CN112321034A - Device and method for synchronously electrolyzing/membrane separating/advanced oxidizing and cooperatively treating ammonium sulfate-containing wastewater and organic wastewater - Google Patents
Device and method for synchronously electrolyzing/membrane separating/advanced oxidizing and cooperatively treating ammonium sulfate-containing wastewater and organic wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/06—Contaminated groundwater or leachate
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Abstract
The invention discloses a device and a method for synchronously electrolyzing/separating membrane/oxidizing at high grade to process waste water containing ammonium sulfate and organic waste water, wherein the device comprises an ammonium sulfate waste water treatment chamber, an organic waste water treatment chamber, an anode membrane electrode, a cathode membrane electrode and a power supply system, and the method leads the organic waste water containing ammonium sulfate into the power supply systemIn the ammonium sulfate wastewater treatment chamber, large-particle suspended substances in wastewater are intercepted under the action of membrane separation, organic matters in the wastewater are removed through interception, direct oxidation and indirect oxidation under the synergistic action of membrane separation and anodic oxidation, ammonium sulfate in the wastewater is electrolyzed on the surface of an anode membrane electrode and in a pore channel to generate ammonium persulfate, and then ammonium persulfate solution is electrically activated on the surface of a cathode membrane electrode and in the pore channel to generate SO4·‑And OH, etc., so that the organic matters in the wastewater are subjected to multiple treatments such as radical oxidation, electrochemical oxidation-reduction, membrane separation and the like to obtain purified water.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a device and a method for treating ammonium sulfate-containing wastewater and organic wastewater by virtue of synchronous electrolysis/membrane separation/advanced oxidation.
Background
In recent years, with the rapid development of modern society, the water environment pollution is becoming a serious problem. In industrial production, agricultural activities and human life, a large amount of organic pollutants are generated, and the pollutants enter underground water and surface water through various ways and further enter a food chain, so that the life health of animals, plants and human bodies is seriously threatened and damaged. On the other hand, the national standards for wastewater discharge and water quality are becoming more and more strict, and the traditional water treatment technology is difficult to meet the requirements.
At present, the advanced chemical oxidation technology is one of effective technologies for treating organic wastewater. Wherein, the electrochemical oxidation technology and the persulfate advanced oxidation technology depend on the strong oxidizing property of the generated hydroxyl free radical and the generated persulfate free radical, and can efficiently degrade organic pollutants into biodegradable or harmless micromolecular organic matters until the organic pollutants are finally mineralized into inorganic H2O and CO2. However, in practical applicationIn the process, the electrochemical oxidation technology and the persulfate advanced oxidation technology respectively face the problems of low current efficiency, high electric energy consumption and large addition amount of persulfate medicament. Therefore, the electrochemical cooperation of persulfate technology and the direct or indirect utilization of electric energy to activate persulfate to degrade pollutants in water is considered to be a feasible improvement. CN105347445A discloses a method for removing micropollutants in water by activating persulfate through an iron electrode, which utilizes iron anode to dissolve to generate Fe2+The persulfate is activated to remove the micro-pollutants in water, however, the method has the defects of anode material consumption, iron flocculating constituent generation, reaction under a specific pH condition and larger required reaction current. The method for treating organic wastewater by activating persulfate through electrochemical synergy of Ni-Fe-LDH/rGO catalyst disclosed by CN105731606A, the method for treating printing and dyeing wastewater by strengthening persulfate radicals through an electric field disclosed by CN109721138A and the method for removing organic pollutants in wastewater through electrochemical synergy of persulfate disclosed by CN108726640A are both used for activating persulfate through the catalyst under the electrochemical synergy to improve the capacity of degrading the organic pollutants in the wastewater, and the methods all face the problem of recovery of the treated catalyst. In view of the above, CN110627168A discloses "a method for electrochemically treating wastewater" and CN110104758A discloses "a method for deeply treating organic matters in high-salt wastewater by using electricity in cooperation with persulfate", which utilizes the principle that persulfate directly performs electron transfer on the surface of an electrode to activate, thereby avoiding the problems of secondary pollution of an activator and self-quenching of free radicals.
