Electrochemical confinement catalytic treatment filler for dissolved organic matter wastewater as well as preparation method and use method of electrochemical confinement catalytic treatment filler

Abstract

The invention discloses a dissolved organic matter wastewater electrochemical confinement catalytic treatment filler and a preparation and use method thereof, and belongs to the technical field of water treatment.The preparation method comprises the steps that a substrate is placed in a polypyrrole elementary substance solution, after oxidation reaction, centrifugal separation, washing and drying are conducted, the substrate is added into a TiO2 precursor solution, gel aging and secondary drying are conducted, and a TiO2 / TiO2 composite material is obtained; and sintering at high temperature to obtain the dissolved organic matter wastewater electrochemical confinement catalytic treatment filler. Hydroxyl and carbonyl groups carried by TiO2 can quickly interact with soluble organic matters in water, so that pollutants are adsorbed and removed. The filler is put into an electrochemical reactor, countless micro electrolytic cells are formed by polarization under the action of an electric field, efficient output of current in the catalytic filler is realized by conductive particles with high specific surface area, and the current is transmitted to the interior of a TiO2 polypyrrole complex through conductive polypyrrole, so that the current in the filler is effectively transmitted to adsorbed soluble organic matter molecules; and carrying out catalytic decomposition.

Description

Technical Field

[0001] The present invention belongs to the technical field of water treatment, and in particular relates to a filler for electrochemical confined catalytic treatment of soluble organic wastewater and a preparation and use method thereof. Background Art

[0002] In today's increasingly severe global environment, the protection and management of water resources has become the focus of attention of governments and all sectors of society. Dissolved organic matter (DOM), as an important type of pollutant in water bodies, has a wide range of sources, including industrial wastewater discharge, agricultural fertilizer and pesticide loss, domestic sewage, and natural biological processes. These dissolved organic matter not only affects the sensory quality of water bodies, such as color, turbidity and odor, but may also act as precursors and be converted into more toxic compounds, such as disinfection by-products, through a series of complex physical and chemical reactions in the water environment, posing a potential threat to aquatic ecosystems and human health. Therefore, the effective removal of dissolved organic matter in water bodies is of great significance for ensuring drinking water safety, maintaining water ecological balance, and promoting sustainable development.

[0003] For the treatment of dissolved organic matter, traditional methods such as physical treatment methods such as coagulation, precipitation, filtration, and biological treatment processes can remove some organic matter to a certain extent, but the removal effect of difficult-to-degrade and low-concentration dissolved organic matter is limited. In recent years, electrochemical advanced oxidation technology (EAOP) has shown great potential in the treatment of difficult-to-degrade organic matter due to its high efficiency and environmental protection. This technology applies an electric field and uses strong oxidants (such as hydroxyl radicals) generated by electrode reactions to oxidize and decompose organic matter, converting it into harmless or low-toxic substances. In particular, by optimizing electrode materials, electrolyte composition, and reaction conditions, the oxidation efficiency and treatment effect can be significantly improved. Among them, the selection and modification of electrode materials are the key to improving the efficiency of electrochemical oxidation. Researchers are constantly exploring new electrode materials, such as supported catalysts, nanomaterials, and composite materials, in order to obtain higher catalytic activity and stability.

[0004] Although electrochemical advanced oxidation technology has made significant progress in the treatment of dissolved organic matter, there are still some problems that need to be solved. On the one hand, although traditional electrode materials such as metal anodes have good conductivity, they have limited specific surface area and insufficient active sites, which limits the improvement of catalytic efficiency. On the other hand, the loading of a single catalyst is often difficult to meet the requirements of high catalytic activity and good stability at the same time, especially in long-term operation and complex water conditions, problems such as catalyst shedding and deactivation often occur. In addition, how to efficiently transmit current to the catalyst surface and ensure that the current can be evenly distributed to each catalytic site is also a key problem in improving the efficiency of electrochemical oxidation. Therefore, the development of a new catalytic filler with high specific surface area, rich active sites, good conductivity and stability is of great significance to improving the treatment efficiency of electrochemical advanced oxidation technology. Summary of the invention

