An electrochemical confined catalytic treatment filler for dissolved organic matter wastewater and a method for preparing and using the same

Abstract

The application discloses a kind of solubility organic matter wastewater electrochemical limited catalytic treatment fillers and its preparation and use method, belong to water treatment technical field, preparation method includes placing substrate in polypyrrole elemental solution, after oxidation reaction, centrifugal separation, washing, drying, add to TiO2 precursor solution, after aging gel, secondary drying, after high-temperature sintering, obtain solubility organic matter wastewater electrochemical limited catalytic treatment filler.TiO2 Carrying hydroxyl and carbonyl group can quickly interact with solubility organic matter in water, realize the adsorption removal of pollutants.Filler is put into electrochemical reactor, and a large number of micro electrolytic cells are formed by using electric field effect polarization, and the high specific surface area of conductive particles realizes the efficient output of current in the catalytic filler, which is transmitted to the inside of TiO2 polypyrrole complex through conductive polypyrrole, to ensure that the current in the filler is effectively transmitted to the adsorbed solubility organic matter molecules, so that they are catalytically decomposed.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, specifically relating to an electrochemical confined catalytic treatment packing for dissolved organic wastewater and its preparation and application methods. Background Technology

[0002] Against the backdrop of increasingly severe global environmental problems, the protection and management of water resources has become a focal point of attention for governments and societies worldwide. Dissolved organic matter (DOM), a significant pollutant in water bodies, originates from a wide range of sources, including industrial wastewater discharge, agricultural fertilizer and pesticide runoff, domestic sewage, and natural biological processes. These DOMs not only affect the sensory quality of water bodies, such as color, turbidity, and odor, but can also act as precursors, undergoing a series of complex physicochemical reactions in the aquatic environment to transform into more toxic compounds, such as disinfection byproducts, posing a potential threat to aquatic ecosystems and human health. Therefore, effectively removing DOM from water bodies is of great significance for ensuring drinking water safety, maintaining aquatic ecological balance, and promoting sustainable development.

[0003] Traditional methods for treating dissolved organic matter, such as physical treatments like coagulation, sedimentation, and filtration, as well as biological treatment processes, can remove some organic matter to a certain extent, but their effectiveness is limited for treating recalcitrant or low-concentration dissolved organic matter. In recent years, advanced electrochemical oxidation (EAOP) has shown great potential in treating recalcitrant organic matter due to its high efficiency and environmental friendliness. This technology uses an electric field to oxidize and decompose organic matter using strong oxidants (such as hydroxyl radicals) generated by electrode reactions, converting them into harmless or low-toxic substances. In particular, optimizing electrode materials, electrolyte composition, and reaction conditions can significantly improve oxidation efficiency and treatment effect. The selection and modification of electrode materials are key to improving electrochemical oxidation efficiency, and researchers are constantly exploring novel electrode materials, such as supported catalysts, nanomaterials, and composite materials, to achieve higher catalytic activity and stability.

[0004] Despite significant progress in treating dissolved organic matter using advanced electrochemical oxidation (ACO) technologies, several challenges remain. Firstly, traditional electrode materials, such as metal anodes, while exhibiting good conductivity, suffer from limited specific surface area and insufficient active sites, hindering catalytic efficiency. Secondly, the loading of a single catalyst often fails to simultaneously meet the requirements of high catalytic activity and good stability, particularly during long-term operation and under complex water conditions, leading to issues like catalyst shedding and deactivation. Furthermore, efficiently transferring current to the catalyst surface and ensuring uniform current distribution across every catalytic site are also critical challenges for improving electrochemical oxidation efficiency. Therefore, developing novel catalytic packing materials with high specific surface area, abundant active sites, good conductivity, and stability is of great importance for enhancing the treatment efficiency of ACO technologies. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater and its preparation and use method, so as to solve the technical problem of how to efficiently transmit current to the catalyst surface and ensure that the current can be evenly distributed to each catalytic site to improve the electrochemical oxidation efficiency.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] This invention discloses a method for preparing an electrochemical confined catalytic treatment packing for dissolved organic wastewater, comprising: placing a substrate in a polypyrrole elemental solution, subjecting it to an oxidation reaction, centrifuging, washing, drying, adding it to a TiO2 precursor solution, aging the gel, drying it a second time, and sintering it at high temperature to obtain the electrochemical confined catalytic treatment packing for dissolved organic wastewater.