The persulfate is typically dosed several to ten times more than the organic contaminant during the treatment to pass excess SO4·-The effective removal of organic pollutants is realized, the operation cost is obviously increased by the input of a large amount of persulfate, and the problem of secondary pollution is caused by overhigh concentration of the sulfate in the effluent, so that the application of the technology is limited. CN108707921A discloses a device and a method for electrolyzing and simultaneously generating persulfate and activator ferrous ions thereof, CN110902776A discloses a method for generating sulfate radical oxidation pollutants by in-situ electrocatalysis, and CN108503097A discloses a method for treating water polluted by organic matters. The methods are based on the principle that ammonium sulfate can be electrolyzed on the surface of an anode, and the electrolysis of the ammonium sulfate is coupled with the cooperation of electricity and persulfate degradation organic wastewater so as to realize the generation and the use of the persulfate.
However, the electrodes used in the above-mentioned electric-assisted persulfate oxidation and ammonium sulfate electrolysis apparatus are all plate electrodes, and because the area of the reaction electrode plate is limited, there are often defects that the conductivity of the water body is low, the mass transfer of the system is poor, microbubbles of oxygen and hydrogen generated by side reaction electrolyzed water adhere to the surface of the electrode to affect the current efficiency, and the like. CN109867334A discloses a method for activating persulfate by catalytic particle electrodes under the drive of an electric field and application thereof, and CN110921785A discloses a method for treating persulfate water by electro-filtration and catalysis and a method for treating water by using the same, wherein three-dimensional electrodes and an electro-filtration device are adopted to strengthen mass transfer SO as to improve the electrochemical synergy of persulfate activation to generate SO4·-The efficiency of (c). However, in both of the two inventions, persulfate is directly added as an oxidant, and the electrolysis of ammonium sulfate, the treatment of other insoluble impurities and organic matters in the ammonium sulfate wastewater and the treatment of virtual floating particles in the organic wastewater are not involved.
Disclosure of Invention
The invention provides a device and a method for synchronously electrolyzing/membrane separating/advanced oxidizing and treating ammonium sulfate-containing wastewater and organic wastewater efficiently, which are used for improving the removal efficiency of organic pollutants in industrial wastewater, agricultural wastewater, domestic wastewater, underground water or surface water by membrane separation on a cathode membrane electrode and coupling persulfate advanced oxidation through membrane separation, anodic oxidation and ammonium sulfate electrolysis on an anode membrane electrode to generate pure ammonium persulfate solution, and ensure that no risk of secondary pollution exists in the whole process, thereby realizing the reutilization of resources in the wastewater.
The technical scheme adopted by the invention is as follows:
a device for synchronously electrolyzing/membrane separating/advanced oxidizing and cooperatively treating waste water containing ammonium sulfate and organic waste water comprises an ammonium sulfate waste water treatment chamber, an organic waste water treatment chamber, an anode membrane electrode, a cathode membrane electrode and a power supply system; the anode membrane electrode is arranged in the ammonium sulfate wastewater treatment chamber, the cathode membrane electrode is arranged in the organic wastewater treatment chamber, the water inlet side of the anode membrane electrode is communicated with the ammonium sulfate wastewater inlet, the water outlet side of the anode membrane electrode is communicated with the water inlet side of the cathode membrane electrode, the water outlet side of the cathode membrane electrode is communicated with the organic wastewater and the water outlet, the anode of the power supply system is connected with the anode membrane electrode, and the cathode of the power supply system is connected with the cathode membrane electrode.
Preferably, the anode membrane electrode is one of a platinum electrode, a titanium-based platinum-plated electrode, a boron-doped diamond electrode, a titanium dioxide electrode, a titanium-based titanium dioxide electrode and a lead electrode, and the cathode membrane electrode is one of a metal electrode, a metal composite electrode, a graphite electrode, an activated carbon electrode and a carbon-based material electrode.
Preferably, the cathode and anode membrane electrode is a porous microfiltration membrane, and the pore diameter is 0.1-1 μm.
Preferably, the electrode area of the anode membrane electrode and the cathode membrane electrode is 0.001-10 m2The electrode distance is 0.01-50 cm.
Preferably, the vacuum pump in the tubular membrane electrode treatment system is positioned between the water outlet side of the anode membrane electrode and the water inlet side of the cathode membrane electrode, and the vacuum pump in the plate membrane electrode treatment system is positioned behind the water outlet of the device or in front of the ammonium sulfate wastewater inlet of the device.