[0005] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a filler for electrochemical confined catalytic treatment of soluble organic wastewater and a method for preparing and using the filler, 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] In order to achieve the above object, the present invention adopts the following technical solutions: The invention discloses a preparation method of a filler for electrochemical confined catalytic treatment of soluble organic wastewater, comprising: placing a substrate in a polypyrrole single substance solution, subjecting the substrate to an oxidation reaction, centrifuging, washing, drying, and adding a TiO 2 In the precursor solution, after aging gel, secondary drying and high-temperature sintering, the electrochemical confined catalytic treatment filler for soluble organic wastewater is obtained.

[0007] Preferably, the substrate is pretreated wood spherical activated carbon; the pretreatment conditions are: the wood spherical activated carbon is pretreated by boiling a KOH solution with a concentration greater than 1.0 mol / L for 2 to 3 times.

[0008] Preferably, the polypyrrole single substance solution is prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2-4).

[0009] Preferably, the temperature of the oxidation reaction is 15-35° C.; the time of the oxidation reaction is 10-12 h; the temperature of the drying is 50-60° C.; and the time of the drying is more than 24 h.

[0010] Preferably, TiO 2 The precursor solution is prepared by a sol-gel method; specifically comprising: The anhydrous ethanol, deionized water and concentrated hydrochloric acid were stirred and mixed to obtain liquid A; Anhydrous ethanol, acetic acid and tetrabutyl titanate are stirred and mixed uniformly to prepare liquid B; Liquid A was added dropwise to liquid B, and after stirring and reacting, TiO 2 Precursor solution.

[0011] Further preferably, in liquid A, the volume ratio of anhydrous ethanol, deionized water and concentrated hydrochloric acid is (35-40): (30-35): (0.5-1); in liquid B, the volume ratio of anhydrous ethanol, acetic acid and tetrabutyl titanate is (60-70): (20-30): (30-40); liquid A is added dropwise to liquid B at a rate of 4-6 mL / min; the stirring reaction conditions are: stirring the reaction at a rate of 500-1000 r / min for 20-30 min.

[0012] Preferably, the gel aging time is 2 to 3 days; the secondary drying temperature is 100 to 110° C.; and the secondary drying time is 7 to 10 h.

[0013] Preferably, the high temperature sintering conditions are: under nitrogen protection, first raise the temperature to 150-250°C within 20-40 minutes, then calcine at 150-250°C for 1-2 hours, then raise the temperature to 500-600°C within 40 minutes, and finally calcine at 500-600°C for 2-3 hours.

[0014] The present invention also discloses a filler for electrochemical confined catalytic treatment of wastewater with dissolved organic matter, which is prepared by the above-mentioned preparation method. The filler for electrochemical confined catalytic treatment of wastewater with dissolved organic matter consists of a core and a surface load; the core is a conductive particle with a high specific surface area; the surface load is TiO 2 Polypyrrole complex.

[0015] The present invention also discloses a method for using a filler for electrochemical confined catalytic treatment of soluble organic wastewater, comprising: firstly passing the organic wastewater into an electrochemical reactor (1) to ensure continuous water inflow, then adding the filler for electrochemical confined catalytic treatment of soluble organic wastewater (3) into the electrochemical reactor (1), starting a direct current power supply (4) to allow the electrocatalytic oxidation electrode (2) to operate stably, degrading the soluble organic matter in the organic wastewater after an electrocatalytic reaction, discharging the treated water, and completing the entire purification process.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The invention discloses a preparation method of a filler for electrochemical confined catalytic treatment of soluble organic wastewater. The loaded or coupled confined catalytic conductive particles have high specific surface area conductive particles as the core, and TiO2 is loaded on the surface. 2Polypyrrole complex has simple synthesis process, excellent conductivity, high temperature resistance and good antioxidant properties. The conductive particles with high specific surface area ensure the efficient output of current inside the filler for electrochemical confined catalytic treatment of soluble organic wastewater, as well as the high conductivity of TiO 2 Efficient loading of polypyrrole composites and electrochemical confined catalytic treatment of dissolved organic wastewater on the surface of filler TiO 2 The hydroxyl and carbonyl groups carried can interact with soluble organic matter to achieve the adsorption of pollutants. As a polymer compound, polypyrrole has special electrical and optical properties, which can ensure that the current in the electrochemical confined catalytic treatment filler of soluble organic wastewater is effectively transmitted to the adsorbed soluble organic molecules, so that they are catalytically decomposed.