[0008] Preferably, the substrate is pretreated wood-based spherical activated carbon; the pretreatment conditions are: pretreatment of the wood-based spherical activated carbon by boiling in a KOH solution with a concentration greater than 1.0 mol / L 2 to 3 times.

[0009] Preferably, the polypyrrole solution is prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2~4).

[0010] Preferably, the oxidation reaction temperature is 15~35℃; the oxidation reaction time is 10~12h; the drying temperature is 50~60℃; and the drying time is more than 24h.

[0011] Preferably, the TiO2 precursor solution is prepared using a sol-gel method; specifically including:

[0012] Anhydrous ethanol, deionized water and concentrated hydrochloric acid were stirred and mixed evenly to prepare solution A.

[0013] Anhydrous ethanol, acetic acid and tetrabutyl titanate were stirred and mixed evenly to prepare solution B.

[0014] Solution A was added dropwise to solution B, and after stirring and reacting, a TiO2 precursor solution was obtained.

[0015] More preferably, in solution A, the volume ratio of anhydrous ethanol, deionized water, and concentrated hydrochloric acid is (35~40):(30~35):(0.5~1); in solution B, the volume ratio of anhydrous ethanol, acetic acid, and tetrabutyl titanate is (60~70):(20~30):(30~40); solution A is added dropwise to solution B at a rate of 4~6 mL / min; the reaction conditions are: stirring at a rate of 500~1000 r / min for 20~30 min.

[0016] Preferably, the gel is aged for 2-3 days; the secondary drying temperature is 100-110℃; and the secondary drying time is 7-10 hours.

[0017] Preferably, the conditions for high-temperature sintering are as follows: under nitrogen protection, the temperature is first raised to 150-250°C within 20-40 minutes, then calcined at 150-250°C for 1-2 hours, then raised to 500-600°C within 40 minutes, and finally calcined at 500-600°C for 2-3 hours.

[0018] The present invention also discloses an electrochemical confined catalytic treatment packing for dissolved organic wastewater, which is prepared by the above-mentioned method. The packing consists of a core and a surface load; the core is a conductive particle with a high specific surface area; and the surface load is a TiO2 polypyrrole composite.

[0019] The present invention also discloses a method for using a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater, comprising: firstly, feeding the organic wastewater into an electrochemical reactor (1) to ensure continuous water intake, then adding the packing material (3) for electrochemical confinement catalytic treatment of dissolved organic wastewater into the electrochemical reactor (1), starting the DC power supply (4) to make the electrocatalytic oxidation electrode (2) operate stably, and after electrocatalytic reaction, the dissolved organic matter in the organic wastewater is degraded, and the treated water is discharged to complete the entire purification process.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] This invention discloses a method for preparing a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater. The method involves supported or coupled confined catalytic conductive particles with a high specific surface area conductive particle core and a TiO2-polypyrrole composite loaded on the surface. The synthesis process is simple, exhibiting excellent conductivity, high temperature resistance, and good oxidation resistance. The high specific surface area conductive particles ensure efficient current output within the packing material and efficient loading of the TiO2-polypyrrole composite. The hydroxyl and carbonyl groups carried by the TiO2 on the surface of the packing material can interact with dissolved organic matter, thereby achieving pollutant adsorption. Polypyrrole, as a polymer compound, possesses unique electrical and optical properties, ensuring effective current transfer to the adsorbed dissolved organic molecules within the packing material, leading to their catalytic decomposition.

