CN214141734U

CN214141734U - H2O2Solution electrocatalysis preparation and sewage treatment integrated system

Info

Publication number: CN214141734U
Application number: CN202022960216.6U
Authority: CN
Inventors: 卜云飞; 王耀彬; 盖鑫磊; 李峰; 赵云霞; 蔡炜
Original assignee: Nanjing University of Information Science and Technology
Current assignee: Nanjing University of Information Science and Technology
Priority date: 2020-12-11
Filing date: 2020-12-11
Publication date: 2021-09-07
Anticipated expiration: 2030-12-11

Abstract

The utility model discloses a H₂O₂The solution electrocatalysis preparation and sewage treatment integrated system comprises H₂O₂Preparation apparatus and wastewater treatment apparatus, H₂O₂The preparation device comprises an anode, a cathode and a storage tank, wherein a solid electrolyte layer is arranged between the anode and the cathode, and the storage tank is connected with the anode and the cathodeOn the solid electrolyte layer, sewage treatment plant includes the equalizing basin, is provided with the inlet on the equalizing basin and advances the waste water mouth, and the holding vessel is connected to the equalizing basin top, and the bottom links to each other through liquid outlet and oxidation reaction pond, and oxidation reaction pond bottom is provided with the outlet. The system uses hydrogen and oxygen as raw materials, hydrogen peroxide is prepared through electrolysis, no organic solvent is added, the preparation process is green and environment-friendly, and the production rate of the hydrogen peroxide reaches 3.4mmol/cm²The concentration of the solution is up to 20%, purification is not needed, the dangerousness in storage and transportation is reduced, the solution can be used during production, dye wastewater and medical wastewater can be effectively treated, dye and bacterial colonies are degraded, and the dual effects of degradation and disinfection are achieved.

Description

H2O2Solution electrocatalysis preparation and sewage treatment integrated system

Technical Field

The utility model relates to a solution, integrative system of sewage treatment, more specifically relates to a H₂O₂Solution electrocatalysis preparation and sewage treatment integrated system.

Background

The methods for industrially treating dye wastewater mainly include precipitation, oxidation, membrane separation, activated carbon, carbon nanotube adsorption, fenton oxidation, wet oxidation, etc., but these techniques are difficult to be widely used due to low efficiency, high price, etc. For example, the effect of treating the cationic dye wastewater by coagulating sedimentation is poor, and the amount of mud generated by coagulation is large; membrane separation is expensive; the adsorption is carried out by using activated carbon, because of the particularity of cationic dye molecules, the adsorption efficiency of the activated carbon is generally low, and the activated carbon is adsorbed by using carbon nano tubes with larger specific surface area, although the adsorption efficiency is higher, the activated carbon is expensive and has certain toxicity, the Fenton oxidation is utilized, the amount of mud generated in the subsequent process is larger, and the subsequent treatment difficulty and cost are increased; the wet oxidation reaction needs high temperature and high pressure, which increases the equipment requirement and treatment cost, the advanced oxidation technology for treating dye wastewater takes hydroxyl radical as main oxidant to realize the degradation process of organic matter, the key of the technology is to prepare high-efficiency and stable catalyst, hydrogen peroxide H₂O₂Is a raw material or product suitable for various industrial applications, and the aqueous solution of the water-soluble chitosan has strong oxidizing property and is suitable for medical use, food and environmental disinfection. Conventional peroxygenThe preparation method of hydrogen peroxide H by anthraquinone process₂O₂The method usually produces hydrogen peroxide mixture with concentration of 1-2 wt%, and the method has complex process, low yield, expensive purification and distillation, and concentrated infrastructure, so that the hydrogen peroxide solution is safe to transport, store and use.

Disclosure of Invention

Utility model purpose: the utility model aims at providing a preparation process safety, preparation result concentration are high, can directly use sewage treatment, avoid the H of the safety risk in transportation and the storage process₂O₂Solution electrocatalysis preparation and sewage treatment integrated system.

The technical scheme is as follows: h of the utility model₂O₂The solution electrocatalysis preparation and sewage treatment integrated system comprises H₂O₂Preparation apparatus and wastewater treatment apparatus, H₂O₂The preparation device comprises an anode, a cathode and a storage tank, wherein a solid electrolyte layer is arranged between the anode and the cathode, the storage tank is connected to the solid electrolyte layer, the sewage treatment device comprises an adjusting tank, a liquid inlet and a waste water inlet are formed in the adjusting tank, the top of the adjusting tank is connected with the storage tank, the bottom of the adjusting tank is connected with an oxidation reaction tank through the liquid outlet, and a water outlet is formed in the bottom of the oxidation reaction tank.