[0017] The present invention also discloses a filler for electrochemical confined catalytic treatment of soluble organic wastewater prepared by the above-mentioned preparation method. By adding the filler for electrochemical confined catalytic treatment of soluble organic wastewater in an electrochemical reactor, numerous micro-electrolyzers can be polarized under the action of an electric field, thereby providing sufficient 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, greatly improving the oxidation / reduction efficiency of wastewater. In addition, since the specific surface area of ​​the filler for electrochemical confined catalytic treatment of soluble organic wastewater is much higher than that of the metal anode, and the doping or modification of the metal anode cannot greatly increase the active sites on its surface, the use of loaded or coupled confined catalytic fillers can effectively solve the problem of low mass of active substances participating in the electrocatalytic reaction of organic matter.

[0018] The present invention also discloses a method for using the above-mentioned electrochemical confined catalytic treatment filler for soluble organic wastewater. In water treatment, the hydroxyl and carbonyl groups carried by the titanium dioxide on the surface of the electrochemical confined catalytic treatment filler for soluble organic wastewater can quickly interact with the soluble organic matter in the water, thereby achieving the adsorption and removal of pollutants. The electrochemical confined catalytic treatment filler for soluble organic wastewater is placed in an electrochemical reactor, and the electric field is used to polarize to form countless micro-electrolyzers. The conductive particles with high specific surface area realize the efficient output of the current inside the electrochemical confined catalytic treatment filler for soluble organic wastewater, and the current is transferred to the TiO 2 Inside the polypyrrole complex, it is ensured that the current in the filler for electrochemical confined catalytic treatment of soluble organic wastewater is effectively transmitted to the adsorbed soluble organic molecules, so that they are catalytically decomposed. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic diagram of the method for using the electrochemical confined catalytic treatment filler for wastewater with dissolved organic matter disclosed in the present invention; Figure 2The SEM images of the filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter disclosed in the present invention are as follows; wherein (a) is a magnification of 5000 times, and (b) is a magnification of 10000 times.

[0020] Wherein: 1-electrochemical reactor; 2-electrocatalytic oxidation electrode; 3-electrochemical confined catalytic treatment filler for soluble organic wastewater; 4-DC power supply. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiment of the present invention. Obviously, the described embodiment is only an embodiment of a part of the present invention, rather than all embodiments. The components of the embodiment of the present invention generally described and shown in the drawings here can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the scope of protection of the present invention.

[0022] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0023] In the description of the embodiments of the present invention, it should be noted that if the terms "upper", "lower", "horizontal", "inner", etc. indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the product of the invention is usually placed when in use, it is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0024] In addition, if the term "horizontal" appears, it does not mean that the component must be absolutely horizontal, but can be slightly tilted. For example, "horizontal" only means that its direction is more horizontal than "vertical", which does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0025] In the description of the embodiments of the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "set", "install", "connect", and "connect" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal connection of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0026] The present invention is further described in detail below in conjunction with the accompanying drawings: The invention discloses a filler for electrochemical confined catalytic treatment of wastewater with dissolved organic matter, comprising a loaded or coupled confined catalytic filler with high specific surface area conductive particles as the core, loaded with TiO 2 Polypyrrole complex, in water treatment, the hydroxyl and carbonyl groups carried by titanium dioxide on the surface of the filler can quickly interact with soluble organic matter in the water, thereby achieving the adsorption and removal of pollutants. The filler is placed in an electrochemical reactor, and the electric field is used to polarize to form countless micro-electrolyzers. The conductive particles with high specific surface area of ​​the filler realize the efficient output of the current inside the catalytic filler, which is transferred to the TiO 2 Inside the polypyrrole complex, the current in the filler is effectively transmitted to the adsorbed soluble organic molecules, causing them to be catalytically decomposed.