[0022] This invention also discloses an electrochemical confined catalytic packing material for treating dissolved organic wastewater prepared by the above-mentioned method. By adding this packing material to the electrochemical reactor, numerous micro-electrolytic cells can be polarized under an electric field, thereby providing ample active sites for the electrocatalytic reaction, increasing the generation of free radicals, and shortening the mass transfer of organic matter between the positive and negative electrodes, significantly improving the oxidation / reduction efficiency of the wastewater. Furthermore, since the specific surface area of ​​the electrochemical confined catalytic packing material for treating dissolved organic wastewater is much higher than that of the metal anode, and doping or modification of the metal anode cannot significantly increase the active sites on its surface, the use of supported or coupled confined catalytic packing materials can effectively solve the problem of insufficient active matter participating in the electrocatalytic reaction of organic matter.

[0023] This invention also discloses a method for using the aforementioned electrochemical confined catalytic treatment packing material for dissolved organic wastewater. In water treatment, the hydroxyl and carbonyl groups carried by the titanium dioxide on the surface of the packing material can rapidly interact with dissolved organic matter in the water, thereby achieving the adsorption and removal of pollutants. The packing material is placed in an electrochemical reactor, where it is polarized by an electric field to form numerous micro-electrolytic cells. The high specific surface area of ​​the conductive particles enables efficient current output within the packing material, which is transferred to the TiO2-polypyrrole complex via conductive polypyrrole, ensuring that the current is effectively transmitted to the adsorbed dissolved organic molecules, leading to their catalytic decomposition. Attached Figure Description

[0024] Figure 1 This is a schematic diagram illustrating the method of using the electrochemical confined catalytic treatment packing material for dissolved organic wastewater disclosed in this invention.

[0025] Figure 2 The images shown are SEM images of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater disclosed in this invention; where (a) is magnified by 5000 times and (b) is magnified by 10000 times.

[0026] Wherein: 1-Electrochemical reactor; 2-Electrocatalytic oxidation electrode; 3-Catalyst packing for electrochemical confined catalytic treatment of dissolved organic wastewater; 4-DC power supply. Detailed Implementation

[0027] To enable those skilled in the art to better understand the present invention, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0028] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0029] In the description of the embodiments of the present invention, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. Furthermore, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0030] Furthermore, the use of the term "horizontal" does not imply that the component must be absolutely horizontal, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0031] In the description of the embodiments of the present invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in the present invention according to the specific circumstances.

[0032] The present invention will now be described in further detail with reference to the accompanying drawings:

[0033] This invention discloses an electrochemical confined catalytic packing material for treating dissolved organic wastewater. The material comprises a supported or coupled confined catalytic packing material with high specific surface area conductive particles as its core, supported by a TiO2 polypyrrole complex. In water treatment, the hydroxyl and carbonyl groups carried by the titanium dioxide on the packing surface can rapidly interact with dissolved organic matter in the water, thereby achieving the adsorption and removal of pollutants. The packing material is placed in an electrochemical reactor, where it is polarized by an electric field to form numerous micro-electrolytic cells. The high specific surface area conductive particles of the packing material enable efficient current output within the catalytic packing material, which is transferred to the TiO2 polypyrrole complex via conductive polypyrrole, ensuring that the current is effectively transmitted to the adsorbed dissolved organic molecules, leading to their catalytic decomposition.

[0034] The working principle of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater disclosed in this invention is as follows:

[0035] In water treatment, the hydroxyl and carbonyl groups carried by titanium dioxide on the surface of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater can rapidly interact with dissolved organic matter in the water, thereby achieving the adsorption and removal of pollutants. The packing material is placed in an electrochemical reactor, where it is polarized by an electric field to form numerous micro-electrolytic cells. The high specific surface area of ​​the conductive particles in the packing material enables efficient current output within the catalytic packing material, which is transferred to the TiO2-polypyrrole complex via conductive polypyrrole, ensuring that the current is effectively transmitted to the adsorbed dissolved organic molecules, leading to their catalytic decomposition.

