Catalytic filler, preparation method and application thereof in electrochemical synergistic ozone treatment of high-salinity wastewater

Abstract

This invention belongs to the field of wastewater treatment technology, specifically relating to a catalytic packing material, its preparation method, and its application in the electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater. The catalytic packing material is prepared from the following components in the indicated mass percentages: 5-10% carbon-encapsulated high-entropy perovskite composite material, 10-15% binder, and the balance being a carbon-based support. The carbon-encapsulated high-entropy perovskite composite material is composed of lanthanide high-entropy perovskite oxide and carbon microspheres. This invention also provides a method for electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater using this catalytic packing material. This invention combines electrochemical reactions with ozone reactions, utilizing the catalytic packing material, cathode plate, and anode plate to construct a conductive three-dimensional electrode network. This promotes the synergistic effect of electrochemical reduction reactions and ozone catalytic oxidation during the oxidation process, achieving electrochemical-assisted ozone degradation of stubborn pollutants and better decomposing stubborn organic pollutant molecules.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, specifically relating to a catalytic packing material, its preparation method, and its application in the electrochemical synergistic ozone treatment of organic matter in high-salt wastewater. Background Technology

[0002] Currently, high-salinity, recalcitrant organic wastewater discharged from industries such as chemical, pharmaceutical, and coal chemical engineering has become a serious challenge in the water treatment field. This type of wastewater typically contains high concentrations of inorganic salts such as sodium chloride and sodium sulfate, as well as complex and stable organic pollutants. Therefore, the removal of organic matter from high-salinity wastewater is hampered by salt concentration. This is because the large amounts of chloride and sulfate ions present in the wastewater can significantly consume key reactive species such as hydroxyl radicals and sulfate radicals generated during advanced oxidation processes through free radical quenching effects, leading to a sharp decline in the oxidative degradation efficiency of organic matter and making effective removal difficult.

[0003] Ozone advanced oxidation technology has shown great promise in treating recalcitrant wastewater due to its strong oxidizing power, rapid reaction, and lack of secondary pollution. Its technical principle is mainly based on two pathways: direct oxidation, where ozone molecules selectively attack unsaturated bonds or electron-rich groups in organic molecules; and indirect oxidation, where ozone decomposes under the action of catalysts, light, or alkalis to generate secondary oxidants such as hydroxyl radicals with stronger oxidizing power, achieving indiscriminate and thorough mineralization of organic matter. However, ozone itself has limited solubility in water, and its direct oxidation ability towards some saturated organic matter and aromatic compounds is relatively weak, exhibiting high selectivity, which limits its effectiveness when used alone.

[0004] To improve ozone utilization efficiency and oxidation capacity, catalytic ozone oxidation technology has emerged. This technology aims to promote ozone decomposition to generate more hydroxyl radicals or construct non-radical oxidation pathways by adding a catalyst to the reaction system. Currently, common catalysts include metal oxides (such as MnO2 and Fe2O3) and supported catalysts (such as metal supported on activated carbon). However, these traditional catalysts suffer from problems such as few active sites, poor stability, and metal leaching in high-salinity wastewater environments.

[0005] Therefore, developing a novel ozone catalyst that combines high catalytic activity, excellent structural stability, and strong resistance to salt interference is key to overcoming the bottleneck in the treatment of high-salt and recalcitrant organic wastewater. Summary of the Invention

[0006] The purpose of this invention is to provide a catalytic packing material, its preparation method, and its application in the electrochemical synergistic ozone treatment of organic matter in high-salt wastewater.

[0007] The specific technical solution is as follows:

[0008] A catalytic packing material, which is prepared from the following components in mass percentage:

[0009] Carbon-encapsulated high-entropy perovskite composites contain 5-10% carbon.

[0010] Adhesive 10-15%,

[0011] Carbon-based support is the remainder;

[0012] The carbon-encapsulated high-entropy perovskite composite material is composed of lanthanide high-entropy perovskite oxide and carbon microspheres, wherein the molecular formula of the lanthanide high-entropy perovskite oxide is La(Al) a Mn b Fe c Co d Ni e Cu f Zn g O3, where a, b, c, d, e, f, and g are all between 0.01 and 1.