Preferably, one end of the tubular membrane electrode is in a sealed state, and the edge of the plate-type membrane electrode is in a sealed state with the wastewater treatment chamber.
Preferably, the ammonium sulfate wastewater treatment chamber and the organic wastewater treatment chamber in the tubular membrane electrode treatment system are separated by a perfluorinated sulfonic acid type cation exchange membrane.
Preferably, when the treatment system is used for treating the ammonium sulfate wastewater containing a large number of suspended matters or organic matters with the sizes larger than the membrane aperture, the tubular membrane electrode treatment system is adopted, the water flow direction in the ammonium sulfate treatment chamber is from the outer side of the anode membrane to the inner side of the membrane, and the water flow direction in the organic wastewater treatment chamber is from the inner side of the cathode membrane to the outer side of the membrane.
Preferably, when the treatment system is used for treating organic wastewater containing more suspended particulate matters or organic matters with the sizes larger than the membrane aperture, a tubular membrane electrode treatment system is adopted, the water flow direction in the ammonium sulfate treatment chamber is from the inner side of the anode membrane to the outer side of the membrane, and the water flow direction in the organic wastewater treatment chamber is from the outer side of the cathode membrane to the inner side of the membrane.
Preferably, when the treatment system is used for treating ectopic water with large water amount, a plate-type membrane electrode treatment system is adopted, the water flow direction in the ammonium sulfate wastewater treatment chamber is from one side of the anode membrane to the other side, and the water flow direction in the organic wastewater treatment chamber is from the organic wastewater inlet to the water outlet at the same side of the cathode membrane electrode.
Preferably, when the treatment system is used for in-situ water treatment, a plate type membrane electrode treatment system is adopted, and the water flow direction is from the upper side to the lower side of an anode membrane electrode and then from the upper side of a cathode membrane electrode to a water body.
The method for realizing synchronous electrolysis/membrane separation/advanced oxidation synergistic treatment of the ammonium sulfate-containing wastewater and the organic wastewater by utilizing the device comprises the following steps:
(1) introducing the wastewater containing ammonium sulfate into an ammonium sulfate wastewater treatment chamber, intercepting large-particle suspended matters in the wastewater under the action of membrane separation, removing organic matters in the wastewater through interception, direct oxidation and indirect oxidation under the synergistic action of membrane separation and anodic oxidation, and electrolyzing the ammonium sulfate in the wastewater on the surface of an anode membrane electrode and in a pore channel to generate ammonium persulfate;
(2) ammonium persulfate solution generated at the water outlet side of the anode membrane electrode is pumped by a vacuum pump and introduced into the organic wastewater treatment chamber, and the ammonium persulfate solution is electrically activated on the surface of the cathode membrane electrode and in the pore channel to generate SO4·-And OH, etc., so that the organic matters in the wastewater are subjected to multiple treatments such as radical oxidation, electrochemical oxidation-reduction, membrane separation and the like to obtain purified water.
Preferably, the wastewater containing ammonium sulfate in the step (1) is inorganic or organic wastewater containing ammonium sulfate generated after industrial production, agricultural activities and waste treatment, wherein the content of the ammonium sulfate is 0.01-10 mol/L.
Preferably, the large-particle suspended matters in the wastewater containing ammonium sulfate in the step (1) are inorganic or organic solid particles, complexes, floccules and colloids with the size larger than the pore diameter of the membrane, the organic matters are at least one or more than one of volatile halogenated hydrocarbons, benzene series, phenols, nitrobenzene, anilines, chlorides, polycyclic aromatic hydrocarbons, pesticides, antibiotics, personal care products and endocrine disrupting chemicals dissolved in the wastewater, and the COD concentration is 10-10000 mg/L.
Preferably, the flow rate of the vacuum pump in the step (2) is 1-50L/min.
Preferably, the organic matter in the organic wastewater in the step (2) is at least one or a mixture of more than one of volatile halogenated hydrocarbons, benzene series, phenols, nitrobenzenes, anilines, chlorides, polycyclic aromatic hydrocarbons, pesticides, antibiotics, personal care products and endocrine disrupting chemicals, and the COD concentration is 5-30000 mg/L.
