Preparation method of multi-component electro-wet combined catalytic modification electrode film and sewage treatment device

Abstract

The application provides a preparation method of a multi-component electro-wet combined catalytic modified electrode membrane and a sewage treatment device, and belongs to the field of industrial wastewater treatment. The preparation method comprises the following steps: casting a membrane liquid; scraping a membrane; loading an active component; and modifying a Y-Co / GO / PES membrane. Compared with the prior art, the application has the following advantages: due to the presence of a pore former, the prepared electrode membrane has micropores; experiments show that the membrane has a good physical interception effect and a COD removal capacity, and solves the problem of low COD removal rate in dye wastewater. The application improves the solid-liquid mixing condition after treatment by a traditional advanced oxidation method, saves treatment procedures and time, and simultaneously reduces the treatment cost as much as possible.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of industrial wastewater treatment, and particularly relates to a preparation method of a multi-component electro-humidification combined catalytic modified electrode membrane and a wastewater treatment device. BACKGROUND

[0002] Dyes are widely used in printing and dyeing, leather, papermaking, cosmetics, paint, rubber, plastic, pesticides, wood preservatives and various industries. Generally speaking, the discharge of wastewater containing 10-200 mg / L of dyes into natural water bodies can cause toxicity to organisms and even produce "three effects" (i.e. carcinogenic, mutagenic and teratogenic effects), so it is necessary to develop printing and dyeing wastewater treatment and control technology.

[0003] Traditional printing and dyeing wastewater treatment technologies include ion exchange method, membrane separation method, chemical precipitation method and oxidation-reduction method, which can better degrade and remove dye molecules in printing and dyeing wastewater, and have better effects on treating printing and dyeing wastewater with low COD concentration.

[0004] However, at present, with the increasing maturity of printing and dyeing technology, the biochemical properties of various dyeing dyes are getting better and better, and the printing and dyeing wastewater contains a large amount of organic matter with color groups, and the COD concentration of organic matter in printing and dyeing wastewater is gradually increasing. If the traditional printing and dyeing wastewater treatment technology is used to treat high-COD printing and dyeing wastewater, the COD removal rate in dye wastewater is low, and high COD will affect the effect of traditional printing and dyeing wastewater treatment technology on dye molecules, thus resulting in poor treatment effect of printing and dyeing wastewater. Therefore, it is urgent to develop a process with higher treatment efficiency to meet the current environmental requirements. SUMMARY

[0005] To solve one of the above problems, the application provides a preparation method of a multi-component electro-humidification combined catalytic modified electrode membrane and a wastewater treatment device, which has physical interception and chemical oxidation functions, and under the action of an external voltage, increases the oxidation treatment capacity of the electrode membrane, simultaneously performs physical and chemical treatment on wastewater, solves the problem of poor treatment of high-COD printing and dyeing wastewater by traditional methods, saves treatment procedures and time, and reduces treatment cost as much as possible.

[0006] The technical scheme of the application is as follows:

[0007] The application provides a preparation method of a multi-component electro-humidification combined catalytic modified electrode membrane, which is characterized by comprising the following steps:

[0008] (a) Casting solution preparation: graphene oxide (GO), polyvinylpyrrolidone (PVP) are added to N-methyl pyrrolidone (NMP), ultrasonic dispersion for 1h, then polyether sulfone (PES) is added, then it is transferred into a water bath, kept at 45-50℃, heated and stirred for 12-14h, after polyether sulfone (PES) is completely dissolved, a mixed solution is obtained, the mixed solution is ultrasonic degassed for 2h, a uniform casting solution is prepared, the total amount of polyvinylpyrrolidone (PVP), N-methyl pyrrolidone (NMP) and polyether sulfone (PES) is 100%;

[0009] (b) Film scraping: polyacrylonitrile-based carbon fiber cloth is used as a substrate, the polyacrylonitrile-based carbon fiber cloth is evenly laid on a glass plate, a steam iron is used to iron the polyacrylonitrile-based carbon fiber cloth, transparent adhesive tape is used to fix the polyacrylonitrile-based carbon fiber cloth, the polyacrylonitrile-based carbon fiber cloth is as flat as possible, then the casting solution prepared in step (a) is poured on the polyacrylonitrile-based carbon fiber cloth, the film thickness of the doctor blade is adjusted to 200μm, film scraping is carried out by using a film scraper, after film scraping is completed, it is exposed to air for 20s, an electrode pre-film is prepared, the obtained electrode pre-film is stored in deionized water for standby;

[0010] (c) Loading active components: yttrium oxide and cobalt oxide are dissolved in water to prepare a composite impregnating solution with a concentration of 1mol / L-5mol / L, the electrode pre-film obtained in step (b) is first placed in an aqueous ethanol solution for pretreatment, polyvinylpyrrolidone (PVP) is dissolved to form pores, then deionized water is used for washing, then the electrode pre-film is immersed in the composite impregnating solution, the film is completely immersed in the solution, and after standing for 24h, the electrode pre-film is taken out and washed with deionized water, thereby a Y-Co / GO / PES film is prepared;

[0011] (d) Modification of Y-Co / GO / PES film: the Y-Co / GO / PES film prepared in step (c) is immersed in an ascorbic acid solution, then it is transferred into a constant temperature heating magnetic stirrer, heated in a water bath to 95-100℃, and reacted for 2h, thereby graphene oxide (GO) in the film is reduced to reduced graphene oxide (rGO), and a Y-Co / rGO / PES anode film is obtained, which is a multi-component electro-wet combined catalytic modified electrode film.

[0012] Further, in step (a), the casting solution consists of 0.3% of graphene oxide (GO), 0.5%-10% of polyvinylpyrrolidone (PVP), 15%-20% of polyether sulfone (PES), and the balance of N-methyl pyrrolidone (NMP), the total amount of the above components is 100%.

[0013] Further, in the step (a), the casting solution is composed of 0.3% graphene oxide (GO), 0.5% polyvinylpyrrolidone (PVP), 16% polyethersulfone (PES) and 83.2% N-methylpyrrolidone (NMP) by mass percentage.

[0014] Further, in the step (c), the volume ratio of water to ethanol in the aqueous ethanol solution is 1:4.

[0015] Further, in the step (c), the mass ratio of yttrium oxide to cobalt oxide is 2:1.