[0036] See Figure 1This diagram illustrates the usage of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater disclosed in this invention. As shown, the organic wastewater enters the electrochemical reactor 1 through a dedicated "inlet," marking the beginning of the entire treatment process. Inside the electrochemical reactor 1, the organic wastewater comes into contact with the electrocatalytic oxidation electrode 2 and the electrochemical confined catalytic treatment packing material 3. A DC power supply 4 provides the necessary current to drive the electrochemical reaction. Under the influence of the current, the electrocatalytic oxidation electrode 2 catalyzes the oxidation reaction, promoting the decomposition of dissolved organic matter. The electrochemical confined catalytic treatment packing material 3, through its unique structure and catalytic properties, efficiently treats the dissolved organic matter in the wastewater within a confined space. After electrochemical treatment and catalysis by the electrochemical confined catalytic treatment packing material 3, the dissolved organic matter in the wastewater is effectively degraded, and the treated water is discharged through the "product water" outlet, completing the entire purification process. This method achieves efficient treatment of dissolved organic matter through the synergistic effect of electrochemical reactor and packing material. It is applicable to various wastewater treatment scenarios containing dissolved organic matter, such as industrial wastewater and domestic sewage. It has the advantages of simple operation, high energy utilization rate and significant treatment efficiency.

[0037] Figure 2 The image shows an SEM image of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater disclosed in this invention; where (a) is magnified at 5000x and (b) is magnified at 10000x. As can be seen from the image, polypyrrole and titanium dioxide molecules are uniformly loaded on the surface of wood-based spherical activated carbon, and the polypyrrole and titanium dioxide molecules are arranged alternately and uniformly.

[0038] This invention discloses a method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater, comprising the following steps:

[0039] Step 1: Select wood-based spherical activated carbon with a high specific surface area of ​​more than 1500 m² / g as the substrate;

[0040] Step 2: Place the wood-based spherical activated carbon obtained in Step 1 as a substrate in a polypyrrole solution and oxidize it at 15-35℃ for 10-12 hours. Then, centrifuge to separate the solid, wash it with a large amount of deionized water, and finally dry it at 50-60℃ for more than 24 hours.

[0041] Step 3: Using tetrabutyl titanate as a precursor, a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater was prepared by the sol-gel method. Solution A and solution B were prepared. Solution A was added dropwise to solution B at a rate of 4-6 mL / min, while solution B was stirred at a rate of 500-1000 r / min to accelerate dissolution. After the addition was completed, stirring was continued for 20-30 min to ensure complete reaction, and a TiO2 precursor solution was obtained.

[0042] Step 4: Place the solid separated in Step 2 into the TiO2 precursor solution obtained in Step 3, stir evenly, and let it stand for 2-3 days to age the gel; place the above intermediate in an oven and dry at 100-110℃ for 7-10 h, then transfer it to an atmosphere furnace and sinter at high temperature under nitrogen protection; repeat Step 3 and Step 4 as needed to increase the number of loading times to prepare filler particles with different TiO2 loadings;

[0043] Step 5: During the experiment, record the weight of the unloaded separated solid after the above heat treatment, and calculate the load by subtracting the mass of the separated solid from the mass of the packing material at different loading times.

[0044] In step 1, wood-based spherical activated carbon is pretreated by boiling in a KOH solution with a concentration greater than 1.0 mol / L 2-3 times, and then used for loading the active components.

[0045] In step 2, the polypyrrole solution is prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2~4).

[0046] In step 3, the preparation of solution A is as follows: weigh 35-40 mL of anhydrous ethanol, 30-35 mL of deionized water, and 0.5-1 mL of concentrated hydrochloric acid into a 300 mL beaker, mix them evenly, and stir magnetically until homogeneous (20-30 min); the preparation of solution B is as follows: add 60-70 mL of anhydrous ethanol, 20-30 mL of acetic acid, and 30-40 mL of tetrabutyl titanate (slowly added along the beaker wall) into a 500 mL beaker, and stir evenly.

[0047] In step 4, the heat treatment procedure is as follows: raise the temperature to 150-250℃ within 20-40 minutes, hold at 150-250℃ for 1-2 hours, then raise the temperature from 200℃ to 500-600℃ within 40 minutes, and finally calcine at 500-600℃ for 2-3 hours.

[0048] The present invention discloses a method for using a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater, comprising the following steps:

[0049] Step 1: Add a certain concentration of dissolved organic wastewater electrochemical confined catalytic treatment packing 3 to electrochemical reactor 1;

[0050] Step 2: Continuous inlet and outlet of water in electrochemical reactor 1;

[0051] Step 3: Turn on the DC power supply 4 to make the electrocatalytic oxidation electrode 2 operate stably.