Preferably, the impressed current density on the anode membrane electrode and the cathode membrane electrode is 1000-3。
Preferably, the treatment time of the method is 0.1-10 h.
During the treatment process of the method, the partial chemical reactions involved are as follows:
1) anode film electrode reaction:
ammonium sulfate electrolysis:
（1）
direct oxidation of anode organic contaminants:
（2）
indirect oxidation of organic pollutants at the anode:
（3）
2) cathode film electrode reaction:
electro-activation of ammonium persulfate:
（5）
radical oxidation of organic pollutant sulfate radical of cathode:
（6）
electrochemical oxidation of organic pollutants at the cathode:
（7）
the invention has the following beneficial effects:
1) a special electrochemical system is adopted, the waste water containing ammonium sulfate is electrolyzed to prepare persulfate which is an oxidant for oxidizing the organic waste water, the electrolysis, membrane separation, electrochemical advanced oxidation and persulfate advanced oxidation are synchronously realized in the same system, the resource reutilization is realized while the waste water is treated cooperatively, the utilization rate of electric energy is high, only clean water is obtained after the treatment, no other toxic and harmful byproducts are generated, and the environment is friendly.
2) The porous conductive micro-filtration membrane is used as an electrode, and the electrode interface reaction is effectively promoted by the large surface area on the membrane surface and in the pore channel. Reaction solution penetrates through the membrane electrode in an overflow mode, contact mass transfer of a liquid phase system and the electrode is strengthened, microbubbles generated on the electrode are discharged along with water flow, electrolysis efficiency of sulfate is greatly improved, and electrochemistry is cooperated with persulfate to activate and generate SO4·-The efficiency of (c).
4) The microfiltration membrane has the separation function of effectively intercepting suspended inorganic particles and organic matters in the wastewater, the sizes of which are larger than the membrane pore diameter, and simultaneously generating high-activity free radicals on the surface of the membrane electrode and in the pore canal, thereby effectively inhibiting the generation of membrane pollution phenomenon and keeping high membrane flux, so that the system can be widely applied to the treatment of various types of wastewater.
5) The device has advantages such as simple structure, convenient operation, required energy consumption are less, to different waste water characteristics and processing environment, is applicable in the normal position and the dystopy of industrial waste water, agricultural waste water, domestic waste water, groundwater and surface water after the fine setting structure are handled.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for simultaneous electrolysis/membrane separation/advanced oxidation synergistic treatment of ammonium sulfate-containing wastewater and organic wastewater according to example 1.
In the figure: 1-ammonium sulfate wastewater treatment chamber, 2-organic wastewater treatment chamber, 3-cation exchange membrane, 4-anode membrane electrode, 5-cathode membrane electrode, 6-power supply (power supply system), and 7-vacuum peristaltic pump.
FIG. 2 is a schematic view showing the structure of an apparatus for simultaneous electrolysis/membrane separation/advanced oxidation synergistic treatment of ammonium sulfate-containing wastewater and organic wastewater of example 2.
In the figure: 1-ammonium sulfate wastewater treatment chamber, 2-organic wastewater treatment chamber, 3-cation exchange membrane, 4-anode membrane electrode, 5-cathode membrane electrode, 6-power supply (power supply system), and 7-vacuum peristaltic pump.
FIG. 3 is a schematic view showing the structure of an apparatus for co-treating ammonium sulfate-containing wastewater and organic wastewater by synchronous electrolysis/membrane separation/advanced oxidation in example 3.
In the figure: 1-wastewater treatment chamber, 2-anode membrane electrode, 3-cathode membrane electrode, 4-power supply (power supply system) and 5-vacuum peristaltic pump.
FIG. 4 is a schematic view showing the structure of an apparatus for simultaneous electrolysis/membrane separation/advanced oxidation synergistic treatment of ammonium sulfate-containing wastewater and organic wastewater of example 4.
In the figure: 1-wastewater treatment chamber, 2-anode membrane electrode, 3-cathode membrane electrode, and 4-power supply (power supply system).
Fig. 5 is a schematic diagram of the reactions that mainly occur at the anode and cathode of the membrane electrode.