Wherein, the inlet of equalizing basin is connected with the sulphuric acid pond, and the bottom is provided with the mud discharging port, is connected with the force pump between equalizing basin and the oxidation reaction tank, is connected with the force pump between equalizing basin and the holding vessel, has laid high absorption activated carbon filler in the oxidation reaction tank, and the bottom is provided with aeration pipe and mud discharging port, H₂O₂The preparation device comprises an anode flow channel, a gas diffusion layer, an anode catalyst layer and a cation exchange membrane which are sequentially arranged inside an anode, wherein the cation exchange membrane is tightly attached to the surface of a solid electrolyte layer, the anode flow channel comprises an anode inlet flow channel and an anode outlet flow channel, the anode catalyst layer is IrO₂the/GCN heterogeneous layer is a graphitized carbon nitride GCN nanosheet and IrO₂Synthetic heterostructure layers H₂O₂The preparation device comprises a cathode, a gas flow channel, a gas diffusion layer, a cathode catalyst layer and an anion exchange membrane, wherein the cathode catalyst layer is a carbon black cathode catalyst layer, the gas flow channel comprises a cathode gas inlet channel and a cathode gas outlet channel, the bottom of a solid electrolyte layer is provided with a water inlet, the upper end of the solid electrolyte layer is connected with a storage tank through a water outlet, the solid electrolyte layer is a porous styrene-divinylbenzene sulfonated copolymer with the pore diameter of 50-300 mu m, and an anode and a cathode are connected to a power supply device.

The working principle is as follows: the utility model discloses gas diffusion layer provides gas passage for electrode reaction, has played the effect that supports catalyst layer, stable electrode structure simultaneously, has established the millimeter yardstick from gas flow channel to the bridge between the nanometer yardstick of catalyst, during the preparation hydrogen peroxide, respectively with reactant H₂And O₂After passing through the gas diffusion layers, respectively, the gas diffusion layers enter the functionalized electrode layer, H₂Oxidation to H⁺And electrons, humidified oxygen, O, is injected into the cathode side₂Is reduced to HO^2–Generation of H⁺And HO^2-Then respectively enters the porous solid electrolyte of the central part through the cation exchange membrane and the anion exchange membrane to react to generate H₂O₂Then the water is taken out by the deionized water flow of the middle layer; the oxidation reaction at the anode side is more easily catalyzed by the electrocatalysis and reacted with the cathode 2e^–ORR coupling, the all-solid-state electrolyte can prevent the interference of foreign ions in the electrolyte, eliminate the influence of pH change and other side reactions on the purity of the hydrogen peroxide solution, meanwhile, the porous structure of the solid electrolyte is favorable for ion transmission, and after the porous structure is subjected to sulfonation hydrophilic modification, H can be further improved⁺And OOH^-The ion transmission speed shows the obvious advantages of small internal ohmic loss and high yield after the fast combination of the anions and the cations, so that the prepared hydrogen peroxide has higher purity and higher speed, and the preparation process and the storage process are safer; the graphitized carbon nitride has a unique C site, and particularly, the coordination environment rich in N induces IrO₂And GCN, finally adjusting the electronic structure of the Ir active site with low coordination number, showing excellent OER performance under acidic condition and having extremely high chemical stability to prevent corrosionAnd oxidizing, the anode catalytic layer selects IrO₂the/GCN heterogeneous layer can ensure the output of H + at the anode, the sewage contains nitrogen, phosphorus, sulfur, pathogenic bacteria, organic dye and other components, hydrogen peroxide in the regulating tank generates OH oxidation after being treated by sulfuric acid, and OH adsorbs organic matters in the sewage to generate oxidation reaction to remove pollutants. For pathogenic bacteria, viruses, bacteria and the like can be inactivated due to strong oxidizing property, so that various microorganisms can be killed and inhibited. Due to the oxidation effect, the method also has a good removal effect on COD and NH3-N in the landfill leachate. Mud is discharged bottom the equalizing basin, and the water after the processing is arranged to high adsorptivity active carbon oxidation reaction tank through the force pump, and sewage is through high adsorption active carbon adsorption in high adsorptivity active carbon oxidation reaction tank, further adsorbs organic matter composition in with sewage and gets rid of, can further oxygen contact with water effectively through the effect that the aeration pipe sprayed to make sewage dispersion spray through the aeration pipe, can reduce the active carbon hole again and block up, influence adsorption effect. After treatment, the sewage can be discharged according with the discharge standard, and the generated sludge is discharged through a sludge outlet at the bottom of the oxidation reaction tank.

