CN112723496A - Flow type electrochemical system for generating double oxidants by double electrodes in cooperation for organic wastewater treatment and application - Google Patents
Flow type electrochemical system for generating double oxidants by double electrodes in cooperation for organic wastewater treatment and application Download PDFInfo
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- 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
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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
Abstract
The invention discloses a flow type electrochemical system for generating double oxidants by double electrodes in a synergic manner for organic wastewater treatment, and a use method and application thereof. This electrochemical system produces hydrogen peroxide and anodic oxidation sulfate ion through negative pole reduction oxygen and produces the peroxodisulfate, and the catalytic action of coupling ferrous ion and the advantage of three-dimensional electrode are activated hydrogen peroxide and peroxodisulfate respectively to hydroxyl radical and sulfate radical free radical, and the difficult degradation pollutant in the high-efficient organic waste water of getting rid of. The characteristics are as follows: the electric energy is fully converted into oxidizing chemical energy by utilizing double electrodes of an electrochemical system, and the bond breaking and the damage of the nondegradable organic pollutants are realized by coupling anodic oxidation and strong oxidizing free radicals, so that the effective degradation is realized; the removal efficiency of the organic pollutants by the diradical oxidation is higher; the problem of insufficient oxidation utilization of double electrodes is fundamentally solved, organic wastewater is more effectively treated, and the biodegradability of the wastewater is greatly improved.
Description
Technical Field
The invention relates to an electrochemical system for organic wastewater treatment, in particular to a flow type electrochemical system for generating double oxidants by the cooperation of double electrodes for organic wastewater treatment and a use method and application thereof.
Background
The treatment of organic waste water has been a big problem to be overcome in the field of environmental protection. Billions of tons of organic wastewater can not be effectively treated in China every year and is discharged into natural water, so that serious water pollution events are caused. Therefore, the development of a novel efficient organic wastewater treatment system is not slow enough. An electrochemical system is one of effective ways for treating organic wastewater, and the degradation-resistant organic pollutants in the organic wastewater are oxidized by electric energy, so that the aim of purifying water is fulfilled, such as an anodic oxidation method. The improvement of the degradation efficiency of the electrochemical system also becomes key content which needs to be overcome in scientific research, and the degradation efficiency of pollutants can be greatly improved by combining with free radical oxidation.
The invention fully utilizes the electric energy of the cathode and the anode of an electrochemical system to convert oxygen and electrolyte into oxidative chemical energy, and then utilizes an iron catalyst to activate the oxidative chemical energy to generate oxidative free radicals, thereby finally being used for effectively removing refractory organic matters in organic wastewater. Firstly, adsorbing pollutants on the surface of a cathode by graphene on the cathode by utilizing the strong adsorption effect of the graphene, generating hydrogen peroxide by utilizing the two-electron reduction reaction of oxygen input by an air pump, and directly oxidizing organic pollutants on the surface of the cathode by the generated strong-oxidizing hydroxyl free radicals through the activation effect of a ferrous iron catalyst provided by the graphene and an iron-carbon material to form a limited degradation effect, so that the oxidation efficiency of the hydroxyl free radicals of the cathode is greatly improved; in addition, electrolyte sulfate ions are oxidized into peroxydisulfate by the anode, and the peroxydisulfate is activated into sulfate radicals and hydroxyl radicals by using a ferrous iron catalyst provided by an iron-carbon material, and then organic pollutants difficult to degrade are effectively degraded; secondly, the powerful anodic oxidation of the electrochemical system can directly oxidize the organic pollutants by losing electrons, and the removal capability of the electrochemical system to the pollutants is further improved.
