedimentation tank in an overflow mode, the waste water in the sedimentation tank is subjected to solid-liquid separation under an alkaline condition, the separated supernatant flows into the biodegradation system through an overflow port, and the bottom sludge containing heavy metal nickel generated after separation is pressed into a plate frame sludge press by a sludge pressing pump through a sludge outlet arranged at the bottom of the sedimentation tank.
The biodegradation system consists of a three-stage hydrolysis acidification device and a two-stage contact oxidation device, wherein,
the three-stage hydrolysis acidification device is formed by connecting three biodegradation tanks in series, and performs anaerobic biochemical treatment on supernatant pumped by the solid-liquid separation sedimentation tank, wherein the three biodegradation tanks sequentially comprise a mud-water mixing stirring tank, a mud-water mixing reaction tank and a solid-liquid separation tank, and the three biodegradation tanks are hydraulically stayed for 8-10 hours respectively;
the two-stage contact oxidation device is formed by connecting two attached oxidation tanks in series, aerobic biochemical treatment is carried out on the supernatant treated by the three-stage hydrolysis acidification device, a plurality of soft fillers or elastic fillers are suspended in each attached oxidation tank, sludge collecting cavities for active sludge to sink are respectively arranged at the bottoms of the two attached oxidation tanks, the active sludge in the sludge collecting cavities is pumped back to a first biodegradation tank in the three-stage hydrolysis acidification system through a sludge pump, and the two attached oxidation tanks are hydraulically stayed for 6 hours respectively.
The biochemical effluent purifying system consists of a biochemical effluent collecting tank and a filter, wherein,
and the biochemical effluent collecting tank is used for collecting the wastewater treated by the second attached oxidation tank and sending the wastewater into the filter in an overflow mode.
The method for treating nickel-containing electroplating wastewater is characterized by comprising the following steps: the processing steps are as follows:
1) adding acid to the collected nickel-containing electroplating wastewater stock solution for adjusting the pH value of the nickel-containing electroplating wastewater stock solution under an acidic condition;
2) for the wastewater stock solution with well adjusted pH valueCarrying out three-dimensional electrolytic reaction treatment, wherein the reaction process comprises the following steps of under the electrolytic environment with the electrolytic voltage of 30-40V and the aeration process: using new ecology [ H ]]And Fe2+Oxidation-reduction of (C), electrochemical properties of Fe-C, C and Fe3+The flocculation adsorption of the three components can act together to break the chains of organic macromolecules in the raw liquid of the wastewater and decompose the organic macromolecules; at the same time, the free nickel ion after oxidation and decomplexation is formed into precipitable granular Ni (OH)2；
3) Carrying out secondary pH adjustment on the wastewater treated by the three-dimensional electrolytic reaction to ensure that the pH value of the wastewater is acidic, and carrying out Fenton oxidation reaction on the wastewater to ensure that organic matters which are difficult to degrade generate organic free radicals;
4) adjusting the pH value of the wastewater treated by the Fenton oxidation reaction to make the pH value of the wastewater under the alkaline condition, and making the granular Ni (OH) in the wastewater2Growing up in an alkaline environment, and then adding a flocculating agent to grow large particles of Ni (OH)2Precipitation of (4);
5) carrying out biodegradation treatment on the supernatant subjected to Fenton oxidation reaction, so that insoluble organic matters in the supernatant are hydrolyzed into soluble organic matters, and macromolecular substances which are difficult to biodegrade are converted into micromolecular substances which are easy to biodegrade;
6) and filtering the effluent after the biodegradation treatment to remove fine suspended matters and colloidal particles in the effluent, and then discharging the filtered water into a municipal drainage pipe network.
In the method for treating nickel-containing electroplating wastewater, the Fenton oxidation reaction is carried out under the condition that the pH value is 2.0-4.0.
In the method for treating nickel-containing electroplating wastewater, the pH value of the precipitation flocculation treatment after the Fenton oxidation reaction is 7.0-8.0.
In the method for treating nickel-containing electroplating wastewater, the cathode plate and the anode plate adopted by the three-dimensional electrolytic reaction are graphite plates, and the particle electrodes adopted by the three-dimensional electrolytic reaction are iron-containing carbon-based catalyst particles.