[0016] Further, in the step (d), the mass percentage of ascorbic acid in the ascorbic acid solution is 10%.

[0017] The application further discloses a sewage treatment device, which is characterized by comprising a reaction tank, an anode membrane assembly placed in the reaction tank and connected with a positive electrode of a power supply, and a cathode carbon plate connected with a negative electrode of the power supply, wherein an aeration head is arranged at the bottom of the reaction tank, the aeration head is connected with a gas supply source outside the reaction tank through a gas pipe, one end of a water inlet pipe is connected to a raw water tank, and the other end of the water inlet pipe extends into the reaction tank, a first peristaltic pump is arranged on the water inlet pipe, one end of a water outlet pipe is connected to a clean water tank, and the other end of the water outlet pipe is connected with the anode membrane assembly, a second peristaltic pump is arranged on the water outlet pipe, and the anode membrane assembly comprises the multi-component electro-hygroscopic combined catalytic modified electrode membrane obtained by the preparation method.

[0018] Further, the anode membrane assembly comprises front glass plates, middle glass plates and rear glass plates which are arranged in parallel and are of the same size, the first multi-component electro-hygroscopic combined catalytic modified electrode membrane is clamped between the front glass plates and the middle glass plates, and the second multi-component electro-hygroscopic combined catalytic modified electrode membrane is clamped between the rear glass plates and the middle glass plates, water holes are arranged in the centers of the front glass plates and the rear glass plates, the middle glass plates are provided with liquid storage cavities, one end of the water outlet pipe is connected with the liquid storage cavities, and raw water in the reaction tank sequentially passes through the water holes and the multi-component electro-hygroscopic combined catalytic modified electrode membrane and enters the liquid storage cavities, and clean water in the liquid storage cavities is discharged through the water outlet pipe and the second peristaltic pump.

[0019] Further, the reaction tank is a water bath pot, and the gas supply source is an air compressor.

[0020] Further, the front glass plates, the middle glass plates and the rear glass plates are screwed together by plastic screws.

[0021] Further, the water holes are square holes with a size of 5cm*6cm.

[0022] Further, the water outlet mode of the water inlet pipe and the water outlet pipe is peristaltic pump pressurized water outlet.

[0023] Further, the membrane water flow is 1.25 mL / min.

[0024] Further, the polar plate material uses graphite plate as the cathode.

[0025] Further, the aeration mode is bottom aeration, and an air compressor is used for aeration stirring to eliminate concentration polarization.

[0026] Further, the power supply is a direct current power supply.

[0027] Further, the power supply current is controlled at 20 mA.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] (1) In the preparation method of the multi-component electro-wet combined catalytic modified electrode membrane, the casting solution contains the pore-forming agent polyvinylpyrrolidone (PVP), and the electrode pre-membrane is first placed in an aqueous ethanol solution for pretreatment, and the pore-forming agent polyvinylpyrrolidone (PVP) is dissolved to form pores. Due to the presence of the pore-forming agent, the prepared electrode membrane has micropores. Experiments show that the membrane has good physical interception effect and can remove COD. The problem of low COD removal rate in dye wastewater is solved. (2) Using the preparation method of the multi-component electro-wet combined catalytic modified electrode membrane, the modified electrode membrane prepared by loading active catalytic components on the surface and micropores of the membrane can perform chemical oxidation, and the membrane material can simultaneously perform physical interception and chemical oxidation, thereby saving treatment procedures and time and reducing treatment costs as much as possible. (3) Using the preparation method of the multi-component electro-wet combined catalytic modified electrode membrane, the electrode membrane material is complexly loaded with Y and Co elements, which reduces the reaction activation energy and improves the oxidation-reduction capacity of the membrane. (4) The wet catalytic active components are loaded on the electrode membrane, which discards the traditional filler method and directly performs catalytic oxidation on the electrode membrane. The micropores on the membrane increase the contact area of the catalyst, and the pump-out water method can improve the oxidation efficiency and reduce energy waste. (5) The addition of graphene material to the membrane material makes the membrane have good electrical conductivity. The catalytic effect of the wet catalytic active components on the membrane material, combined with the external power supply, stimulates the generation of light-based free radicals through electrochemical reaction, and promotes the further activation of organic molecules adsorbed on the active sites of the catalyst. The combined effect of the two is much greater than the sum of the removal efficiencies of the two single reactions, and there is a synergistic effect. (6) A sewage treatment device, the anode membrane assembly includes the multi-component electro-wet combined catalytic modified electrode membrane obtained by the preparation method described above, which can simultaneously perform physical interception and chemical oxidation on the membrane material, thereby simultaneously performing physical and chemical treatment on wastewater, improving the solid-liquid mixing condition after traditional advanced oxidation treatment, saving treatment procedures and time, and reducing treatment costs as much as possible. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings required to be used in the specific embodiments or prior art description will be briefly introduced below. In all the drawings, similar elements or parts are generally identified by similar reference signs. In the drawings, the elements or parts are not necessarily drawn according to the actual scale;

[0031] Figure 1 is a whole structural diagram of a sewage treatment device;

[0032] Figure 2 is a detection result diagram of the anode film assembly prepared in Examples 1-6;

[0033] Figure 3 is a detection result diagram of the anode film assembly prepared in Examples 2, 7-12;

[0034] Figure 4 is a detection result diagram of the anode film assembly prepared in Examples 2, 13-14;

[0035] Figure 5 is a detection result diagram of Example 16;

[0036] Figure 6 is a detection result diagram of Example 17;

[0037] Figure 7 is a detection result diagram of Example 18;

[0038] Figure 8 is a detection result diagram of Example 19;

[0039] Figure 9 is a detection result diagram of Example 20; DETAILED DESCRIPTION

[0040] In order to make the preparation method of the present application more clear, the use effect and product advantages more clear, the technical solutions of the present application will be described in detail below. Next, the examples described are only a part of the examples of the present application, not all the examples. The examples are helpful to interpret and define the inventive content of the present application, and other embodiments obtained by other researchers in the art without making a more outstanding creative effort all belong to the scope of the present application.