At present, most of electrochemical systems for treating organic wastewater utilize expensive and complex modified electrodes, and only utilize hydroxyl radicals to effectively remove refractory organic pollutants, so that electric energy resources are greatly wasted. For example: the three-dimensional electrode in chinese patent (patent No. CN 106966465 a) is used to construct an electrochemical system, which only uses hydroxyl radical oxidation to remove the pollutants in the wastewater, and the fact cannot overcome the extremely low treatment efficiency of the electrochemical system under alkaline conditions, and the electrode modification is expensive, and the electrode modification is very complex and does not achieve the ideal effect. Chinese patent (patent number: CN 103553188A) is based on an electrochemical system of an electrocatalytic particle electrode material, and the electrochemical system has greatly reduced degradation efficiency of pollutants because the coupling effect of a cathode and an anode in the aspect of combining free radical oxidation is ignored, and the electrode modification is very complicated and is not easy to popularize.
The development of an electrochemical system for organic wastewater treatment, which has a simple structure, can fully utilize energy and has low cost, is the first problem to be solved urgently. The invention is based on the principles of graphene adsorption limited domain degradation, anode sulfate radical degradation, anodic oxidation and cathode hydroxyl radical oxidation, and is characterized in that: the electric energy is fully converted into oxidizing chemical energy by utilizing double electrodes of an electrochemical system, and the bond breaking and the damage of the nondegradable organic pollutants are realized by coupling anodic oxidation and strong oxidizing free radicals, so that the effective degradation is realized; the removal efficiency of the organic pollutants by the diradical oxidation is higher; the problem of insufficient oxidation utilization of double electrodes is fundamentally solved, organic wastewater is more effectively treated, and the biodegradability of the wastewater is greatly improved.
Disclosure of Invention
The invention mainly aims to provide an electrochemical system for treating organic wastewater, and secondly aims to provide application of a flow type electrochemical system for cooperatively generating double oxidants by double electrodes for treating organic wastewater.
The invention is based on the principles of graphene adsorption limited domain degradation, anode sulfate radical degradation, anodic oxidation and cathode hydroxyl radical oxidation, and is characterized in that: the electric energy is fully converted into oxidizing chemical energy by utilizing double electrodes of an electrochemical system, and the bond breaking and the damage of the nondegradable organic pollutants are realized by coupling anodic oxidation and strong oxidizing free radicals, so that the effective degradation is realized; the removal efficiency of the organic pollutants by the diradical oxidation is higher; the problem of insufficient oxidation utilization of double electrodes is fundamentally solved, organic wastewater is more effectively treated, and the biodegradability of the wastewater is greatly improved.
The technical scheme of the invention is as follows.
A flow-type electrochemical system for generating double oxidants by double electrodes in a synergic manner for organic wastewater treatment comprises a reaction tank body, a peroxydisulfate self-generating anode plate, an anode current lead, a hydrogen peroxide self-generating cathode, a copper lead, a direct current power supply, a high-pressure air pump, an air delivery hose, an air diffusion air chamber, a cation exchange membrane, a cathode electro-Fenton reaction tank, an anode sulfate Fenton reaction tank and a water inlet feed inlet;
the hydrogen peroxide self-generating cathode divides the reaction tank body into an air diffusion air chamber and a Fenton reaction tank, and the cation exchange membrane divides the Fenton reaction tank into a cathode electro-Fenton reaction tank and an anode sulfate radical Fenton reaction tank; a peroxodisulfate self-producing anode plate is arranged in the anode sulfate Fenton reaction tank; the hydrogen peroxide self-generating cathode is connected with the negative electrode of a direct current power supply through a lead, and the peroxydisulfate self-generating anode plate is connected with the positive electrode of the direct current power supply through an anode current lead.
Furthermore, the top parts of the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank are provided with water inlet feed inlets, and the bottom parts of the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank are provided with water outlets; the feed inlet is communicated with the water outlet through a wastewater circulating delivery pipe, and a peristaltic pump is arranged on the wastewater circulating delivery pipe; the wastewater circulating delivery pipe is also provided with a wastewater outlet.
The invention also comprises a cathode chamber water outlet valve and an anode chamber water outlet valve; and the cathode chamber water outlet valve and the anode chamber water outlet valve are respectively arranged at the water outlet of the cathode electro-Fenton reaction tank and the water outlet of the anode sulfate Fenton reaction tank.