[0027] The working principle of the electrochemical confined catalytic treatment filler for soluble organic wastewater disclosed in the present invention is as follows: In water treatment, the hydroxyl and carbonyl groups carried by titanium dioxide on the surface of the filler for electrochemical confined catalytic treatment of soluble organic wastewater can quickly interact with soluble organic matter in water, thereby achieving adsorption and removal of pollutants. The filler is placed in an electrochemical reactor, and the electric field is used to polarize to form countless micro-electrolyzers. The conductive particles with high specific surface area of ​​the filler achieve efficient current output inside the catalytic filler, which is transferred to TiO through conductive polypyrrole. 2 Inside the polypyrrole complex, the current in the filler is effectively transmitted to the adsorbed soluble organic molecules, causing them to be catalytically decomposed.

[0028] See also Figure 1The present invention discloses a schematic diagram of the method for using the electrochemical confined catalytic treatment filler for soluble organic wastewater; as can be seen from the figure, the organic wastewater enters the electrochemical reactor 1 through a special "water inlet", which is the beginning of the entire treatment process. Inside the electrochemical reactor 1, the organic wastewater contacts the electrocatalytic oxidation electrode 2 and the electrochemical confined catalytic treatment filler 3 for soluble organic wastewater. The DC power supply 4 provides the necessary current to drive the electrochemical reaction. Under the action of the current, the electrocatalytic oxidation electrode 2 catalyzes the oxidation reaction and promotes the decomposition of soluble organic matter. The electrochemical confined catalytic treatment filler 3 for soluble organic wastewater efficiently treats the soluble organic matter in the wastewater within the confinement through its special structure and catalytic performance. After electrochemical treatment and catalysis by the electrochemical confined catalytic treatment filler 3 for soluble organic wastewater, the soluble organic matter in the organic wastewater is effectively degraded, and the treated water is discharged through the "water production" port to complete the entire purification process. This method achieves efficient treatment of soluble organic matter through the synergistic effect of electrochemical reactors and fillers. It is suitable for various wastewater treatment scenarios containing soluble organic matter, such as industrial wastewater, domestic sewage, etc. It has the advantages of simple operation, high energy utilization and significant treatment efficiency.

[0029] Figure 2 The SEM images of the filler for electrochemical confined catalytic treatment of soluble organic wastewater disclosed in the present invention are as follows; wherein (a) is a magnification of 5000 times, and (b) is a magnification of 10000 times; it can be seen from the figure that polypyrrole and titanium dioxide molecules are uniformly loaded on the surface of the wood spherical activated carbon, and the polypyrrole and titanium dioxide molecules are staggered and uniformly loaded.