[0013] The carbon-encapsulated high-entropy perovskite composite material is composed of lanthanide high-entropy perovskite oxide and carbon microspheres. The carbon-encapsulated metal interface can modulate the electronic structure of the catalyst, and the multi-metal interface can promote local electron redistribution and form an internal electric field structure with the carbon framework, inducing electron conduction. The multi-metal valence state cycle between high-entropy metals induces interactions between conductive networks, exhibiting a strong activation ability for ozone molecules and improving the decomposition efficiency and catalytic activity of the oxidant. Furthermore, the doping and regulation of the B-sites in the lanthanide (La) series perovskite, through the high-entropy effect formed by multi-metal doping at the B-sites and the synergistic effect with the carbon framework, achieves rapid electron transfer. The high and low valence interactions between the multi-metals at the B-sites lead to efficient ozone activation and rapid degradation of organic pollutants.

[0014] In a further embodiment, the binder is kaolin, wherein the mass ratio of iron in the kaolin is 3-5%; and / or,

[0015] The carbon-based material is biochar, carbon gel, coal coke, or coal powder.

[0016] In a further embodiment, the preparation steps of the carbon-encapsulated high-entropy perovskite composite material are as follows:

[0017] S11. Add water-soluble carbon precursor to water and stir to obtain solution A;

[0018] S12. Add La salt and transition metal salt to water at a molar ratio of 1:1 and stir to obtain a metal salt mixture.

[0019] S13. Mix solution A and the metal salt mixture at a volume ratio of 1:1, then carry out a hydrothermal reaction, and wash, dry and grind the resulting reaction product.

[0020] S14. The ground product is calcined at high temperature to obtain a carbon-encapsulated high-entropy perovskite composite material.

[0021] In a further embodiment, the water-soluble carbon precursor is glucose, cellulose, starch, or citric acid; and / or,

[0022] The transition metal salt is an Al, Mn, Fe, Co, Ni, Cu, or Zn salt; and / or,

[0023] The hydrothermal reaction temperature is 180–220℃ and the time is 10–12 h.

[0024] In a further step, in step S13, the reaction product is repeatedly washed with pure water and ethanol 3-5 times, then freeze-dried, and then ground to 100-300 mesh; and / or,

[0025] The purpose of grinding the reaction product is to ensure that it is fully heated during the calcination process, so that the residual carbon precursor and nitrate can be decomposed by heat.

[0026] In step S14, the high-temperature calcination is carried out under nitrogen protection, first by raising the temperature from room temperature to 200-250°C at a rate of 1-3°C / min; then by continuing to raise the temperature to 600-800°C at a rate of 4-6°C / min; and finally by maintaining the temperature at a constant temperature for 4-8 hours.

[0027] A second objective of this invention is to provide a method for preparing the aforementioned catalytic packing material, comprising the following steps:

[0028] Carbon-encapsulated high-entropy perovskite composite material, binder and carbon-based support are mixed in a certain mass ratio, and water is added and mixed before being pressed into granules; the granules are then dried and calcined to obtain catalytic filler.

[0029] In a further embodiment, the drying is carried out at 60-70°C for 10-12 hours, and the calcination is carried out at 700-900°C for 2-4 hours.

[0030] The catalytic packing has a diameter of 1.5–2.0 cm and a specific gravity of 2–5 g / cm³. 3 The crushing strength is 20-50 N.

[0031] The third objective of this invention is to provide an application of the aforementioned catalytic packing material in the electrochemical synergistic ozone treatment of organic matter in high-salt wastewater.

[0032] A further embodiment of the method for electrochemically synergistically treating organic matter in high-salinity wastewater includes the following steps:

[0033] S21. A catalytic packing material as described above is filled between the anode plate and the cathode plate in the reactor as an intermediate electrode, and the catalytic packing material is driven to rotate between the anode plate and the cathode plate to form a three-dimensional rotating electrode system.

[0034] S22. Pump the high-salt wastewater to be treated into the above reactor;

[0035] S23. Introduce ozone into the reactor and simultaneously turn on the DC power supply to carry out the electrochemical reaction.