Further, the anode plate of the self-produced peroxodisulfate is a boron-doped diamond sheet, a palladium electrode sheet or a platinum electrode sheet.
Further, the anode current lead is made of platinum wires.
Further, the hydrogen peroxide self-generating cathode comprises a hydrophobic air diffusion carbon fiber layer, a graphene catalytic adsorption layer and a corrosion-resistant structure frame layer; the hydrophobic air diffusion carbon fiber layer is located on one side of the inner portion of the corrosion-resistant structure frame layer, and the graphene catalytic adsorption layer is filled in the rest space.
Further, the manufacturing method of the hydrogen peroxide self-generating cathode comprises the following steps: sequentially carrying out ultrasonic dipping on hydrophobic carbon fibers by alcohol and water for 1 hour, drying at 105 ℃ for 3 hours, and mixing graphene, polytetrafluoroethylene and an alcohol solution according to a mass ratio of 2-4: 1-1.5: 20-30, fully stirring, placing the mixture in an environment of 105 ℃ for drying to be pasty, taking out the mixture, uniformly coating the mixture on the surface layer of the treated hydrophobic carbon fiber layer by layer, placing the mixture in an environment of 105 ℃ again for drying to be completely dry, taking out the mixture, placing the mixture in a muffle furnace for activating at 355 ℃ for 2 hours, and placing the mixture in a corrosion-resistant structure frame layer to obtain the composite material.
Further, the rated output voltage of the dc power supply should be higher than 20V.
Further, the input air flow rate of the high-pressure air pump should be higher than 20L/min.
Furthermore, the wastewater circulating delivery pipe is formed by gluing corrosion-resistant polypropylene resin pipes.
Further, electrolytes in the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank are ammonium sulfate and ammonium thiocyanate, wherein the ratio of ammonium sulfate: ammonium thiocyanate: the mass ratio of the wastewater is 300-400: 0.5-1: 1000-1200.
Further, an iron-carbon material is used as a catalytic iron source, and the mass ratio of the iron-carbon material to the wastewater is 1: 5-8; the iron-carbon material is placed in the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank.
The flow type electrochemical system for generating the double oxidants by the cooperation of the double electrodes is applied to organic wastewater treatment.
Compared with the prior art, the invention has the advantages that:
(1) the invention fully utilizes the electric energy of the cathode and the anode of an electrochemical system to convert oxygen and electrolyte into oxidative chemical energy, and then utilizes an iron catalyst to activate the oxidative chemical energy to generate oxidative free radicals, thereby finally being used for effectively removing refractory organic matters in organic wastewater.
(2) Graphene on the cathode utilizes its powerful adsorption to adsorb the pollutant on the cathode surface to utilize the two electron reduction reaction to generate hydrogen peroxide with the oxygen of air pump input, through the activation of the ferrous iron catalyst that graphene and iron carbon material provided, the organic pollutant on the direct oxidation cathode surface of strong oxidizing nature hydroxyl free radical that generates forms the degradation effect of limit territory, has promoted the oxidation efficiency of cathode hydroxyl free radical greatly.
(3) Electrolyte sulfate ions are oxidized into peroxydisulfate by the anode, and the peroxydisulfate is activated into sulfate radicals and hydroxyl radicals by using a ferrous iron catalyst provided by an iron-carbon material, so that the organic pollutants difficult to degrade are effectively degraded.
(4) The powerful anodic oxidation of the electrochemical system can oxidize the organic pollutants directly without electrons, and the removal capacity of the electrochemical system to the pollutants is further improved.