[0041] The present application will be further described below in combination with examples:

[0042] Example 1:

[0043] The present embodiment provides a preparation method of a multi-component electric wet combined catalytic modified electrode film, which comprises the following steps:

[0044] (a) Casting solution preparation: polyvinylpyrrolidone (PVP) is added to N-methyl pyrrolidone (NMP), ultrasonic dispersion for 1 h, then polyethersulfone (PES) is added, then transferred into a water bath, keep constant temperature at 45-50℃, heating and stirring for 12-14 h, after polyethersulfone (PES) is completely dissolved, a mixed solution is obtained, the mixed solution is ultrasonic degassed for 2 h, a uniform casting solution is prepared, the total amount of polyvinylpyrrolidone (PVP), N-methyl pyrrolidone (NMP) and polyethersulfone (PES) is 100%;

[0045] (b) Membrane scraping: polyacrylonitrile-based carbon fiber cloth is used as the substrate, the polyacrylonitrile-based carbon fiber cloth is laid flat on the glass plate, the polyacrylonitrile-based carbon fiber cloth is ironed flat with a steam iron, then the polyacrylonitrile-based carbon fiber cloth is fixed with transparent tape, the polyacrylonitrile-based carbon fiber cloth is as flat as possible, then the casting solution prepared in step (a) is poured on the polyacrylonitrile-based carbon fiber cloth, the thickness of the casting solution is adjusted to 200 μm, the membrane is scraped with a scraper, after the membrane scraping is completed, it is exposed to air for 20 s, an electrode pre-membrane is prepared, and the obtained electrode pre-membrane is stored in deionized water for standby;

[0046] (c) Loading active components: yttrium oxide and cobalt oxide are dissolved in water to prepare a composite impregnating solution with a concentration of 1 mol / L-5 mol / L, the electrode pre-membrane obtained in step (b) is first placed in an aqueous ethanol solution for pretreatment, the pore-forming agent polyvinylpyrrolidone (PVP) is dissolved to form pores, then the electrode pre-membrane is washed with deionized water, and then immersed in the composite impregnating solution, so that the membrane is completely immersed in the solution, and after standing for 24 h, the electrode pre-membrane is taken out and washed with deionized water, thereby a Y-Co / GO / PES membrane is prepared;

[0047] (d) Modification of Y-Co / GO / PES membrane: the Y-Co / GO / PES membrane prepared in step (c) is immersed in an ascorbic acid solution, and then transferred into a constant-temperature heating magnetic stirrer and heated in a water bath to 100℃, and reacted for 2 h, so that the graphene oxide (GO) in the membrane is reduced to reduced graphene oxide (rGO), thereby a Y-Co / rGO / PES anode membrane is obtained, which is a multi-component electro-wet combined catalytic modified electrode membrane.

[0048] Further, in step (a), the casting solution consists of 0.3% graphene oxide (GO), 0.5% polyvinylpyrrolidone (PVP), 15% polyethersulfone (PES), and 84.2% N-methyl pyrrolidone (NMP) by mass percentage.

[0049] Further, in step (c), the volume ratio of water to ethanol in the aqueous ethanol solution is 1:4.

[0050] Further, in the step (c), the mass ratio of yttrium oxide to cobalt oxide is 2:1.

[0051] Further, in the step (d), the mass ratio of ascorbic acid in the ascorbic acid solution is 10%.

[0052] Example 2:

[0053] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is identical to the preparation method in the embodiment 1, and the only difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 16% of polyethersulfone (PES) and 83.2% of N-methylpyrrolidone (NMP).

[0054] Example 3:

[0055] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is identical to the preparation method in the embodiment 1, and the only difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 17% of polyethersulfone (PES) and 82.2% of N-methylpyrrolidone (NMP).

[0056] Example 4:

[0057] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is identical to the preparation method in the embodiment 1, and the only difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 18% of polyethersulfone (PES) and 81.2% of N-methylpyrrolidone (NMP).

[0058] Example 5:

[0059] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is identical to the preparation method in the embodiment 1, and the only difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 19% of polyethersulfone (PES) and 80.2% of N-methylpyrrolidone (NMP).

[0060] Example 6:

[0061] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, the preparation method is consistent with that in embodiment 1, and the difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 20% of polyether sulfone (PES) and 79.2% of N-methylpyrrolidone (NMP).

[0062] Embodiment 7:

[0063] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, the preparation method is consistent with that in embodiment 1, and the difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 20% of polyether sulfone (PES) and 79.2% of N-methylpyrrolidone (NMP).

[0064] Embodiment 8:

[0065] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, the preparation method is consistent with that in embodiment 1, and the difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 20% of polyether sulfone (PES) and 79.2% of N-methylpyrrolidone (NMP).

[0066] Embodiment 9:

[0067] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, the preparation method is consistent with that in embodiment 1, and the difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 20% of polyether sulfone (PES) and 79.2% of N-methylpyrrolidone (NMP).

[0068] Embodiment 10:

[0069] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, the preparation method is consistent with that in embodiment 1, and the difference is that in the step (a), the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 20% of polyether sulfone (PES) and 79.2% of N-methylpyrrolidone (NMP).

[0070] Embodiment 11:

[0071] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is consistent with the preparation method in the embodiment 1, and only differs from the preparation method in the embodiment 1 in that the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 8% of polyvinylpyrrolidone (PVP), 16% of polyethersulfone (PES) and 75.7% of N-methylpyrrolidone (NMP) in the step (a).

[0072] Embodiment 12

[0073] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is consistent with the preparation method in the embodiment 1, and only differs from the preparation method in the embodiment 1 in that the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 10% of polyvinylpyrrolidone (PVP), 16% of polyethersulfone (PES) and 73.7% of N-methylpyrrolidone (NMP) in the step (a).

[0074] Embodiment 13

[0075] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is consistent with the preparation method in the embodiment 1, and only differs from the preparation method in the embodiment 1 in that the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 16% of polyethersulfone (PES) and 83.2% of N-methylpyrrolidone (NMP) in the step (a), and the mass ratio of yttrium oxide to cobalt oxide is 1:2 in the step (c).

[0076] Embodiment 14

[0077] The embodiment provides a preparation method of a multi-component electro-humidification combined catalytic modification electrode film, which is consistent with the preparation method in the embodiment 1, and only differs from the preparation method in the embodiment 1 in that the casting solution is composed of the following raw materials in percentage by mass: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 16% of polyethersulfone (PES) and 83.2% of N-methylpyrrolidone (NMP) in the step (a), and the mass ratio of yttrium oxide to cobalt oxide is 1:1 in the step (c).