[0030] The present invention discloses a method for preparing a filler for electrochemical confined catalytic treatment of soluble organic wastewater, comprising the following steps: Step 1: Select wood spherical activated carbon with a high specific surface area of ​​more than 1500㎡ / g as the substrate; Step 2: Place the wood spherical activated carbon obtained in step 1 as a substrate in a polypyrrole single substance solution for oxidation reaction at 15-35°C for 10-12 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 50-60°C for more than 24 hours; Step 3: Tetrabutyl titanate was used as a precursor to prepare fillers for electrochemical confined catalytic treatment of soluble organic wastewater by the sol-gel method. Liquid A and liquid B were prepared, and liquid A was added to liquid B at a rate of 4-6 mL / min, while liquid B was stirred at a speed of 500-1000 r / min to accelerate dissolution; after the addition was completed, stirring was continued for 20-30 min to ensure sufficient reaction, and TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2The precursor solution was stirred evenly and then placed for 2-3 days to age the gel; the intermediate was placed in an oven at 100-110°C for 7-10 h and then transferred to an atmosphere furnace for high-temperature sintering under nitrogen protection; steps 3 and 4 were repeated as needed to increase the number of loading times to prepare different TiO 2 Loading amount of filler particles; Step 5: During the experiment, the weight of the unloaded separated solid after the above heat treatment is recorded, and the loading amount is calculated by subtracting the mass of the separated solid from the mass of the filler at different loading times.

[0031] Wherein, in step 1, wood spherical activated carbon is selected and pretreated by boiling a KOH solution with a concentration greater than 1.0 mol / L for 2 to 3 times, and then used for loading the active component.

[0032] In step 2, a polypyrrole single substance solution is prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2-4).

[0033] In step 3, the process for preparing liquid A is as follows: weigh 35-40 mL of anhydrous ethanol + 30-35 mL of deionized water + 0.5-1 mL of concentrated hydrochloric acid in a 300 mL beaker, mix evenly, and stir magnetically until uniform (20-30 min); the process for preparing liquid B is as follows: 60-70 mL of anhydrous ethanol + 20-30 mL of acetic acid + 30-40 mL of tetrabutyl titanate (slowly added along the wall of the beaker) in a 500 mL beaker and stir evenly.

[0034] In step 4, the heat treatment procedure is as follows: heating to 150-250°C within 20-40 min, keeping at 150-250°C for 1-2 h, then heating from 200°C to 500-600°C within 40 min, and finally calcining at 500-600°C for 2-3 h.

[0035] The present invention discloses a method for using a filler for electrochemical confined catalytic treatment of soluble organic wastewater, comprising the following steps: Step 1: adding a certain concentration of electrochemical confined catalytic treatment filler 3 for wastewater containing dissolved organic matter into the electrochemical reactor 1; Step 2: In the electrochemical reactor 1, water is continuously introduced into and discharged from the electrochemical reactor; Step 3: Start the DC power supply 4 to ensure that the electrocatalytic oxidation electrode 2 operates stably.

[0036] Example 1 A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter comprises the following steps: Step 1: The wood spherical activated carbon was pretreated twice by boiling a 1.0 mol / L KOH solution and used as a substrate; Step 2: Place the wood spherical activated carbon pretreated in step 1 in a polypyrrole single substance solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:3, and perform oxidation reaction at 35°C for 10 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 50°C for 24 hours; 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 and stir magnetically for 20 min until uniform to obtain solution A; add 70 mL of anhydrous ethanol, 23 mL of acetic acid and 35 mL of tetrabutyl titanate (slowly added along the wall of the beaker) in a 500 mL beaker and stir evenly to obtain solution B; drop solution A into solution B at a rate of 4 mL / min, while keeping solution B stirred at a rate of 500 r / min to accelerate dissolution; continue stirring for 20 min after the addition is completed to ensure sufficient reaction to obtain TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2 After stirring evenly in the precursor solution, the gel was left for 2 days to age; it was placed in an oven and dried at 105°C for 7 h, then transferred to an atmosphere furnace, and under nitrogen protection, the temperature was first raised to 200°C within 30 min, then calcined at 200°C for 1 h, then heated to 550°C within 40 min, and finally calcined at 550°C for 2 h. After high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater was obtained.