Drawings
FIG. 1 is a flow-type electrochemical system for the co-generation of dual oxidants with dual electrodes for organic wastewater treatment in accordance with the present invention;
FIG. 2 is a diagram showing the accumulated amount of hydrogen peroxide generated by a hydrogen peroxide self-generating cathode in the system without adding an iron-carbon catalyst;
FIG. 3 shows the amount of peroxodisulfate accumulated in the system without the addition of an iron-carbon catalyst in the present invention;
FIG. 4 is a process curve of the TOC of wastewater containing persistent pesticide organic pollutants decreasing with time during the treatment of a flow-type electrochemical system according to the present invention;
FIG. 5 is a schematic diagram of the structure of the hydrogen peroxide self-generating cathode of the present invention.
The various components in the figure are as follows:
the hydrogen peroxide self-production anode plate 1, the anode current lead 2, the hydrogen peroxide self-production cathode 3, the hydrophobic air diffusion carbon fiber layer 4, the graphene catalytic adsorption layer 5, the corrosion-resistant structure frame layer 6, the copper lead 7, the direct current power supply 8, the high-pressure air pump 9, the air delivery hose 10, the air diffusion air chamber 11, the cation exchange membrane 12, the cathode electro-Fenton reaction tank 13, the anode sulfate radical Fenton reaction tank 14, the water inlet feed inlet 15, the cathode chamber water outlet valve 16, the anode chamber water outlet valve 17, the wastewater discharge outlet 18, the peristaltic pump 19 and the wastewater circulation delivery pipe 20.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
The manufacturing method of the hydrogen peroxide self-generating cathode comprises the following steps: the hydrophobic carbon fiber is sequentially subjected to ultrasonic immersion for 1 hour by alcohol and water and then dried for 3 hours at 105 ℃. Mixing graphene, polytetrafluoroethylene and an alcohol solution according to a mass ratio of 4: 1: 30, fully stirring, drying to be pasty at 105 ℃, taking out, uniformly coating the mixture on the surface layer of the treated hydrophobic carbon fiber layer by layer, and drying to be completely dry at 105 ℃. Taking out, putting into a muffle furnace, activating for 2 hours at 355 ℃, and then putting into a corrosion-resistant structure frame layer 6;
in the attached drawings of the specification, fig. 2 is an accumulated amount of hydrogen peroxide generated by a hydrogen peroxide self-generating cathode in a system without adding an iron-carbon catalyst, and shows that the flow electrochemical system can generate a large amount of hydrogen peroxide through an oxygen reduction reaction at the cathode, and further activate the hydrogen peroxide into an oxidizing free radical, such as a hydroxyl free radical. FIG. 3 is a graph showing the amount of peroxodisulfate accumulated in the system from the anode plate without the addition of an iron-carbon catalyst, showing that the flow electrochemical system can generate a large amount of peroxodisulfate by sulfate oxidation at the anode, which is then activated into oxidizing radicals, such as hydroxyl radicals and sulfate radicals. FIG. 4 is a process curve of the decrease of the wastewater TOC of the persistent pesticide organic pollutants with time in the treatment process of the flow-type electrochemical system, which shows that the flow-type electrochemical system still has a very strong degradation effect on the refractory organic pollutants, and the mineralization rate is higher than 99%.