Detailed Description
The invention is described in more detail below with reference to the figures and the examples, but the scope of the invention is not limited to the description.
Example 1
A method for synchronously electrolyzing/membrane separating/advanced oxidizing and co-processing ammonium sulfate-containing wastewater and organic wastewater is disclosed, the device is shown in figure 1, and the construction comprises the following steps:
(1) selecting a porous tubular platinum electrode as an anode membrane electrode (average pore diameter of 0.42 μm, electrode area of 31.4 cm)2) The porous tubular titanium electrode is a cathode membrane electrode (the average pore diameter is 0.61 mu m, and the electrode area is 31.4 cm)2) And a power supply system (current density of 800A/m)3And the electrode spacing is 10 cm). The anode membrane electrode is arranged in the ammonium sulfate wastewater treatment chamber, and the cathode membrane electrode is arranged in the organic wastewater treatment chamber. Introducing the waste liquid containing ammonium sulfate and used for electrosynthesis of p-aminophenol (the concentration of the ammonium sulfate is 0.55 mol/L, the main organic pollutants are nitrobenzene, aniline and p-aminophenol, and the concentration of COD is 5127 mg/L) into an ammonium sulfate waste water treatment chamber, intercepting large-particle suspended substances in the waste water under the action of membrane separation, and removing organic substances in the waste water through interception, direct oxidation and indirect oxidation under the synergistic action of membrane separation and anodic oxidation, wherein the ammonium sulfate in the waste water is electrolyzed on the surface of an anode membrane electrode and in a pore channel to generate ammonium persulfate;
(2) ammonium persulfate solution generated at the inner side of the anode membrane electrode is pumped into the cathode membrane electrode under the suction of a vacuum pump (the flow rate is 8L/min), and the ammonium persulfate solution is electrically activated in the inner surface and pore channels of the cathode membrane electrode to generate SO4·-And OH and other free radicals, and is used for treating industrial dye wastewater (the main organic pollutant is rhodamine B, and the COD concentration is 328 mg/L), so that the molecules of the organic pollutant in the wastewater are subjected to multiple treatments such as free radical oxidation, electrochemical oxidation reduction, membrane separation and the like to obtain purified water. The removal rate of COD after 6 hours of treatment reaches 97.5 percent.
Example 2
A method for synchronously electrolyzing/membrane separating/advanced oxidizing and co-processing ammonium sulfate-containing wastewater and organic wastewater is disclosed, the device is shown in figure 2, and the construction comprises the following steps:
(1) a porous tubular titanium dioxide electrode is selected as an anode membrane electrode (the average pore diameter is 0.52 mu m, and the electrode area is 75.36 cm)2) The porous tubular graphite electrode was a cathode membrane electrode (average pore diameter 0.57 μm, electrode area 75.36 cm)2) And a power supply system (current density of 600A/m)3And the electrode spacing was 15 cm). The anode membrane electrode is arranged in the ammonium sulfate wastewater treatment chamber, and the cathode membrane electrode is arranged in the organic wastewater treatment chamber. Introducing desulfurization and denitrification absorption liquid (the concentration of ammonium sulfate is 0.86 mol/L) containing ammonium sulfate into an anode membrane electrode, intercepting large-particle suspended substances in the wastewater under the action of membrane separation, removing organic matters in the wastewater through interception, direct oxidation and indirect oxidation under the synergistic action of the membrane separation and anodic oxidation, and electrolyzing the ammonium sulfate in the wastewater on the surface of the anode membrane electrode and in a pore channel to generate ammonium persulfate to enter an ammonium persulfate wastewater treatment chamber;
(2) ammonium persulfate solution in the ammonium sulfate wastewater treatment chamber is pumped into the organic wastewater treatment chamber by a vacuum pump (the flow rate is 10L/min), and the ammonium persulfate solution is electrically activated on the outer surface of the cathode membrane electrode and in the pore channel to generate SO4·-OH and other free radicals are used for treating pesticide production wastewater (main organic pollutants are hexachloro cyclohexane, DDT and epoxy heptachlor, and the COD concentration is 3346 mg/L), so that organic pollutant molecules in the wastewater are subjected to multiple treatments of free radical oxidation, electrochemical oxidation reduction, membrane separation and the like to obtain purified water. The removal rate of COD after 8 hours of treatment reaches 90.1 percent.