Has the advantages that: compared with the prior art, the utility model, its advantage is: 1. the raw materials are hydrogen and oxygen, the hydrogen peroxide is prepared by electrolysis, and no organic solvent is added, so that the preparation process is green and environment-friendly; 2. the productivity of hydrogen peroxide reaches 3.4mmol/cm²The concentration of the solution is up to 20 percent, purification is not needed, the danger in storage and transportation is reduced, and the solution is used after production; 3. can effectively treat dye wastewater and medical wastewater, degrade dye and bacterial colonies, and have dual effects of degradation and disinfection.

Drawings

Fig. 1 is a schematic structural diagram of the present invention.

Detailed Description

As shown in FIG. 1, H₂O₂The solution electrocatalysis preparation and sewage treatment integrated system comprises H₂O₂Preparation apparatus and wastewater treatment apparatus, H₂O₂The preparation device comprises an anode, a cathode and a storage tank 13, wherein the anode and the cathode are connected on a power supply 18 and between the anode and the cathodeThe device is provided with a solid electrolyte layer 14, a water inlet 15 is arranged at the bottom of the solid electrolyte layer 14, the upper end of the solid electrolyte layer is connected with a storage tank 13 through a water outlet, the solid electrolyte layer 14 is a porous styrene-divinylbenzene sulfonated copolymer with the aperture of 120 mu m, an anode flow channel, a gas diffusion layer 3, an anode catalysis layer 4 and a cation exchange membrane 5 are sequentially arranged inside an anode, the cation exchange membrane 5 is tightly attached to the surface of the solid electrolyte layer 14, the anode flow channel comprises an anode inlet flow channel 7 and an anode outlet flow channel 6, the anode catalysis layer 4 is formed by graphitized carbon nitride GCN nanosheets and IrO₂Synthetic IrO₂A gas flow channel, a gas diffusion layer 3, a cathode catalyst layer 11 and an anion exchange membrane 12 are sequentially arranged in a cathode, the cathode catalyst layer 11 is a carbon black cathode catalyst layer, the gas flow channel comprises a cathode inlet flow channel 9 and a cathode outlet flow channel 10, and a storage tank 13 is connected to a solid electrolyte layer 14; sewage treatment plant includes equalizing basin 8, be provided with inlet 1 and the waste water inlet 2 of connecting the sulphuric acid pond on the equalizing basin 8, hold-up vessel 13 is connected through the force pump in the 8 tops of equalizing basin, the bottom links to each other with oxidation reaction tank 17 through the liquid outlet, be connected with the force pump between equalizing basin 8 and the oxidation reaction tank 17, oxidation reaction tank 17 bottom is provided with outlet 16, it is 3 mm's high adsorption active carbon filler to have laid the particle diameter in oxidation reaction tank 17, highly occupy the 30% of oxidation reaction tank 17 height, bulk density is 1g/ml, specific surface area is 800m²And the bottom of the aerator is provided with an aeration pipe and a sludge discharge port.

When in use, the reactants H are respectively added₂And O₂An anode inlet flow channel 7 and a cathode inlet flow channel 9 are respectively introduced into the anode inlet flow channel 7 and the cathode inlet flow channel 9, and respectively enter the gas diffusion layer 3 and then enter the IrO₂The anode catalyst layer 4 and the cathode catalyst layer 11 of the/GCN have the following reactions:

H₂oxidation reaction HOR: h₂→2H⁺+2e^–

H⁺The cathode side was injected with humidified oxygen, O, of 50sccm through the cation exchange membrane into the solid electrolyte layer 14₂Is reduced to HO^2–The following reaction takes place:

2e^–O₂reduction reaction 2e^–-ORR：O₂+H₂O+2e^–→HO^2–+OH^–

Generated HO^2-The solid electrolyte 14 is reacted to produce H by passing through the anion exchange membrane into the porous solid electrolyte 14 in the center portion₂O₂，

H₂O₂The synthesis reaction of (1): HO^2–+H⁺→H₂O₂

Then the deionized water flow in the middle layer is taken out to a storage tank 13 for storage, and the productivity of the hydrogen peroxide reaches 3.4mmol/cm²The solution concentration is up to 20 percent.

Wherein, IrO₂The preparation process of the/GCN anode catalyst layer 4 is as follows:

1.0g of melamine was placed in a muffle furnace at 3 ℃ for min^-1Heating at 550 ℃ for 2h, cooling to room temperature in a furnace to obtain massive Graphitized Carbon Nitride (GCN), immersing the synthesized massive GCN in 6M HCl, performing ultrasonic treatment for 1h, stirring at room temperature for 6h, centrifugally collecting functionalized GCN nanosheets, washing with deionized water, and drying at 60 ℃ to obtain GCN nanosheets; adding 7mg of K to 30ml of deionized water₂IrCl₆And 10mg of GCN nanoplatelets, the mixture was heated to 80 ℃ and continuously stirred for 6 hours, and then transferred to a 50ml stainless steel autoclave and maintained at 180 ℃ for 4 hours. The resulting product was collected by centrifugation and rinsed several times with deionized water. The final sample was dried at 80 ℃ and then annealed in air at 350 ℃ for 2h to obtain IrO₂a/GCN heterogeneous layer.