The invention provides a physical-chemical-biological three-stage comprehensive treatment system aiming at the water quality condition of nickel-containing wastewater, and effectively removes nickel ions and organic pollutants in the nickel-containing wastewater. After wastewater is sequentially treated by four treatment modules, namely a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system, the indexes of pollutants in effluent can reach the discharge limit value standard shown in table 3 of GB21900-2008 'discharge Standard for electroplating pollutants'. Compared with a single Fenton advanced oxidation treatment technology, the treatment process has high treatment efficiency and small sludge production, has strong impact load resistance and high system stability compared with the traditional activated sludge treatment technology, and is suitable for the advanced treatment of electroplating comprehensive wastewater.
Drawings
FIG. 1 is a block diagram of a processing system of the present invention.
Detailed Description
The system for treating nickel-containing electroplating wastewater is a system for treating wastewater containing high-concentration nickel and COD harmful substances generated by industrial electroplating (hereinafter, untreated wastewater is referred to as wastewater stock solution), and can effectively remove nickel existing in a complex state and a plurality of organic matters (such as phosphorus, various organic acids and the like) which are difficult to decompose and seriously pollute the environment in the wastewater stock solution.
As shown in figure 1, the system comprises four treatment modules, namely a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system.
One-dimensional and three-dimensional electrolytic reaction system
The three-dimensional electrolytic reaction system consists of a primary pH adjusting tank and a three-dimensional electrolytic reaction tank.
1. And a primary pH adjusting tank, namely, pumping the waste water stock solution stored in the waste water collecting tank into the adjusting tank for homogenizing and homogenizing, adding acid and stirring, adjusting the pH value of the waste water stock solution to be 4.0-5.0 under an acidic condition, and automatically adding the acid amount into the primary pH adjusting tank by adopting a pH automatic controller for adjusting the pH value.
Is adjusted to be beneficial to generating strong oxidant H in the three-dimensional electrolytic reaction tank2O2The raw wastewater is pumped into a three-dimensional electrolytic reaction tank by stirring evenly in an acidic state.
2. And the three-dimensional electrolytic reaction tank is used for pumping the wastewater stock solution with the well adjusted pH value in the primary pH adjusting tank into the three-dimensional electrolytic reaction tank.
The three-dimensional electrolytic reaction tank consists of an electrolytic tank, a cathode plate, an anode plate, a particle electrode and an aeration device, wherein the cathode plate and the anode plate adopt graphite plates, and the particle electrode is iron-containing carbon-based catalyst particles. The three-dimensional electrolytic reaction tank is characterized in that a wastewater stock solution flows in from one side of the three-dimensional electrolytic reaction tank and then flows out from the other side, the flow directions of the cathode plate and the anode plate are parallel to the wastewater stock solution, the particle electrode is filled between the cathode plate and the anode plate, the aeration device adopts a Roots blower for aeration, the aeration is sprayed out from the bottom of the three-dimensional electrolytic reaction tank, and the hydraulic retention time of the wastewater in the three-dimensional electrolytic reaction tank is 1-2 hours.
Under an acidic condition, carrying out three-dimensional electrolytic reaction on the wastewater stock solution, and breaking chains of organic macromolecules in the wastewater stock solution to decompose so that the complex nickel is broken into free-state positive divalent free nickel;
three-dimensional electrolytic reaction tank utilizing new ecology [ H ]]And Fe2+Oxidation-reduction of (2), electrochemistry of Fe-C, C and Fe3+The flocculation adsorption of the three components can lead organic macromolecules in the raw liquid of the waste water, such as organic additives like citric acid, malic acid and the like, to be broken and decomposed into micromolecules, thus reducing the whole COD, improving the biodegradability of the waste water and providing possibility for subsequent biochemical use. At the same time, the free nickel ion after oxidation and decomplexation is formed into precipitable granular Ni (OH)2。
The electrolysis principle is as follows:
fe in the particle electrode loses electrons to produce Fe2+Molecular oxygen to produce H by electron reduction2O2Rapidly react with Fe2+The reaction forms OH and Fe with strong oxidizability3+。
OH can oxidize and decompose macromolecular organic matters in the wastewater into small molecules, complex nickel breaks the complex, and particularly, unsaturated bonds of chromium-containing dye molecules which are difficult to degrade can be broken to break the structures of chromophoric groups and chromophoric groups. Free Ni for making Ni and Cr in complex state into free state2+And Cr3+. Under acidic conditions, molecular oxygen is more prone to produce H2O2With addition of Fe2+Presence of H2O2The speed of converting into OH free radicals is accelerated, the removal rate is improved, and the electrocatalytic oxidation effect is better under the acidic condition.