[0078] Embodiment 15

[0079] The embodiment provides a sewage treatment device, which comprises a sewage treatment device as shown in the embodiment 1. Figure 1As shown, including the reaction tank (3), also includes placed in the reaction tank (3) and respectively with the positive electrode of the power supply (6) anode film assembly (1) and with the negative electrode of the power supply (6) cathode carbon plate (2), the bottom of the reaction tank (3) is provided with aeration head (4), aeration head (4) through the air pipe with the reaction tank (3) outside the gas supply source is communicated, one end of the water inlet pipe is connected to the raw water tank, the other end extends into the reaction tank (3), the water inlet pipe has a first peristaltic pump, one end of the water outlet pipe is connected to the clean water tank, the other end is connected with the anode film assembly (1), the water outlet pipe has a second peristaltic pump, the anode film assembly (1) includes a plurality of components obtained by the preparation method of the above embodiment 1-14.

[0080] Further, the anode film assembly (1) includes front glass plate, middle glass plate and rear glass plate which are arranged in parallel and equal size, and the first multi-component electro-hygroscopic combined catalytic modified electrode film clamped between the front glass plate and the middle glass plate, and the second multi-component electro-hygroscopic combined catalytic modified electrode film clamped between the rear glass plate and the middle glass plate, the center of the front glass plate and the rear glass plate is provided with a water permeable hole, and the middle glass plate has a liquid storage cavity, one end of the water outlet pipe is communicated with the liquid storage cavity, the raw water in the reaction tank (3) passes through the water permeable hole and the multi-component electro-hygroscopic combined catalytic modified electrode film into the liquid storage cavity in turn, and the clean water in the liquid storage cavity is discharged through the water outlet pipe and the second peristaltic pump. The reaction tank (3) is a water bath kettle; the gas supply source is an air compressor (5); the cathode carbon plate (2) is a graphite plate.

[0081] Using the above sewage treatment device, dye wastewater experiments are simulated respectively. The content of rhodamine B in raw water is 5 mg / L, and COD = 7.79 mg / L. Rhodamine B is a widely used artificial synthetic triphenylmethane dye, which not only has great biological toxicity, but also has carcinogenic effect.

[0082] The multi-component electro-hygroscopic combined catalytic modified electrode film prepared by the above embodiment 1-14 is used to process the corresponding anode film assembly (1), and the anode film assembly (1) is used as an anode and the graphite plate is used as a cathode. The control variable method is used, that is, when a certain experimental variable is changed, the remaining variables remain unchanged, in order to explore the influence of the change of each variable on the experimental results.

[0083] The specific operation method is to use an electrochemical reaction device and apply certain experimental conditions. The COD of the water sample is determined by the national standard method "Determination of chemical oxygen demand-potassium dichromate method" (GB11914-89). When measuring, 1.5 mL of water sample is taken, COD reagent is added, and mixed. When the temperature is 20-25°C, the water sample is heated in a digestion instrument for 15 min. Then when the temperature is 60-65°C, the water sample is heated for 2 h. ​The absorbance value was measured by using a COD determination instrument (CM-02) with pure water as a reference at a wavelength of 600 nm. The raw water was also measured for COD, which was used for comparison with the effluent COD to analyze the removal effect.

[0084] COD removal rate = (COD0-COD) / COD0 COD0 is the COD concentration of the raw water, and COD is the COD concentration of the effluent after treatment.

[0085] Figure 2 The detection results of the anode membrane assemblies prepared in Examples 1-6 are shown in the following figures. Figure 2 The data show that, when the content of polyvinylpyrrolidone (PVP) is kept constant, the treatment effect of the device first increases and then decreases in the optimal content interval, and the COD removal effect is better than that of other contents when the content of polyether sulfone (PES) is 16% in the interval, which can meet the experimental effect.

[0086] Figure 3 The detection results of the anode membrane assemblies prepared in Examples 2, 7-12 are shown in the following figures. Figure 3 The data show that, when the content of polyether sulfone (PES) is kept constant, the treatment effect of the device first enters a relatively stable stage, and then the treatment effect rapidly decreases with the increase of the content of polyvinylpyrrolidone (PVP). The content of polyvinylpyrrolidone (PVP) can be selected as 0.5% to meet the experimental effect.

[0087] Figure 4 The detection results of the anode membrane assemblies prepared in Examples 2, 13-14 are shown in the following figures. Figure 4 The data show that the mass ratio of yttrium oxide to cobalt oxide can affect the treatment effect of the device. The three ratios with better effects in the above examples are compared, and the results show that the device has the best treatment effect when the mass ratio of yttrium oxide to cobalt oxide is 2:1, which can meet the experimental effect.

[0088] In summary, the detection results of the anode membrane assemblies prepared in Examples 1-14 show that the COD removal effect of the wastewater treatment device is obvious, which can meet the experimental requirements.

[0089] The content of graphene oxide (GO) can be selected as 0.3%, the content of polyether sulfone (PES) can be selected as 16%, the content of polyvinylpyrrolidone (PVP) can be selected as 0.5%, the content of N-methylpyrrolidone (NMP) can be selected as 83.2%, and the mass ratio of yttrium oxide to cobalt oxide can be selected as 2:1 for effect test experiments. The above-mentioned contents can meet the experimental requirements and have the best treatment effect.

[0090] Example 16

[0091] This embodiment provides a wastewater treatment device, such as... Figure 1 As shown, the reaction tank (3) includes an anode membrane assembly (1) placed in the reaction tank (3) and connected to the positive terminal of the power supply (6) and a cathode carbon plate (2) connected to the negative terminal of the power supply (6). An aeration head (4) is provided at the bottom of the reaction tank (3). The aeration head (4) is connected to the air supply source outside the reaction tank (3) through an air pipe. One end of the water inlet pipe is connected to the raw water tank and the other end extends into the reaction tank (3). The water inlet pipe has a first peristaltic pump. One end of the water outlet pipe is connected to the purified water tank and the other end is connected to the anode membrane assembly (1). The water outlet pipe has a second peristaltic pump. The anode membrane assembly (1) includes a multi-component electro-wet combined catalytic modified electrode membrane obtained by the preparation method in Embodiment 2 above.