[0052] Example 1

[0053] A method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater includes the following steps:

[0054] Step 1: The wood-based spherical activated carbon is pretreated twice by boiling in a 1.0 mol / L KOH solution and then used as a substrate;

[0055] Step 2: The wood-based spherical activated carbon pretreated in Step 1 was placed in a polypyrrole solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:3. After oxidation at 35°C for 10 hours, the solid was separated by centrifugation, washed with a large amount of deionized water, and finally dried at 50°C for 24 hours.

[0056] Step 3: Mix 35 mL of anhydrous ethanol, 32 mL of deionized water, and 0.6 mL of concentrated hydrochloric acid in a 300 mL beaker until homogeneous, and stir magnetically for 20 min to obtain solution A; mix 70 mL of anhydrous ethanol, 23 mL of acetic acid, and 35 mL of tetrabutyl titanate (added slowly along the beaker wall) in a 500 mL beaker and stir until homogeneous to obtain solution B; add solution A dropwise to solution B at a rate of 4 mL / min, while stirring solution B at a rate of 500 r / min to accelerate dissolution; after the addition is complete, continue stirring for 20 min to ensure complete reaction, and obtain TiO2 precursor solution;

[0057] Step 4: The solid separated in Step 2 is placed in the TiO2 precursor solution obtained in Step 3 and stirred evenly. The gel is then aged for 2 days. After drying in an oven at 105℃ for 7 h, it is transferred to an atmosphere furnace. Under nitrogen protection, the temperature is first raised to 200℃ within 30 min, then calcined at 200℃ for 1 h, then raised to 550℃ within 40 min, and finally calcined at 550℃ for 2 h. After high-temperature sintering, the electrochemical confinement catalytic treatment packing for dissolved organic wastewater is obtained.

[0058] Example 2

[0059] A method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater includes the following steps:

[0060] Step 1: The wood-based spherical activated carbon is pretreated by boiling in a 1.5 mol / L KOH solution three times and then used as a substrate;

[0061] Step 2: The wood-based spherical activated carbon pretreated in Step 1 was placed in a polypyrrole solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:2. After oxidation at 25°C for 11 hours, the solid was separated by centrifugation, washed with a large amount of deionized water, and finally dried at 55°C for 25 hours.

[0062] Step 3: Mix 36 mL of anhydrous ethanol, 30 mL of deionized water, and 0.5 mL of concentrated hydrochloric acid in a 300 mL beaker until homogeneous, and stir magnetically for 20 min to obtain solution A; mix 60 mL of anhydrous ethanol, 20 mL of acetic acid, and 30 mL of tetrabutyl titanate (added slowly along the beaker wall) in a 500 mL beaker and stir until homogeneous to obtain solution B; add solution A dropwise to solution B at a rate of 5 mL / min, while stirring solution B at a rate of 600 r / min to accelerate dissolution; after the addition is complete, continue stirring for 25 min to ensure complete reaction, and obtain the TiO2 precursor solution;

[0063] Step 4: The solid separated in Step 2 is placed in the TiO2 precursor solution obtained in Step 3 and stirred evenly. The gel is then aged for 3 days. After drying in an oven at 100°C for 8 hours, it is transferred to an atmosphere furnace. Under nitrogen protection, the temperature is first raised to 150°C within 20 minutes, then calcined at 150°C for 2 hours, then raised to 500°C within 40 minutes, and finally calcined at 500°C for 3 hours. After high-temperature sintering, the electrochemical confined catalytic treatment packing for dissolved organic wastewater is obtained.

[0064] Example 3

[0065] A method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater includes the following steps:

[0066] Step 1: The wood-based spherical activated carbon is pretreated twice by boiling in a 1.5 mol / L KOH solution and then used as a substrate;

[0067] Step 2: The wood-based spherical activated carbon pretreated in Step 1 was placed in a polypyrrole solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:4. After oxidation at 15°C for 12 hours, the solid was separated by centrifugation, washed with a large amount of deionized water, and finally dried at 60°C for 26 hours.