In addition, the particle electrode is a carbon-based catalyst particle which has the characteristic of large specific surface area, and the porous structure of the particle electrode can better adsorb colored dye molecules so as to achieve the aim of removing chromaticity.
The reaction process of the micro-electrolysis reaction is as follows:
H2O→·OH+H++e－(1)
O2+2H++2e－→H2O2(2)
Fe－2e－→Fe2+(3)
Fe2++H2O2→Fe3++·OH+OH－(4)
·OH+RH→·R+H2O (5)
Fe3++OH－→Fe(OH)3(6)
wherein RH represents an organic substance, and R represents an organic radical.
Two, deep oxidation system
The system consists of a Fenton oxidation system and a solid-liquid separation sedimentation tank.
1. The Fenton oxidation system is sequentially arranged by four treatment tanks of a secondary pH adjusting tank, a Fenton oxidation tank, a precipitation reaction tank and a flocculation tank in a serial connection mode.
And (4) conveying the wastewater treated by the previous treatment tank to the next treatment tank in an overflow mode from the second-stage pH adjusting tank to the flocculation tank, wherein the hydraulic retention time of the wastewater in each treatment tank is 1 hour.
1) And a secondary pH adjusting tank, wherein the effluent of the wastewater treated by the three-dimensional electrolytic reaction tank is pumped into the adjusting tank, acid is added for stirring, the effluent of the wastewater is adjusted to be under an acidic condition, the pH value is preferably 2.0-4.0, and the pH value can be adjusted by automatically adding acid into the primary pH adjusting tank by adopting a pH automatic controller.
2) Fenton oxidation pond
Adjusting the second-level pH value in a poolAnd pumping the wastewater with the well-adjusted pH value into the oxidation pond, and then mixing the wastewater with the water according to the mass ratio of (1-1.5): and (3) putting the ferrous sulfate and hydrogen peroxide of the step (1) into the Fenton oxidation pond to carry out a Fenton reaction. Fenton reaction under acidic condition, Fe2+Catalysis H2O2OH with strong oxidation electric property and high reaction activity is generated, and the OH reacts with the refractory organic matters in the aqueous solution to destroy the structure of the refractory organic matters, and finally the refractory organic matters are oxidized and decomposed. At the same time, the nickel in the complex state is converted into free nickel ions.
3) Sedimentation reaction tank (also called coagulation reaction tank)
And pumping the effluent of the wastewater after the Fenton oxidation reaction into the precipitation reaction tank.
Adding alkali into the precipitation reaction tank to adjust the pH value to 7.0-8.0, and automatically adding alkali into the precipitation reaction tank by adopting a pH automatic controller to adjust the pH value.
Under alkaline condition, free state nickel ion in the waste water is generated into precipitable granular Ni (OH)2。
4) Flocculation basin
Will contain granular Ni (OH) after being treated by a precipitation reaction tank2Pumping the effluent of the wastewater into the flocculation tank, adding a nonionic polymeric flocculant PAM polyacrylamide into the flocculation tank, and keeping the pH value at 7-8.
Granulating Ni (OH)2Grown up while in Fe (OH)3And adsorbing iron phosphate precipitate particles under the action of colloid flocculation, and removing the iron phosphate precipitate particles through precipitation.
2. Solid-liquid separation sedimentation tank
The solid-liquid separation sedimentation tank consists of a sedimentation tank and a mud press.
1) And the sedimentation tank is used for conveying the wastewater treated by the flocculation tank into the sedimentation tank in an overflow mode for solid-liquid separation, an overflow port is arranged at the top of the sedimentation tank, the supernatant after the solid-liquid separation flows into the biodegradation system through the overflow port, and the precipitate (also called bottom sludge) containing heavy metal nickel generated after the separation is conveyed into a plate and frame sludge press by a sludge pressing pump through a sludge outlet arranged at the bottom of the sedimentation tank.