[0092] Furthermore, the anode membrane assembly (1) includes a front glass plate, a middle glass plate, and a rear glass plate arranged parallel to each other and of equal size, as well as a first multi-component electro-wet combined catalytic modification electrode membrane sandwiched between the front glass plate and the middle glass plate, and a second multi-component electro-wet combined catalytic modification electrode membrane sandwiched between the rear glass plate and the middle glass plate. The front glass plate and the rear glass plate are each provided with a water-permeable hole in their center, and the middle glass plate has a liquid storage chamber in its center. One end of the water outlet pipe is connected to the liquid storage chamber. The raw water in the reaction tank (3) enters the liquid storage chamber in sequence through the water-permeable hole and the multi-component electro-wet combined catalytic modification electrode membrane. The purified water in the liquid storage chamber is discharged through the water outlet pipe and the second peristaltic pump.

[0093] Furthermore, the reaction tank (3) is a water bath; the air supply source is an air compressor (5); and the cathode carbon plate (2) is a graphite plate.

[0094] The above-mentioned wastewater treatment device was used to simulate dye wastewater experiments.

[0095] The anode membrane assembly (1) is used as the anode, and the graphite plate is used as the cathode. The anode and cathode are connected to the positive and negative terminals of the power supply (6), respectively, and the power supply (6) provides an external constant current. The second peristaltic pump controls the peristaltic pump speed to 1.5 rpm, at which time the membrane outlet water flow rate is 1.25 mL / min. At the same time, the first peristaltic pump controls the inlet water to the same flow rate to keep the liquid level in the reaction tank (3) stable.

[0096] The original solution to be treated in the raw water tank has a neutral pH, a Rhodamine B concentration of 5 mg / L, an absorbance of 1.088, and an electrolyte sodium sulfate concentration of 0.05 mmol / L.

[0097] The air compressor aeration stirring was used to eliminate the concentration polarization, the reaction tank (3) had a content volume of 1450 mL, the reaction water bath temperature was kept at 20 DEG C, in order to eliminate the influence of anode adsorption, the sampling was started after 40 min of operation, and then the sampling was carried out every 30 min.

[0098] The applied current was adjusted to 5 mA, 10 mA, 15 mA, 20 mA and 22 mA respectively, the influence of different applied currents on the degradation effect of SnO2 / rGO / PVDF anode film on rhodamine B was investigated, and the experimental results were as shown in Figure 5

[0099] It can be known from Figure 5

[0100] When the rhodamine effluent absorbance change curve changed smoothly at 5 mA, the maximum removal efficiency was 71.97%, the minimum removal efficiency was 69.21%, and the average removal efficiency was 71.21%.

[0101] When the rhodamine effluent absorbance change curve changed smoothly at 10 mA, the maximum removal efficiency was 73.07%, the minimum removal efficiency was 72.15%, and the average removal efficiency was 72.68%.

[0102] When the rhodamine effluent absorbance change curve changed smoothly at 15 mA, the maximum removal efficiency was 76.65%, the minimum removal efficiency was 75.46%, and the average removal efficiency was 76.29%.

[0103] When the rhodamine effluent absorbance change curve changed smoothly at 20 mA, the maximum removal efficiency was 86.12%, the minimum removal efficiency was 85.39%, and the average removal efficiency was 85.71%.

[0104] When the rhodamine effluent absorbance change curve changed smoothly at 22 mA, the maximum removal efficiency was 84.83%, the minimum removal efficiency was 83.55%, and the average removal efficiency was 83.86%.

[0105] Because the calculation of the maximum and minimum removal efficiency of rhodamine was obtained at the time when the effluent result was unstable, the average removal efficiency was used for result analysis. With the increase of the applied current, the effluent absorbance was smaller and smaller, and the degradation effect on rhodamine B was better and better, but the effluent absorbance at 22 mA was larger than that at 20 mA, at this time, the degradation effect began to be poor, and if the current was continuously increased, the anode voltage would exceed 1.5 V, at this time, the water would be electrolyzed, so that the experimental result was meaningless. Therefore, it was concluded that the best current for the modified electrochemical anode film to degrade rhodamine B was about 20 mA.

[0106] Example 17 ​​

[0107] A simulated dye wastewater experiment was conducted using a wastewater treatment device provided in Example 16.

[0108] The anode membrane assembly (1) was used as an anode, and a graphite plate was used as a cathode. The anode and the cathode were connected to the positive and negative poles of a power supply (6), respectively. The power supply (6) provided an external constant current of 20 mA.

[0109] The pH of the raw solution to be treated in the raw water tank was neutral, the concentration of rhodamine B was 5 mg / L, the absorbance was 1.088, and the concentration of the electrolyte sodium sulfate was 0.05 mmol / L.

[0110] Air compressor aeration stirring was used to eliminate concentration polarization. The internal volume of the device was 1450 mL, and the reaction water bath temperature was maintained at 20°C. To eliminate the influence of anode adsorption, sampling was started after 40 minutes of operation, and then sampling was performed every 30 minutes.

[0111] The second peristaltic pump was used to control the water outlet, and the first peristaltic pump was used to control the water inlet at the same flow rate to maintain the liquid level in the reaction tank (3). The water outlet flow rate was adjusted to 1.25 mL / min, 2.4 mL / min, 3.6 mL / min, 4.9 mL / min, and 6.0 mL / min, respectively, to investigate the effect of different water outlet flow rates on the degradation of rhodamine B by the SnO2 / rGO / PVDF anode membrane. The results are shown in Figure 6 .

[0112] As can be seen from Figure 6 ,

[0113] At 1.25 mL / min, the rhodamine outlet absorbance change curve changed smoothly, and the maximum removal efficiency was 86.12%, the minimum removal efficiency was 85.39%, and the average removal efficiency was 85.71%.

[0114] At 2.4 mL / min, the rhodamine outlet absorbance change curve changed greatly. The initial outlet absorbance was very low, even lower than that at 1.25 mL / min. However, the outlet absorbance gradually increased, and after the curve changed smoothly, the outlet absorbance was still greater than that at 1.25 mL / min. The maximum removal efficiency was 88.33%, the minimum removal efficiency was 78.13%, and the average removal efficiency after the curve changed smoothly was 78.34%.