[0037] Example 2 A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter comprises the following steps: Step 1: The wood spherical activated carbon was pretreated by boiling a 1.5 mol / L KOH solution for three times and then used as a substrate; Step 2: Place the wood spherical activated carbon pretreated in step 1 in a polypyrrole single substance solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:2, and perform oxidation reaction at 25°C for 11 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 55°C for 25 hours; 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 and stir magnetically for 20 min until uniform to obtain solution A; add 60 mL of anhydrous ethanol, 20 mL of acetic acid and 30 mL of tetrabutyl titanate (slowly added along the wall of the beaker) in a 500 mL beaker and stir evenly to obtain solution B; drop solution A into solution B at a rate of 5 mL / min, while keeping solution B stirred at a rate of 600 r / min to accelerate dissolution; continue stirring for 25 min after the addition is completed to ensure sufficient reaction to obtain TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2 After stirring evenly in the precursor solution, the gel was allowed to age for 3 days; it was placed in an oven and dried at 100°C for 8 h, then transferred to an atmosphere furnace. Under nitrogen protection, the temperature was first raised to 150°C within 20 min, then calcined at 150°C for 2 h, then raised to 500°C within 40 min, and finally calcined at 500°C for 3 h. After high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater was obtained.

[0038] Example 3 A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter comprises the following steps: Step 1: The wood spherical activated carbon was pretreated twice by boiling a 1.5 mol / L KOH solution and used as a substrate; Step 2: Place the wood spherical activated carbon pretreated in step 1 in a polypyrrole single substance solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:4, and perform oxidation reaction at 15°C for 12 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 60°C for 26 hours; 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 and stir magnetically for 20 min until uniform 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) in a 500 mL beaker and stir evenly to obtain solution B; drop solution A into solution B at a rate of 6 mL / min, while keeping solution B stirred at 700 r / min to accelerate dissolution; continue stirring for 30 min after the addition to ensure sufficient reaction to obtain TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2 After stirring evenly in the precursor solution, the gel was aged for 2.5 days; it was placed in an oven and dried at 110°C for 9 h, then transferred to an atmosphere furnace. Under nitrogen protection, the temperature was first raised to 250°C within 40 min, then calcined at 250°C for 1.5 h, then raised to 600°C within 40 min, and finally calcined at 600°C for 2 h. After high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater was obtained.

[0039] Example 4 A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter comprises the following steps: Step 1: The wood spherical activated carbon was pretreated by boiling a 1.5 mol / L KOH solution for three times and then used as a substrate; Step 2: Place the wood spherical activated carbon pretreated in step 1 in a polypyrrole single substance solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:3, and perform oxidation reaction at 20°C for 11.5 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 58°C for 27 hours; 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 and stir magnetically for 20 min until uniform to obtain solution A; add 64 mL of anhydrous ethanol, 25 mL of acetic acid and 33 mL of tetrabutyl titanate (slowly added along the beaker wall) in a 500 mL beaker and stir evenly to obtain solution B; drop solution A into solution B at a rate of 5.5 mL / min, while keeping solution B stirred at 800 r / min to accelerate dissolution; continue stirring for 27 min after the addition is complete to ensure sufficient reaction to obtain TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2 After stirring evenly in the precursor solution, the gel was allowed to age for 3 days; it was placed in an oven and dried at 103°C for 9 hours and then transferred to an atmosphere furnace. Under nitrogen protection, the temperature was first raised to 220°C within 25 minutes, then calcined at 220°C for 1.5 hours, then raised to 520°C within 40 minutes, and finally calcined at 520°C for 3 hours. After high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater was obtained.