2) The mud press is conventional equipment, presses the bottom mud fed into the mud press into a filter cake to be transported outwards, and conveys the residual liquid to the sedimentation tank or a biodegradation system through a pipeline.
Third, biodegradation system
The biodegradation system consists of a three-stage hydrolysis acidification device and a two-stage contact oxidation device.
The insoluble organic matter is hydrolyzed into soluble organic matter by microorganisms, and macromolecular substances which are difficult to biodegrade are converted into micromolecular substances which are easy to biodegrade.
A pH adjusting tank is also arranged
1. Three-stage hydrolysis acidification device
Three biodegradation tanks are arranged in parallel in a serial connection mode. Adjusting the pH value of the supernatant effluent of the solid-liquid separation sedimentation tank to 6-7, and then carrying out anaerobic biochemical treatment on the supernatant effluent.
The first biodegradation tank is a mud-water mixing and stirring tank, supernatant liquid of the solid-liquid separation and sedimentation tank is pumped into the first biodegradation tank, the supernatant liquid is fully contacted with activated sludge under the action of aeration and stirring, the activated sludge contains a large amount of microorganisms, and the hydraulic retention time is 8-10 hours.
The second biodegradation tank is a muddy water mixing reaction tank, and muddy water mixed liquor in the first biodegradation tank is pumped into the muddy water mixing reaction tank in an overflow mode and stands for 8 to 10 hours. Under the action of a large number of microorganisms (such as hydrolytic bacteria, acidifying bacteria, fermentation bacteria, hydrogen bacteria, sulfate reducing bacteria and the like), insoluble organic matters are hydrolyzed into soluble organic matters, and macromolecular substances (polymers) which are difficult to biodegrade are converted into micromolecular substances (monomers) which are easy to biodegrade, so that the biodegradability of the wastewater is improved.
And the third biodegradation tank is a solid-liquid separation tank, the sludge water which is treated in the second biodegradation tank and takes the shape of flocculation is pumped into the third biodegradation tank, the third biodegradation tank stands for 8 to 10 hours to precipitate the particles formed in the sludge water, and the supernatant is pumped into the two-stage contact oxidation device.
The activated sludge is a general name of microbial communities and organic substances and inorganic substances attached to the microbial communities, complex microorganisms in the activated sludge and organic nutrients in wastewater form a complex food chain, and the aeration is used for fully mixing and contacting the activated sludge consisting of the microorganisms and organic pollutant substances in the wastewater, so as to degrade, absorb and decompose the activated sludge, and is the core of an activated sludge process. Meanwhile, the aeration supplies oxygen necessary for the growth and decomposition of the organic matters to the microorganisms, and the active sludge and the organic matters are fully contacted under the action of mixing and stirring.
2. Two-stage contact oxidation device
The two attached oxidation ponds are arranged in parallel, the supernatant treated by the three-stage hydrolysis acidification device is subjected to aerobic biochemical treatment, a plurality of soft fillers or elastic fillers are suspended in each attached oxidation pond, the bottoms of the two attached oxidation ponds are respectively provided with a sludge collecting cavity in which activated sludge sinks, the activated sludge in the sludge collecting cavity is pumped back to a first biodegradation pond in the three-stage hydrolysis acidification system through a sludge pump, and the two attached oxidation ponds are hydraulically stayed for 6 hours respectively.
Hydrolytic acidification microorganisms are attached to and grow on the soft filler or the elastic filler, and organic matters in the supernatant pumped into the hydrolytic acidification microorganisms are degraded and decomposed again and then precipitated.
Four, biochemical effluent water purification system
The biochemical effluent purification system consists of a biochemical effluent collecting tank and a filter.
And the biochemical effluent collecting tank is used for collecting the supernatant which is treated by the second attached oxidation tank and then precipitated again, and the supernatant is sent to the filter in an overflow mode.
The filter precision of the filter element is 5 u. The device is used for filtering fine suspended matters and colloidal particles in the effluent of the biochemical effluent collecting tank and discharging standard wastewater (wherein heavy metal nickel and COD both reach the relevant discharge regulations of national standards) into a municipal drainage pipe network.
According to the system for treating nickel-containing electroplating wastewater, disclosed by the invention, the pH value is monitored on line by adopting the pH monitoring controller in each link, the acid or alkali adding amount of the metering pump is automatically controlled, the medicine consumption is reduced to the minimum, the stability of the treatment effect is ensured, and the influence of human factors is reduced.