[0115] At 3.6 mL / min, the rhodamine outlet absorbance change curve changed smoothly, and the maximum removal efficiency was 83.36%, the minimum removal efficiency was 72.24%, and the average removal efficiency was 72.43%.

[0116] 4.9 mL / min, the change curve of the effluent absorbance of rhodamine was stable, the maximum removal efficiency was 67.37%, the minimum removal efficiency was 54.41%, and the average removal efficiency was 54.41%.

[0117] 6.0 mL / min, the change curve of the effluent absorbance of rhodamine was very large, the initial effluent absorbance was very low, even lower than that at 4.9 mL / min, but then the effluent absorbance gradually increased, and even after the curve changed stably, the effluent absorbance was still greater than that at 4.9 mL / min. The maximum removal efficiency was 72.98%, the minimum removal efficiency was 52.30%, and the average removal efficiency after stabilization was 52.53%.

[0118] Because the calculation of the maximum and minimum removal efficiency of rhodamine was somewhat obtained when the effluent results were unstable, the average removal efficiency after stabilization was used for result analysis. With the increase of the effluent flow, the final stable value of the effluent absorbance was larger and larger (although the initial sampling results of the effluent absorbance at 1.25 mL / min and 2.4 mL / min, 4.9 mL / min and 6.0 mL / min did not conform to this rule, but the rule was stable after stabilization), and the effect of the modified electrochemical anode membrane on the degradation of rhodamine B was worse. Further reducing the effluent flow would make the effluent stay in the membrane for too long, and thus the probability of side reactions would be larger, and the results would be inaccurate. It was concluded that the best flow of the modified electrochemical anode membrane for degrading rhodamine B was 1.25 mL / min.

[0119] Example 18

[0120] A wastewater treatment device provided in Example 16 was used to simulate a dye wastewater experiment.

[0121] The anode membrane assembly (1) was used as an anode, and a graphite plate was used as a cathode. The anode and the cathode were connected to the positive and negative poles of a power supply (6), respectively, and the power supply (6) provided an external constant current of 20 mA. The second peristaltic pump controlled the rotation speed of the peristaltic pump to be 1.5 rpm, at which time the membrane effluent flow was 1.25 mL / min. At the same time, the first peristaltic pump controlled the water inlet to be the same flow, and the liquid level in the reaction tank (3) was kept stable.

[0122] The pH of the raw solution to be treated in the raw water tank was neutral, the concentration of rhodamine B was 5 mg / L, the absorbance was 1.088, and the concentration of the electrolyte sodium sulfate was 0.05 mmol / L.

[0123] Air compressor aeration stirring was used to eliminate concentration polarization. The content volume of the device was 1450 mL, the reaction water bath temperature was kept at 20°C, in order to eliminate the influence of anode adsorption, sampling was started after 40 min of operation, and then sampling was performed every 30 min.

[0124] The pH of the original solution to be treated was adjusted to 4.0, 7.0 and 10.0, respectively, to investigate the effect of different pH values on the degradation of rhodamine B by the SnO2 / rGO / PVDF anode membrane, and the results are shown in Figure 7 .

[0125] As can be seen from Figure 7 , although the absorbance value of the effluent increased with increasing pH value at the beginning of sampling, the absorbance value of the effluent under acidic and alkaline conditions was higher than that under neutral conditions, and the degradation effect was poor, that is, the degradation effect of the anode membrane on rhodamine B was best when the original rhodamine B was neutral.

[0126] When the pH was 4.0, the rhodamine effluent absorbance curve changed greatly, the effluent absorbance was very low at the beginning, but then the effluent absorbance gradually increased, and even higher than that when the pH was 7.0 after the curve changed smoothly. After 190 min of operation, the effluent rhodamine B concentration reached a stable state, and the maximum removal efficiency was 90.07%, the minimum removal efficiency was 84.01%, and the average removal rate after stabilization was 84.01%.

[0127] When the pH was 7.0, the rhodamine effluent absorbance curve changed smoothly, and the maximum removal efficiency was 86.12%, the minimum removal efficiency was 85.39%, and the average removal efficiency was 85.71%.

[0128] When the pH was 10.0, the rhodamine effluent absorbance curve changed smoothly, and the maximum removal efficiency was 85.48%, the minimum removal efficiency was 83.55%, and the average removal efficiency was 83.55%.

[0129] It is worth noting that when the pH was 4.0, the initial effluent rhodamine B concentration of the membrane was very low, and then increased significantly with the running time, and the effluent rhodamine B concentration of the membrane did not reach a stable state until 180 min of operation, which indicated that under acidic conditions, the adsorption of rhodamine B by the anode membrane was more significant.

[0130] Example 19

[0131] A wastewater treatment device provided in Example 16 was used to simulate a dye wastewater experiment.

[0132] The anode membrane assembly (1) was used as the anode, and the graphite plate was used as the cathode. The anode and the cathode were connected to the positive and negative poles of the power supply (6), respectively, and the power supply (6) provided an external constant current of 20 mA. The second peristaltic pump controlled the peristaltic pump speed to be 6.0 rpm, at which the membrane effluent flow rate was 4.8 mL / min. At the same time, the first peristaltic pump controlled the water inlet to be the same flow rate, and the liquid level in the reaction tank (3) was kept stable.

[0133] The pH of the raw solution to be treated in the raw water tank was neutral, the concentration of rhodamine B was 5 mg / L, the absorbance was 1.088, and the concentration of electrolyte sodium sulfate was 0.05 mmol / L.

[0134] The air compressor was used for aeration and stirring to eliminate concentration polarization, the internal volume of the device was 1450 mL, and the reaction water bath temperature was kept at 20℃.

[0135] The concentration of electrolyte sodium sulfate was adjusted to 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L and 0.10 mol / L respectively, and the influence of different concentrations of sodium sulfate on the voltage of the electrolytic cell and the anode potential was investigated, and the results are shown in Figure 8 .

[0136] As can be seen from Figure 8 , with the increase of the concentration of sodium sulfate, the positive voltage changes little and basically remains unchanged, but the voltage between the positive and negative electrodes gradually decreases. Since the applied current is a constant current of 20 mA, it can be concluded that the resistance between the positive and negative electrodes decreases with the increase of the concentration of sodium sulfate. That is, the greater the concentration of sodium sulfate, the greater the concentration of electrolyte, and the better the degradation effect under the same conditions. When the concentration of sodium sulfate is greater than 0.04 mol / L, the trend of the change of the applied voltage and the anode potential with the concentration of sodium sulfate obviously slows down. Considering factors such as energy consumption, water salinity and reagent cost, the optimal concentration of sodium sulfate should be controlled at 0.05 mol / L.