[0040] Example 5 A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter comprises the following steps: Step 1: The wood spherical activated carbon was pretreated by boiling a 2 mol / L KOH solution for three times and then used as a substrate; Step 2: Place the wood spherical activated carbon pretreated in step 1 in a polypyrrole single substance solution prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:4, and perform oxidation reaction at 30°C for 10.5 hours, then centrifuge to separate the solid, wash with a large amount of deionized water, and finally dry at 52°C for 30 hours; 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 and stir magnetically for 20 min until uniform 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 wall of the beaker) in a 500 mL beaker and stir evenly to obtain solution B; drop solution A into solution B at a rate of 4.5 mL / min, while keeping solution B stirred at a rate of 1000 r / min to accelerate dissolution; continue stirring for 30 min after the addition is completed to ensure sufficient reaction to obtain TiO 2 Precursor solution; Step 4: Place the solid separated in step 2 on the TiO 2 After stirring evenly in the precursor solution, the gel was allowed to age for 3 days; it was placed in an oven and dried at 108°C for 10 hours and then transferred to an atmosphere furnace. Under nitrogen protection, the temperature was first raised to 240°C within 35 minutes, then calcined at 240°C for 2 hours, then raised to 580°C within 40 minutes, and finally calcined at 580°C for 2.5 hours. After high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater was obtained.

[0041] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter, characterized in that: include: The substrate is placed in a polypyrrole single substance solution, subjected to an oxidation reaction, centrifuged, washed, dried, and then added to a TiO2 precursor solution. After aging the gel, secondary drying, and high-temperature sintering, a filler for electrochemical confined catalytic treatment of soluble organic wastewater is obtained.

2. The method for preparing the electrochemical confined catalytic treatment filler for soluble organic wastewater according to claim 1, characterized in that: The substrate is pretreated wood spherical activated carbon; the pretreatment conditions are: pretreatment of the wood spherical activated carbon by boiling a KOH solution with a concentration greater than 1.0 mol / L for 2 to 3 times.

3. The method for preparing the electrochemical confined catalytic treatment filler for soluble organic wastewater according to claim 1 is characterized in that: The polypyrrole single substance solution is prepared by mixing sulfuric acid and pyrrole in a molar ratio of 1:(2-4).

4. The method for preparing the electrochemical confined catalytic treatment filler for soluble organic wastewater according to claim 1 is characterized in that: The temperature of the oxidation reaction is 15-35°C; the time of the oxidation reaction is 10-12h; the temperature of the drying is 50-60°C; and the time of the drying is more than 24h.

5. The method for preparing the electrochemical confined catalytic treatment filler for soluble organic wastewater according to claim 1, characterized in that: The TiO2 precursor solution is prepared by a sol-gel method; specifically comprising: The anhydrous ethanol, deionized water and concentrated hydrochloric acid were stirred and mixed to obtain liquid A; Anhydrous ethanol, acetic acid and tetrabutyl titanate are stirred and mixed uniformly to prepare liquid B; Liquid A is added dropwise to liquid B, and after stirring and reacting, a TiO2 precursor solution is obtained.

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

7. The method for preparing the electrochemical confined catalytic treatment filler for wastewater containing dissolved organic matter according to claim 1, characterized in that: The gel aging time is 2 to 3 days; the secondary drying temperature is 100 to 110° C.; and the secondary drying time is 7 to 10 hours.

8. The method for preparing the electrochemical confined catalytic treatment filler for soluble organic wastewater according to claim 1, characterized in that: The high temperature sintering conditions are: under nitrogen protection, first heating to 150-250°C within 20-40 minutes, then calcining at 150-250°C for 1-2 hours, then heating to 500-600°C within 40 minutes, and finally calcining at 500-600°C for 2-3 hours.

9. A filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter, characterized in that: The preparation method according to any one of claims 1 to 8 is adopted, wherein the electrochemical confined catalytic treatment filler for soluble organic wastewater 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 complex.

10. A method for using a filler for electrochemical confined catalytic treatment of wastewater containing dissolved organic matter, characterized in that: include: First, the organic wastewater is introduced into the electrochemical reactor (1) to ensure continuous water inflow, and then the electrochemical confined catalytic treatment filler (3) for the soluble organic wastewater is added into the electrochemical reactor (1), and the DC power supply (4) is started to make the electrocatalytic oxidation electrode (2) operate stably. After the electrocatalytic reaction, the soluble organic matter in the organic wastewater is degraded, and the treated water is discharged, completing the entire purification process.

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