Preferably, the system further comprises a control unit and a certain number of wastewater monitoring elements, wherein the wastewater monitoring elements are installed in the three-dimensional electrolytic reaction tank, the three-stage hydrolysis acidification device and the two-stage contact oxidation device and are in signal connection with an input end of a controller, and a signal at an output end of the controller can be in circuit connection with an interactive display screen to realize remote control; in addition, the controller can be connected with a lifting motor to control the lifting of the undercarriage bearing the soft filler or the elastic filler in the two-stage contact oxidation device, and the automation degree is high.
In this example, the wastewater used was from electronic limited, Jiangxi, and the treatment results are shown in Table 1:
table 1: results of wastewater treatment
To sum up: by adopting the system, each pollution index of the effluent can reach the limit discharge standard in the table 3 of GB21900-2008 discharge Standard of electroplating pollutants.
Claims (9)
1. The utility model provides a system for handle nickeliferous electroplating effluent, is including depositing waste water collecting pit and the effluent disposal system of nickeliferous waste water stoste, its characterized in that: the wastewater treatment system consists of a three-dimensional electrolytic reaction system, a deep oxidation system, a biodegradation system and a biochemical effluent purification system, wherein,
the three-dimensional electrolytic reaction system is used for carrying out three-dimensional electrolytic reaction on the wastewater stock solution under an acidic condition, and breaking chains of organic macromolecules in the wastewater stock solution to decompose the organic macromolecules so as to break the complex nickel into free-state positive divalent free nickel;
the deep oxidation system is used for carrying out structural destruction and oxidative decomposition on organic matters which are difficult to degrade in the wastewater treated by the three-dimensional electrolytic reaction system so as to enable free-state nickel ions in the wastewater to generate precipitable granular Ni (OH)2；
The biodegradation system adopts microorganisms to hydrolyze insoluble organic matters into soluble organic matters and converts macromolecular substances which are difficult to biodegrade into micromolecular substances which are easy to biodegrade;
and the biochemical effluent purification system is used for collecting the effluent treated by the biodegradation system, filtering out fine suspended matters and colloidal particles in the effluent and discharging the standard-reaching wastewater into a municipal drainage pipe network.
2. The system for treating nickel-containing electroplating wastewater according to claim 1, characterized in that: the three-dimensional electrolytic reaction system consists of a primary pH adjusting tank and a three-dimensional electrolytic reaction tank, wherein,
the primary pH adjusting tank is used for adjusting the pH value of the wastewater stock solution pumped into the primary pH adjusting tank from the wastewater collecting tank to be beneficial to the pH adjusting tank to be capable of generating hydroxyl radicals in the three-dimensional electrolytic reaction tank under the acidic condition, and the wastewater stock solution is pumped into the three-dimensional electrolytic reaction tank through stirring uniformly;
the three-dimensional electrolytic reaction tank consists of an electrolytic tank, a cathode plate, an anode plate, a particle electrode and an aeration device, wherein the cathode plate and the anode plate are parallel to the flowing direction of a wastewater stock solution, the particle electrode is filled between the cathode plate and the anode plate, the aeration device is arranged at the bottom of the three-dimensional electrolytic reaction tank, and the hydraulic retention time of wastewater in the three-dimensional electrolytic reaction tank is 1-2 hours.
3. The system for treating nickel-containing electroplating wastewater according to claim 2, characterized in that: the deep oxidation system consists of a Fenton oxidation system and a solid-liquid separation sedimentation tank, wherein,
the Fenton oxidation system consists of four treatment tanks which are arranged in parallel, wherein the four treatment tanks are respectively a secondary pH adjusting tank (2.0-4.0), a Fenton oxidation tank, a precipitation reaction tank (7.0-8.0) and a flocculation tank which are connected in series, the wastewater treated by the previous treatment tank is conveyed to the next treatment tank in an overflow mode, and the hydraulic retention time of the wastewater in each treatment tank is 1 hour;
the waste water treated by the Fenton oxidation system is sent into the sedimentation tank in an overflow mode, the waste water in the sedimentation tank is subjected to solid-liquid separation under an alkaline condition, the separated supernatant flows into the biodegradation system through an overflow port, and the bottom sludge containing heavy metal nickel generated after separation is pressed into a plate frame sludge press by a sludge pressing pump through a sludge outlet arranged at the bottom of the sedimentation tank.