[0068] Step 3: Mix 37 mL of anhydrous ethanol, 31 mL of deionized water, and 0.7 mL of concentrated hydrochloric acid in a 300 mL beaker until homogeneous, and stir magnetically for 20 min to obtain solution A; add 62 mL of anhydrous ethanol, 30 mL of acetic acid, and 40 mL of tetrabutyl titanate (slowly added along the beaker wall) to a 500 mL beaker and stir until homogeneous to obtain solution B; add solution A dropwise to solution B at a rate of 6 mL / min, while stirring solution B at 700 r / min to accelerate dissolution; after the addition is complete, continue stirring for 30 min to ensure complete reaction, and obtain TiO2 precursor solution;

[0069] Step 4: The solid separated in Step 2 is placed in the TiO2 precursor solution obtained in Step 3 and stirred evenly. The gel is then aged for 2.5 days. After drying in an oven at 110℃ for 9 h, it is transferred to an atmosphere furnace. Under nitrogen protection, the temperature is first raised to 250℃ within 40 min, then calcined at 250℃ for 1.5 h, then raised to 600℃ within 40 min, and finally calcined at 600℃ for 2 h. After high-temperature sintering, the electrochemical confinement catalytic treatment packing for dissolved organic wastewater is obtained.

[0070] Example 4

[0071] A method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater includes the following steps:

[0072] Step 1: The wood-based spherical activated carbon is pretreated by boiling in a 1.5 mol / L KOH solution three times and then used as a substrate;

[0073] Step 2: The wood-based spherical activated carbon pretreated in Step 1 was placed in a polypyrrole solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:3. After oxidation at 20°C for 11.5 h, the solid was separated by centrifugation, washed with a large amount of deionized water, and finally dried at 58°C for 27 h.

[0074] Step 3: Mix 38 mL of anhydrous ethanol, 34 mL of deionized water, and 0.9 mL of concentrated hydrochloric acid in a 300 mL beaker until homogeneous, and stir magnetically for 20 min to obtain solution A; mix 64 mL of anhydrous ethanol, 25 mL of acetic acid, and 33 mL of tetrabutyl titanate (added slowly along the beaker wall) in a 500 mL beaker and stir until homogeneous to obtain solution B; add solution A dropwise to solution B at a rate of 5.5 mL / min, while stirring solution B at 800 r / min to accelerate dissolution; after the addition is complete, continue stirring for 27 min to ensure complete reaction, and obtain the TiO2 precursor solution;

[0075] Step 4: The solid separated in Step 2 is placed in the TiO2 precursor solution obtained in Step 3 and stirred evenly. The gel is then aged for 3 days. After drying in an oven at 103℃ for 9 hours, it is transferred to an atmosphere furnace. Under nitrogen protection, the temperature is first raised to 220℃ within 25 minutes, then calcined at 220℃ for 1.5 hours, then raised to 520℃ within 40 minutes, and finally calcined at 520℃ for 3 hours. After high-temperature sintering, the electrochemical confinement catalytic treatment packing for dissolved organic wastewater is obtained.

[0076] Example 5

[0077] A method for preparing a packing material for electrochemical confinement catalytic treatment of dissolved organic wastewater includes the following steps:

[0078] Step 1: The wood-based spherical activated carbon is pretreated by boiling in a 2 mol / L KOH solution three times, and then used as a substrate;

[0079] Step 2: The wood-based spherical activated carbon pretreated in Step 1 was placed in a polypyrrole solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:4. After oxidation at 30°C for 10.5 h, the solid was separated by centrifugation, washed with a large amount of deionized water, and finally dried at 52°C for 30 h.