H carried over by the flow of deionized water₂O₂The solution flows to a storage tank 13 for storage, the storage tank 13 is communicated with a regulating reservoir 8, and H is pumped by a pressure pump₂O₂The solution is introduced into an adjusting tank 8, sulfuric acid and H flow into the adjusting tank 8 through a liquid inlet 1₂O₂The molar concentration ratio of the solution is 1: 3, the wastewater enters the regulating reservoir 8 through the wastewater inlet 2, after mixing and sedimentation, the liquid is introduced into the oxidation reaction tank 17 through the pressure pump, the sludge is discharged through a sludge discharge port at the bottom of the regulating reservoir 8, the liquid is subjected to adsorption by the high adsorption activated carbon filler and full reaction treatment by the aeration pipe in the oxidation reaction tank 17, and the sludge is discharged through a discharge outletThe water gap 16 discharges, and tests show that the system has a quick disinfection effect on escherichia coli, the sterilization rate is 43% in 5 minutes, the sterilization rate reaches more than 99.9999% in 120 minutes, and sludge in the oxidation reaction tank 17 is discharged through a sludge discharge port at the bottom in the oxidation reaction tank 17.

Claims

1. H₂O₂The solution electrocatalysis preparation and sewage treatment integrated system is characterized by comprising H₂O₂Preparation apparatus and sewage treatment apparatus, said H₂O₂The preparation facilities includes positive pole, negative pole and holding vessel (13), be provided with solid electrolyte layer (14) between positive pole and the negative pole, holding vessel (13) are connected on solid electrolyte layer (14), sewage treatment plant includes equalizing basin (8), be provided with inlet (1) and waste water inlet (2) on equalizing basin (8), holding vessel (13) are connected at equalizing basin (8) top, and the bottom links to each other through liquid outlet and oxidation reaction pond (17), oxidation reaction pond (17) bottom is provided with outlet (16).

2. H according to claim 1₂O₂Solution electro-catalysis is prepared, integrative system of sewage treatment, its characterized in that, sulphuric acid pond is connected in inlet (1) of equalizing basin (8), and the bottom is provided with the mud discharging mouth, be connected with the force pump between equalizing basin (8) and oxidation reaction pond (17), be connected with the force pump between equalizing basin (8) and holding vessel (13).

3. H according to claim 1₂O₂The integrated system for the electro-catalysis preparation of the solution and the sewage treatment is characterized in that high-adsorption activated carbon filler with the particle size of 2-4mm is paved in the oxidation reaction tank (17), and an aeration pipe and a sludge discharge port are arranged at the bottom.

4. H according to claim 1₂O₂The solution electrocatalysis preparation and sewage treatment integrated system is characterized in that the H₂O₂The anode of the preparation device is internally provided with an anode flow passage, a gas diffusion layer (3), an anode catalyst layer (4) and cations in sequenceAnd the cation exchange membrane (5) is tightly attached to the surface of the solid electrolyte layer (14).

5. H according to claim 4₂O₂The integrated system for preparing the solution by electro-catalysis and treating the sewage is characterized in that the anode flow channel comprises an anode inlet flow channel (7) and an anode outlet flow channel (6), and the anode catalysis layer (4) is IrO₂a/GCN heterogeneous layer.

6. H according to claim 1₂O₂The solution electrocatalysis preparation and sewage treatment integrated system is characterized in that the H₂O₂The cathode of the preparation device is internally provided with a gas flow channel, a gas diffusion layer (3), a cathode catalyst layer (11) and an anion exchange membrane (12) in sequence, wherein the cathode catalyst layer (11) is a carbon black cathode catalyst layer.

7. H according to claim 6₂O₂The integrated system for the electro-catalysis preparation of the solution and the sewage treatment is characterized in that the gas flow channel comprises a cathode gas inlet flow channel (9) and a cathode gas outlet flow channel (10).

8. H according to claim 1₂O₂Solution electro-catalysis prepares, integrative system of sewage treatment, its characterized in that, solid electrolyte layer (14) bottom is equipped with water inlet (15), and the upper end passes through the delivery port and connects holding vessel (13).

9. H according to claim 1₂O₂The integrated system for solution electrocatalysis preparation and sewage treatment is characterized in that the solid electrolyte layer (14) is a porous styrene-divinylbenzene sulfonated copolymer with the pore diameter of 50-300 mu m.

10. H according to claim 1₂O₂The integrated system for preparing the solution by electrocatalysis and treating the sewage is characterized in that the anode and the cathode are connected with a power supply (18).