[0137] Example 20

[0138] A wastewater treatment device provided in Example 16 was used to simulate dye wastewater experiments.

[0139] The anode membrane assembly (1) was used as the anode, and the graphite plate was used as the cathode. The anode and the cathode were connected to the positive and negative poles of the power supply (6) respectively, and the power supply (6) provided an applied constant current of 20 mA.

[0140] The second peristaltic pump controlled the rotation speed of the peristaltic pump to be 1.5 rpm, at which time the membrane water flow was 1.25 mL / min. At the same time, the first peristaltic pump controlled the water inlet to be the same flow, and the liquid level in the reaction tank (3) was kept stable.

[0141] The pH of the raw solution to be treated in the raw water tank was neutral, the concentration of rhodamine B was 20 mg / L, and the concentration of electrolyte sodium sulfate was 0.05 mmol / L.

[0142] Air compressor aeration stirring to eliminate concentration polarization, the reaction pool (3) content volume is 1450 mL, the reaction water bath temperature is kept at 20 DEG C, in order to eliminate the influence of anode adsorption, after running 40 min, start sampling, then every 30 min sampling once, its result is shown in Figure 9

[0143] From Figure 9 It is known that the COD concentration of raw water is 31.16 mg / L, in the running 160 min time, the effluent COD concentration is stable, the average COD concentration of effluent is 15.23 mg / L, the maximum removal efficiency is 54.08%, the minimum removal efficiency is 46.63%, and the average removal efficiency is 51.12%. From the figure, the effluent COD concentration is obviously reduced compared with the raw water concentration, it is known that the modified electrochemical anode membrane has obvious COD removal effect on rhodamine B, which proves that part of rhodamine B is mineralized to carbon dioxide and water under the operation condition.

[0144] The above optimal reaction condition is selected to carry out actual wastewater experiment.

[0145] Example 21

[0146] Only the membrane assembly in the sewage treatment device provided in example 16 is used, no power supply is added, and no active components such as yttrium oxide and cobalt oxide are added on the membrane, and wastewater experiment is carried out.

[0147] Actual industrial wastewater application test: taking the industrial wastewater of a chemical company, COD = 18000 mg / L, turbidity = 2.85 NTU, the unmodified membrane assembly is put into the water, no power supply is added, the peristaltic pump is used to control the peristaltic pump rotation number to be 1.5 rpm, at this time the membrane effluent flow is 1.25 mL / min, at the same time another peristaltic pump is used to control the water inlet flow to be the same flow, and the liquid level in the reaction device is kept stable.

[0148] Air compressor aeration stirring to eliminate concentration polarization, the device content volume is 1450 mL, the reaction water bath temperature is kept at 20 DEG C, in order to eliminate the influence of anode adsorption, sampling is determined after running 1 h, the result shows that the wastewater COD = 17200 mg / L, the turbidity = 0.006 NTU.

[0149] The results show that without adding wet catalytic active components and power supply, simply using membrane to treat wastewater can play a physical interception role, the wastewater turbidity is greatly reduced, but the organic matter index COD treatment effect is very small and can be ignored, so it is proved that the simple membrane action has poor organic matter degradation effect.

[0150] Example 22

[0151] A kind of sewage treatment device provided in example 16 is used to carry out actual wastewater experiment. ​

[0152] The reaction conditions provided in Examples 16-20 were used to carry out industrial production wastewater experiments.

[0153] Actual industrial wastewater application experiment: The industrial production wastewater of a chemical company in Example 21 was taken, COD = 18000 mg / L, turbidity = 2.85 NTU, the modified electrochemical membrane assembly was used as an anode, a graphite plate was used as a cathode, under the control of an applied constant current, a peristaltic pump was used to control the peristaltic pump speed to 1.5 rpm, at this time the membrane water flow was 1.25 mL / min, another peristaltic pump was used to control the water inlet to the same flow, the liquid level in the reaction device was kept stable, the applied current was adjusted to 20 mA, and the electrolyte sodium sulfate concentration was 0.05 mol / L.

[0154] Air compressor aeration stirring was used to eliminate concentration polarization, the device content volume was 1450 mL, the reaction water bath temperature was kept at 20°C, in order to eliminate the influence of anode adsorption, sampling was carried out after 1 h of operation, and the results showed that the wastewater COD was 8800 mg / L, and the turbidity was 0.006 NTU.

[0155] The results show that under the action of wet catalysis combined with electric field, the organic matter in the wastewater can be degraded while the physical interception of the membrane is achieved, and the organic matter index COD can be reduced by 51%. Therefore, it is proved that under the action of wet catalysis combined with electric field, combined with the physical interception of the membrane, the wastewater can be physically and chemically treated, and the effect is good.

[0156] Example 23

[0157] A sewage treatment device provided in Example 16 was used to carry out actual wastewater experiments.

[0158] The reaction conditions provided in Examples 16-20 were used to carry out industrial production wastewater experiments.

[0159] Actual industrial wastewater application experiment: The industrial production wastewater of a chemical company in Example 21 was taken, COD = 18000 mg / L, turbidity = 2.85 NTU, the modified electrochemical membrane assembly was used as an anode, a graphite plate was used as a cathode, under the control of an applied constant current, a peristaltic pump was used to control the peristaltic pump speed to 1.5 rpm, at this time the membrane water flow was 1.25 mL / min, another peristaltic pump was used to control the water inlet to the same flow, the liquid level in the reaction device was kept stable, the applied current was adjusted to 20 mA, and the electrolyte sodium sulfate concentration was 0.05 mol / L.

[0160] Air compressor aeration stirring was used to eliminate concentration polarization, the device content volume was 1450 mL, the reaction water bath temperature was kept at 20°C, in order to eliminate the influence of anode adsorption, sampling was carried out after 1 h of operation, and the results showed that the wastewater COD was 8800 mg / L, and the turbidity was 0.006 NTU.