4. The system for treating nickel-containing electroplating wastewater according to claim 3, characterized in that: the biodegradation system consists of a three-stage hydrolysis acidification device and a two-stage contact oxidation device, wherein,
the three-stage hydrolysis acidification device is formed by connecting three biodegradation tanks in series, and performs anaerobic biochemical treatment on supernatant pumped by the solid-liquid separation sedimentation tank, wherein the three biodegradation tanks sequentially comprise a mud-water mixing stirring tank, a mud-water mixing reaction tank and a solid-liquid separation tank, and the three biodegradation tanks are hydraulically stayed for 8-10 hours respectively;
the two-stage contact oxidation device is formed by connecting two attached oxidation tanks in series, aerobic biochemical treatment is carried out on the supernatant treated by the three-stage hydrolysis acidification device, a plurality of soft fillers or elastic fillers are suspended in each attached oxidation tank, sludge collecting cavities for active sludge to sink are respectively arranged at the bottoms of the two attached oxidation tanks, the active sludge in the sludge collecting cavities is pumped back to a first biodegradation tank in the three-stage hydrolysis acidification system through a sludge pump, and the two attached oxidation tanks are hydraulically stayed for 6 hours respectively.
5. The system for treating nickel-containing electroplating wastewater according to claim 4, characterized in that: the biochemical effluent purifying system consists of a biochemical effluent collecting tank and a filter, wherein,
and the biochemical effluent collecting tank is used for collecting the wastewater treated by the second attached oxidation tank and sending the wastewater into the filter in an overflow mode.
6. A method for treating nickel-containing electroplating wastewater is characterized by comprising the following steps: the processing steps are as follows:
1) adding acid to the collected nickel-containing electroplating wastewater stock solution for adjusting the pH value of the nickel-containing electroplating wastewater stock solution under an acidic condition;
2) carrying out three-dimensional electrolytic reaction treatment on the wastewater stock solution with the adjusted pH value, and electrolyzingThe voltage is 30-40V and the reaction process is as follows under the electrolysis environment of the aeration process: using new ecology [ H ]]And Fe2+Oxidation-reduction of (C), electrochemical properties of Fe-C, C and Fe3+The flocculation adsorption of the three components can act together to break the chains of organic macromolecules in the raw liquid of the wastewater and decompose the organic macromolecules; at the same time, the free nickel ion after oxidation and decomplexation is formed into precipitable granular Ni (OH)2；
3) Carrying out secondary pH adjustment on the wastewater treated by the three-dimensional electrolytic reaction to ensure that the pH value of the wastewater is acidic, and carrying out Fenton oxidation reaction on the wastewater to ensure that organic matters which are difficult to degrade generate organic free radicals;
4) adjusting the pH value of the wastewater treated by the Fenton oxidation reaction to make the pH value of the wastewater under the alkaline condition, and making the granular Ni (OH) in the wastewater2Growing up in an alkaline environment, and then adding a flocculating agent to grow large particles of Ni (OH)2Precipitation of (4);
5) carrying out biodegradation treatment on the supernatant subjected to Fenton oxidation reaction, so that insoluble organic matters in the supernatant are hydrolyzed into soluble organic matters, and macromolecular substances which are difficult to biodegrade are converted into micromolecular substances which are easy to biodegrade;
6) and filtering the effluent after the biodegradation treatment to remove fine suspended matters and colloidal particles in the effluent, and then discharging the filtered water into a municipal drainage pipe network.
7. The method for treating nickel-containing electroplating wastewater according to claim 6, characterized in that: the Fenton oxidation reaction is carried out under the condition that the pH value is 2.0-4.0.
8. The method for treating nickel-containing electroplating wastewater according to claim 6, characterized in that: the pH value of the precipitation flocculation treatment after the Fenton oxidation reaction is 7.0-8.0.
9. The method for treating nickel-containing electroplating wastewater according to claim 6, characterized in that: the negative plate and the positive plate adopted by the three-dimensional electrolytic reaction are graphite plates, and the adopted particle electrodes are carbon-based catalyst particles containing iron elements.
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