As shown in fig. 1, the flow-type electrochemical system for generating double oxidants by the cooperation of double electrodes for organic wastewater treatment comprises a reaction tank body, a peroxydisulfate self-generating anode plate 1, an anode current lead 2, a hydrogen peroxide self-generating cathode 3, a copper lead 7, a direct current power supply 8, a high-pressure air pump 9, an air delivery hose 10, an air diffusion air chamber 11, a cation exchange membrane 12, a cathode electro-fenton reaction tank 13, an anode sulfate radical-fenton reaction tank 14 and a water inlet feed inlet 15; the hydrogen peroxide self-generating cathode 3 divides the reaction tank body into an air diffusion air chamber 11 and a Fenton reaction tank, and the cation exchange membrane 12 divides the Fenton reaction tank into a cathode electro-Fenton reaction tank 13 and an anode sulfate radical Fenton reaction tank 14; a peroxodisulfate self-generating anode plate 1 is arranged in the anode sulfate Fenton reaction tank 14; the hydrogen peroxide self-generating cathode 3 is connected with the negative electrode of the direct current power supply 8 through a lead, and the peroxydisulfate self-generating anode plate 1 is connected with the positive electrode of the direct current power supply 8 through an anode current lead 2. The top parts of the cathode electro-Fenton reaction tank 13 and the anode sulfate Fenton reaction tank 14 are provided with water inlet feed inlets 15, and the bottom parts are provided with water outlets; the feed inlet is communicated with the water outlet through a wastewater circulating delivery pipe 20, and a peristaltic pump 19 is arranged on the wastewater circulating delivery pipe 20; the wastewater circulating and conveying pipe 20 is also provided with a wastewater outlet 18. The invention also comprises a cathode chamber water outlet valve 16 and an anode chamber water outlet valve 17; and the cathode chamber water outlet valve 16 and the anode chamber water outlet valve 17 are respectively arranged at the water outlet of the cathode electro-Fenton reaction tank 13 and the water outlet of the anode sulfate radical Fenton reaction tank 14. The peroxodisulfate self-producing anode plate 1 is a boron-doped diamond sheet, a palladium electrode sheet or a platinum electrode sheet; the anode current lead 2 is a platinum wire. The hydrogen peroxide self-generating cathode 3 comprises a hydrophobic air diffusion carbon fiber layer 4, a graphene catalytic adsorption layer 5 and a corrosion-resistant structure frame layer 6; the hydrophobic air diffusion carbon fiber layer 4 is located on one side inside the corrosion-resistant structure frame layer 6, and the rest space is filled with the graphene catalytic adsorption layer 5. The manufacturing method of the hydrogen peroxide self-generating cathode 3 comprises the following steps: sequentially carrying out ultrasonic dipping on hydrophobic carbon fibers by alcohol and water for 1 hour, drying at 105 ℃ for 3 hours, and mixing graphene, polytetrafluoroethylene and an alcohol solution according to a mass ratio of 2-4: 1-1.5: 20-30, fully stirring, placing the mixture in an environment of 105 ℃ for drying to be pasty, taking out the mixture, uniformly coating the mixture on the surface layer of the treated hydrophobic carbon fiber layer by layer, placing the mixture in an environment of 105 ℃ again for drying to be completely dry, taking out the mixture, placing the mixture in a muffle furnace for activating at 355 ℃ for 2 hours, and placing the mixture in a corrosion-resistant structure frame layer 6 to obtain the composite material. The rated output voltage of the direct current power supply 8 is higher than 20V; the speed of the input air flow of the high-pressure air pump 9 is higher than 20L/min; the wastewater circulating and conveying pipe 20 is formed by gluing corrosion-resistant polypropylene resin pipes. The electrolytes in the cathodic electro-Fenton reaction tank 13 and the anodic sulfate radical Fenton reaction tank 14 are ammonium sulfate and ammonium thiocyanate, wherein the ratio of ammonium sulfate: ammonium thiocyanate: the mass ratio of the wastewater is 300-400: 0.5-1: 1000-1200. An iron-carbon material is used as a catalytic iron source, and the mass ratio of the iron-carbon material to the wastewater is 1: 5-8; the iron-carbon material is placed in the cathode electro-Fenton reaction tank 13 and the anode sulfate radical Fenton reaction tank 14.
Example 1
20L of wastewater which is collected by a certain organization and is rich in persistent pesticide organic pollutants is accurately measured by a COD detector and a TOC detector, and the COD in the obtained mixed solution is 2650mg/L and the TOC is 1790 mg/L.