[0161] The results show that the dyeing wastewater can be treated under the effect of the wet catalytic combined electric field, the organic matter index COD can be reduced by 58.8%, and the colority of the dyeing wastewater can be removed, and the effect is good.

[0162] It can be known from the combination of embodiments 22 and 23 that the electrode film has a treatment effect on the chemical oxygen demand of the actual wastewater, the degradation rate can be more than 50%, and has a decolorization effect on the dye wastewater, and the colority of the dye wastewater can be completely removed.

[0163] The above embodiments are only used to illustrate the technical solutions of the present application, but not limit the present application; although the present application has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solutions recorded in the above embodiments can be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should be covered in the scope of the claims and the specification of the present application; any alternative improvement or change made by those skilled in the art to the embodiments of the present application falls within the protection scope of the present application.

[0164] The parts not described in the present application are the known technology of those skilled in the art.

Claims

1. A method for preparing a multi-component electro-hydrated combined catalytic modified electrode membrane, characterized in that, The preparation method comprises the following steps: (a) casting solution preparation: graphene oxide (GO), polyvinylpyrrolidone (PVP) are added into N-methylpyrrolidone (NMP), ultrasonic dispersion is carried out for 1h, then polyethersulfone (PES) is added, and then it is transferred into a water bath, kept at constant temperature of 45-50℃, heated and stirred for 12-14h, after complete dissolution of polyethersulfone (PES), a mixed solution is obtained, the mixed solution is ultrasonic degassed for 2h, a uniform casting solution is prepared, and the total amount of polyvinylpyrrolidone (PVP), N-methylpyrrolidone (NMP) and polyethersulfone (PES) is 100%; (b) film scraping: polyacrylonitrile-based carbon fiber cloth is used as a substrate, the polyacrylonitrile-based carbon fiber cloth is evenly laid on a glass plate, a steam iron is used to iron the polyacrylonitrile-based carbon fiber cloth, transparent adhesive tape is used to fix the polyacrylonitrile-based carbon fiber cloth, the polyacrylonitrile-based carbon fiber cloth is as flat as possible, then the casting solution prepared in step (a) is poured on the polyacrylonitrile-based carbon fiber cloth, the film thickness of the doctor blade is adjusted to 200μm, film scraping is carried out by using a film scraper, after film scraping is completed, it is exposed to air for 20s, an electrode pre-film is prepared, and the obtained electrode pre-film is stored in deionized water for standby; (c) loading active components: yttrium oxide and cobalt oxide are dissolved in water to prepare a composite impregnating solution with a concentration of 1mol / L-5mol / L, the electrode pre-film obtained in step (b) is first placed in an aqueous ethanol solution for pretreatment, polyvinylpyrrolidone (PVP) is dissolved to form pores, then deionized water is used for cleaning, then the electrode pre-film is immersed in the composite impregnating solution, the film is completely immersed in the solution, and after standing for 24h, the electrode pre-film is taken out and cleaned with deionized water, and a Y-Co / GO / PES film is prepared. (d) Modification of Y-Co / GO / PES membrane: the Y-Co / GO / PES membrane prepared in step (c) is immersed in an ascorbic acid solution, and then transferred into a constant temperature heating magnetic stirrer for water bath heating to 95-100℃, and reacted for 2h, so that the graphene oxide (GO) in the membrane is reduced to reduced graphene oxide (rGO), thereby obtaining a Y-Co / rGO / PES anode membrane, which is a multi-component electro-hydropneumatic combined catalytic modified electrode membrane, in the step (a), the casting solution is composed of the following raw materials in mass percentage: 0.3% of graphene oxide (GO), 0.5%-10% of polyvinylpyrrolidone (PVP), 15%-20% of polyether sulfone (PES), and the balance of N-methyl pyrrolidone (NMP), the sum of the amounts of the above components is 100%, in the step (a), the casting solution is composed of the following raw materials in mass percentage: 0.3% of graphene oxide (GO), 0.5% of polyvinylpyrrolidone (PVP), 16% of polyether sulfone (PES), and 83.2% of N-methyl pyrrolidone (NMP), in the step (c), the volume ratio of water to ethanol in the aqueous ethanol solution is 1:4, in the step (c), the mass ratio of yttrium oxide to cobalt oxide is 2:1, in the step (d), the mass percentage of ascorbic acid in the ascorbic acid solution is 10%.

2. A sewage treatment apparatus characterised in that, The reaction tank (3) further comprises an anode membrane assembly (1) placed in the reaction tank (3) and connected with the positive electrode of the power supply (6) and a cathode carbon plate (2) connected with the negative electrode of the power supply (6), an aeration head (4) is arranged at the bottom of the reaction tank (3), the aeration head (4) is connected with the air supply source outside the reaction tank (3) through an air pipe, one end of the water inlet pipe is connected to the raw water tank, and the other end extends into the reaction tank (3), the water inlet pipe is provided with a first peristaltic pump, one end of the water outlet pipe is connected to the clean water tank, and the other end is connected with the anode membrane assembly (1), the water outlet pipe is provided with a second peristaltic pump, and the anode membrane assembly (1) comprises a multi-component electro-hydropneumatic combined catalytic modified electrode membrane obtained by the preparation method of any one of claims 1.

3. A sewage treatment apparatus as claimed in claim 2, wherein The anode membrane assembly (1) comprises front, middle and rear glass plates arranged in parallel and with the same size, a first multi-component electro-hydropneumatic combined catalytic modified electrode membrane clamped between the front and middle glass plates, and a second multi-component electro-hydropneumatic combined catalytic modified electrode membrane clamped between the rear and middle glass plates, the center of each of the front and rear glass plates is provided with a water permeable hole, and the middle glass plate is provided with a liquid storage cavity, one end of the water outlet pipe is connected with the liquid storage cavity, and the raw water in the reaction tank (3) sequentially passes through the water permeable hole, the multi-component electro-hydropneumatic combined catalytic modified electrode membrane and enters the liquid storage cavity, and the clean water in the liquid storage cavity is discharged through the water outlet pipe and the second peristaltic pump.

4. A sewage treatment apparatus as claimed in claim 3, wherein The reaction tank (3) is a water bath kettle; and the air supply source is an air compressor (5).

5. A sewage treatment apparatus as claimed in claim 4, wherein The front, middle and rear glass plates are tightened together by plastic screws.

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