[0080] Step 3: Mix 40 mL of anhydrous ethanol, 35 mL of deionized water, and 1 mL of concentrated hydrochloric acid in a 300 mL beaker until homogeneous, and stir magnetically for 20 min to obtain solution A; add 68 mL of anhydrous ethanol, 27 mL of acetic acid, and 37 mL of tetrabutyl titanate (slowly added along the beaker wall) to a 500 mL beaker and stir until homogeneous to obtain solution B; add solution A dropwise to solution B at a rate of 4.5 mL / min, while stirring solution B at 1000 r / min to accelerate dissolution; after the addition is complete, continue stirring for 30 min to ensure complete reaction, and obtain TiO2 precursor solution;

[0081] Step 4: The solid separated in Step 2 is placed in the TiO2 precursor solution obtained in Step 3 and stirred evenly. The gel is then aged for 3 days. After drying in an oven at 108℃ for 10 hours, it is transferred to an atmosphere furnace. Under nitrogen protection, the temperature is first raised to 240℃ within 35 minutes, then calcined at 240℃ for 2 hours, then raised to 580℃ within 40 minutes, and finally calcined at 580℃ for 2.5 hours. After high-temperature sintering, the electrochemical confined catalytic treatment packing for dissolved organic wastewater is obtained.

[0082] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for preparing a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater, characterized in that, include: The substrate was placed in a solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2~4), and after oxidation, it was centrifuged, washed, dried, and then added to a TiO2 precursor solution. After aging and gelation, secondary drying, and high-temperature sintering, a packing material for electrochemical confined catalytic treatment of dissolved organic wastewater was obtained; the substrate was pretreated wood-based spherical activated carbon. The conditions for high-temperature sintering are as follows: under nitrogen protection, the temperature is first raised to 150-250℃ within 20-40 minutes, then calcined at 150-250℃ for 1-2 hours, then raised to 500-600℃ within 40 minutes, and finally calcined at 500-600℃ for 2-3 hours.

2. The preparation method of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater according to claim 1, characterized in that, The pretreatment conditions are as follows: the wood-based spherical activated carbon is pretreated by boiling in a KOH solution with a concentration greater than 1.0 mol / L 2 to 3 times.

3. The preparation method of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater according to claim 1, characterized in that, The oxidation reaction is carried out at a temperature of 15-35°C for 10-12 hours; the drying temperature is 50-60°C for 24 hours or more.

4. The preparation method of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater according to claim 1, characterized in that, The TiO2 precursor solution was prepared using a sol-gel method; specifically, it includes: Anhydrous ethanol, deionized water and concentrated hydrochloric acid were stirred and mixed evenly to prepare solution A. Anhydrous ethanol, acetic acid and tetrabutyl titanate were stirred and mixed evenly to prepare solution B. Solution A was added dropwise to solution B, and after stirring and reacting, a TiO2 precursor solution was obtained.

5. The preparation method of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater according to claim 4, characterized in that, In solution A, the volume ratio of anhydrous ethanol, deionized water, and concentrated hydrochloric acid is (35~40):(30~35):(0.5~1); in solution B, the volume ratio of anhydrous ethanol, acetic acid, and tetrabutyl titanate is (60~70):(20~30):(30~40); solution A is added dropwise to solution B at a rate of 4~6 mL / min; the stirring reaction conditions are: stirring at a rate of 500~1000 r / min for 20~30 min.

6. The preparation method of the electrochemical confined catalytic treatment packing material for dissolved organic wastewater according to claim 1, characterized in that, The aging time for the gel is 2-3 days; the temperature for the secondary drying is 100-110℃; and the time for the secondary drying is 7-10 hours.

7. A packing material for electrochemical confined catalytic treatment of dissolved organic wastewater, characterized in that, The filler material for electrochemical confined catalytic treatment of dissolved organic wastewater, prepared by any one of claims 1 to 6, consists of a core and a surface load; the core is a conductive particle with a high specific surface area; and the surface load is a TiO2 polypyrrole composite.

8. A method of using the electrochemical confined catalytic treatment packing material for dissolved organic wastewater as described in claim 7, characterized in that, include: First, organic wastewater is fed into the electrochemical reactor (1) to ensure continuous water intake. Then, the electrochemical confinement catalytic treatment packing (3) for dissolved organic wastewater is added into the electrochemical reactor (1). The DC power supply (4) is started to make the electrocatalytic oxidation electrode (2) run stably. After electrocatalytic reaction, the dissolved organic matter in the organic wastewater is degraded, and the treated water is discharged to complete the entire purification process.

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