4kg of iron-carbon materials are added into the system, the output voltage is adjusted to 30V, and the flow type electrochemical system for generating double oxidants by the cooperation of the double electrodes for organic wastewater treatment starts to operate. The air input speed of the high-pressure air pump is adjusted to be 20L/min. And starting a sample adding program, enabling the waste liquid to enter the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank from the water inlet and the feed inlet, stopping inputting the waste liquid when the water level reaches the reaction tank part 4/5, and starting the peristaltic pump. And waiting for wastewater treatment, wherein COD and TOC of the wastewater treatment liquid are detected for a plurality of times, the reaction is started for about 5 hours, the TOC of the treatment liquid is close to 0, and the treatment liquid reaches the discharge standard. Opening a valve of a treated wastewater outlet, and discharging a treatment solution; and after the treated liquid is discharged, closing the waste water outlet valve, refilling the organic waste water in the flow type electrochemical system, and starting the next waste water treatment process.
Example 2
30L of coking wastewater collected by a certain mechanism is accurately measured by a COD detector and a TOC detector, the COD in the obtained mixed solution is about 3612mg/L, and the TOC is 2954 mg/L.
6kg of iron-carbon materials are added into the system, the output voltage is adjusted to 35V, and the flow type electrochemical system for generating double oxidants by the cooperation of the double electrodes for organic wastewater treatment starts to operate. The air input speed of the high-pressure air pump is adjusted to be 25L/min. And starting a sample adding program, enabling the waste liquid to enter the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank from the water inlet and the feed inlet, stopping inputting the waste liquid when the water level reaches the reaction tank part 4/5, and starting the peristaltic pump. And waiting for wastewater treatment, wherein COD and TOC of the wastewater treatment liquid are detected for a plurality of times, the reaction is started for about 8 hours, and the TOC of the treatment liquid is reduced to 5.32 mg/L. Opening a valve of a treated wastewater outlet, and discharging a treatment solution; and after the treated liquid is discharged, closing the waste water outlet valve, refilling the organic waste water in the flow type electrochemical system, and starting the next waste water treatment process.
Example 3
The COD detector and the TOC detector are used for accurately measuring 25L of domestic sewage collected by a certain institution, and the COD in the obtained mixed solution is about 3449mg/L and the TOC is 2944 mg/L.
5kg of iron-carbon materials are added into the system, the output voltage is adjusted to 30V, and the flow type electrochemical system for generating double oxidants by the cooperation of the double electrodes for organic wastewater treatment starts to operate. The air input speed of the high-pressure air pump is adjusted to be 25L/min. And starting a sample adding program, enabling the waste liquid to enter the cathode electro-Fenton reaction tank and the anode sulfate radical Fenton reaction tank from the water inlet and the feed inlet, stopping inputting the waste liquid when the water level reaches the reaction tank part 4/5, and starting the peristaltic pump. And waiting for wastewater treatment, detecting COD and TOC of the wastewater treatment liquid for multiple times, and reducing the TOC of the treatment liquid to 23.265mg/L after about 6 hours of reaction. Opening a valve of a treated wastewater outlet, and discharging a treatment solution; and after the treated liquid is discharged, closing the waste water outlet valve, refilling the organic waste water in the flow type electrochemical system, and starting the next waste water treatment process.
Claims (10)
1. A flow type electrochemical system for generating double oxidants by double electrodes in a synergic manner for organic wastewater treatment is characterized by comprising a reaction tank body, a peroxydisulfate self-generating anode plate (1), an anode current lead (2), a hydrogen peroxide self-generating cathode (3), a copper lead (7), a direct current power supply (8), a high-pressure air pump (9), an air delivery hose (10), an air diffusion air chamber (11), a cation exchange membrane (12), a cathode electro-Fenton reaction tank (13), an anode sulfate radical Fenton reaction tank (14) and a water inlet feed inlet (15);
the hydrogen peroxide self-generating cathode (3) divides the reaction tank body into an air diffusion air chamber (11) and a Fenton reaction tank, and the cation exchange membrane (12) divides the Fenton reaction tank into a cathode electro-Fenton reaction tank (13) and an anode sulfate radical Fenton reaction tank (14); a self-produced peroxydisulfate anode plate (1) is arranged in the anode sulfate Fenton reaction tank (14); the hydrogen peroxide self-generating cathode (3) is connected with the negative electrode of a direct current power supply (8) through a lead, and the peroxydisulfate self-generating anode plate (1) is connected with the positive electrode of the direct current power supply (8) through an anode current lead (2).
2. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: the top parts of the cathode electro-Fenton reaction tank (13) and the anode sulfate radical Fenton reaction tank (14) are provided with water inlet feed inlets (15), and the bottom parts are provided with water outlets; the feed inlet is communicated with the water outlet through a wastewater circulating delivery pipe (20), and a peristaltic pump (19) is arranged on the wastewater circulating delivery pipe (20); the wastewater circulating delivery pipe (20) is also provided with a wastewater outlet (18).
3. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: also comprises a cathode chamber water outlet valve (16) and an anode chamber water outlet valve (17); and the cathode chamber water outlet valve (16) and the anode chamber water outlet valve (17) are respectively arranged at the water outlet of the cathode electro-Fenton reaction tank (13) and the water outlet of the anode sulfate radical Fenton reaction tank (14).
4. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: the peroxodisulfate self-producing anode plate (1) is a boron-doped diamond sheet, a palladium electrode sheet or a platinum electrode sheet;
the anode current lead (2) is a platinum wire.
5. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: the hydrogen peroxide self-generating cathode (3) comprises a hydrophobic air diffusion carbon fiber layer (4), a graphene catalytic adsorption layer (5) and a corrosion-resistant structure frame layer (6); the hydrophobic air diffusion carbon fiber layer (4) is located on one side inside the corrosion-resistant structure frame layer (6), and the rest space is filled with the graphene catalytic adsorption layer (5).
6. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 5, wherein: the manufacturing method of the hydrogen peroxide self-generating cathode (3) comprises the following steps: sequentially carrying out ultrasonic dipping on hydrophobic carbon fibers by alcohol and water for 1 hour, drying at 105 ℃ for 3 hours, and mixing graphene, polytetrafluoroethylene and an alcohol solution according to a mass ratio of 2-4: 1-1.5: 20-30, fully stirring, placing the mixture in an environment of 105 ℃ for drying to be pasty, taking out the mixture, uniformly coating the mixture on the surface layer of the treated hydrophobic carbon fiber layer by layer, placing the mixture in an environment of 105 ℃ again for drying to be completely dry, taking out the mixture, placing the mixture in a muffle furnace for activating at 355 ℃ for 2 hours, and placing the mixture in a corrosion-resistant structure frame layer (6) to obtain the composite material.
7. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: the rated output voltage of the direct current power supply (8) is higher than 20V;
the speed of the input air flow of the high-pressure air pump (9) is higher than 20L/min;
the wastewater circulating and conveying pipe (20) is formed by gluing corrosion-resistant polypropylene resin pipes.
8. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: electrolytes in the cathode electro-Fenton reaction tank (13) and the anode sulfate Fenton reaction tank (14) are ammonium sulfate and ammonium thiocyanate, wherein the ratio of ammonium sulfate: ammonium thiocyanate: the mass ratio of the wastewater is 300-400: 0.5-1: 1000-1200.
9. The flow-type electrochemical system for the cooperative generation of dual oxidants by dual electrodes for organic wastewater treatment as claimed in claim 1, wherein: an iron-carbon material is used as a catalytic iron source, and the mass ratio of the iron-carbon material to the wastewater is 1: 5-8; the iron-carbon material is placed in the cathode electro-Fenton reaction tank (13) and the anode sulfate radical Fenton reaction tank (14).
10. The flow type electrochemical system for generating the double oxidant by the double electrode cooperation of claims 1-9 is applied to organic wastewater treatment.
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| CN114481187A (en) * | 2022-02-15 | 2022-05-13 | 中国科学院赣江创新研究院 | electro-Fenton cathode material and preparation method and application thereof |
| CN115180705A (en) * | 2022-06-23 | 2022-10-14 | 湖南新沃环境科技有限公司 | Organic wastewater treatment method and system |
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