Example 3
A method for synchronously electrolyzing/membrane separating/advanced oxidizing and co-processing ammonium sulfate-containing wastewater and organic wastewater is disclosed, the device is shown in figure 3, and the construction comprises the following steps:
(1) selecting porous plate-shaped boron-doped diamond electrode as anode membrane electrode (average pore diameter is 0.68 μm, electrode area is 400 cm)2) The porous plate-shaped carbon-based electrode is a cathode membrane electrode (average pore diameter is 0.61 μm, and electrode area is 400 cm)2) And a power supply system (current density of 1200A/m)3And the electrode spacing was 20 cm). The anode membrane electrode is arranged in the ammonium sulfate wastewater treatment chamber, and the cathode membrane electrode is arranged in the organic wastewater treatment chamber. The method comprises the steps of injecting acrylonitrile production wastewater containing ammonium sulfate (the concentration of the ammonium sulfate is 0.22 mol/L, main organic pollutants are acrylonitrile, acrylic acid, acrolein and acetonitrile, and the concentration of COD is 7127 mg/L) into an ammonium sulfate wastewater treatment chamber, intercepting large-particle suspended substances in the wastewater under the action of membrane separation, removing organic substances in the wastewater through interception, direct oxidation and indirect oxidation under the synergistic action of membrane separation and anodic oxidation, and electrolyzing ammonium sulfate in the wastewater on the surface of an anode membrane electrode and in a pore channel to generate ammonium persulfate to an intermediate chamber.
(2) The ammonium persulfate solution penetrates through the cathode membrane electrode to the organic wastewater treatment chamber, and the ammonium persulfate solution is electrically activated on the outer surface and in the pore channel of the cathode membrane electrode to generate SO4·-And OH and other free radicals, and is used for treating phenol wastewater (the main organic pollutants are phenol, m-cresol, pentachlorophenol and nitrophenol, and the COD concentration is 1542 mg/L), so that the molecules of the organic pollutants in the wastewater are subjected to multiple treatments of free radical oxidation, electrochemical oxidation reduction, membrane separation and the like to obtain purified water. The organic wastewater inlet is positioned at the upper end of the treatment chamber, the water outlet is positioned outside the treatment chamber, clean water is obtained after the organic wastewater is treated and is discharged from the water outlet, and the removal rate of COD after 4 hours of treatment reaches 98.3%.
Example 4
A method for synchronously electrolyzing/membrane separating/advanced oxidizing and co-processing ammonium sulfate-containing wastewater and organic wastewater is disclosed, the device is shown in figure 4, and the construction comprises the following steps:
(1) selecting a porous plate platinum-plated titanium electrode as an anode membrane electrode (average pore diameter is 0.49 mu m, and the electrode area is 640 cm)2) The porous active carbon electrode is a cathode membrane electrode (average pore diameter is 0.86 μm, and electrode area is 640 cm)2) And a power supply system (current density of 1200A/m)3And the electrode spacing was 8 cm). Anode filmThe electrode is arranged in the ammonium sulfate wastewater treatment chamber, the desulfurization and denitrification absorption liquid containing ammonium sulfate (the concentration of the ammonium sulfate is 0.94 mol/L) is injected into the ammonium sulfate wastewater treatment chamber, large-particle suspended substances in the wastewater are intercepted under the action of membrane separation, organic substances in the wastewater are removed through interception, direct oxidation and indirect oxidation under the synergistic action of membrane separation and anodic oxidation, and the ammonium sulfate in the wastewater is electrolyzed on the surface of an anode membrane electrode and in a pore channel to generate ammonium persulfate to the intermediate chamber.
(2) And the ammonium persulfate solution penetrates through the cathode membrane electrode to the water body, and is used for in-situ remediation of organic polluted underground water (main organic pollutants are trichloroethylene, tetrachloroethylene, carbon tetrachloride and 1, 2-dichloroethane, and the COD concentration is 284 mg/L), so that the water body remediation is obtained after the organic pollutants in the underground water are subjected to multiple treatment of free radical oxidation and electrochemical oxidation reduction. The removal rate of COD after 10 hours of treatment reaches 84.5 percent.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
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