[0036] S24. After the ozone catalytic oxidation process and the electrochemical reduction process work synergistically for 30 to 90 minutes, organic matter in the wastewater is removed.

[0037] In a further embodiment, the reactor is an electrochemically enhanced ozone reaction device;

[0038] The catalytic packing is added at a rate of 5–50 g / L relative to the reactor volume; and / or,

[0039] The ozone flow rate is 0.1–1.0 g / min; and / or,

[0040] The DC power supply has a voltage of 1.8–2.8V and a current density of 50–100 mA / cm²; and / or,

[0041] The anode plate is a boron-doped diamond thin film electrode or a composite electrode of titanium-based noble metals and transition metal oxides; the cathode plate is a graphite, graphene, iron electrode or stainless steel electrode.

[0042] The anode plate and cathode plate are symmetrically arranged in the reaction zone of the reactor, with a spacing of 3-5 cm between them; and the catalytic packing is placed in this spacing as an intermediate electrode.

[0043] The TDS (total dissolved solids) in the high-salt wastewater is 5000-500000 mg / L, and the pH value of the high-salt wastewater is 3-11.

[0044] The catalytic packing material of this invention possesses a multi-active-center co-catalytic system and a strong metal support, which interact to give it excellent catalytic activity and stability. Furthermore, using it as an intermediate electrode to construct a three-dimensional rotating electrochemical system enhances ozone catalytic efficiency.

[0045] The carbon-based support material in the catalytic packing prepared in this invention possesses abundant surface functional groups and defect structures. The main active sites on the surface of the carbon-based material participating in catalytic ozonation include oxygen-containing functional groups, heteroatom functional groups, and defect structures in the carbon chain. Red kaolin contains transition metal components such as iron oxides, giving it certain redox catalytic capabilities, making it suitable for partial oxidation reactions or Fenton-like advanced oxidation processes.

[0046] This invention utilizes a carbon-encapsulated high-entropy perovskite composite material, combining the "multi-metal synergy" of high-entropy materials with the "high dispersion" characteristics of carbon supports to achieve a synergistic ozone catalytic effect of "high-entropy structure-oxygen vacancies-carbon defects," overcoming the bottlenecks of low activity and poor stability in traditional ozone catalysts. Furthermore, different metals provide multiple electron transfer pathways to achieve multi-metal synergistic catalysis, while the conductive network of the carbon support promotes rapid electron transfer within the synergistic system.

[0047] This invention combines electrochemical reactions with ozone reactions, using a conductive three-dimensional electrode network constructed from catalytic packing material, cathode plate, and anode plate. This promotes the synergistic effect of electrochemical reduction reaction and ozone catalytic oxidation during the oxidation process, achieving electrochemical-assisted ozone degradation of stubborn pollutants and better decomposing stubborn organic pollutant molecules.

[0048] Therefore, the present invention utilizes catalytic packing material for the synergistic treatment of organic matter in high-salt wastewater through electrochemical and ozone catalysis, achieving unexpected technical effects. Attached Figure Description

[0049] The accompanying drawings, which form part of this invention, are used to aid in understanding the invention. The contents provided in the drawings and their related descriptions in this invention can be used to explain the invention, but do not constitute an improper limitation of the invention.

[0050] Figure 1 Here is the SEM image of the material, where Figure 1 Images a and b in Example 1 are SEM images of the carbon-encapsulated high-entropy perovskite composite material. Figure 1 SEM images of the high-entropy perovskite composite materials prepared in Comparative Examples 1 (c and d);

[0051] Figure 2 The image shows a TEM image of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1. Figure 2 In the image, a is a micrometer-scale TEM image and b is a nanometer-scale TEM image.

[0052] Figure 3 EDS image of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1;

[0053] Figure 4 The images show the XRD patterns of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1.

[0054] Figure 5 XPS full spectra of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1.

[0055] Figure 6Raman spectra of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1;

[0056] Figure 7 FT-IR images of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1;

[0057] Figure 8 The electrochemical performance curves of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1 are shown; wherein Figure 8 In the diagram, a represents the CV cyclic voltammetry curve, and b represents the impedance diagram.

[0058] Figure 9 EDS image of the red clay in Example 1;

[0059] Figure 10 This is an optical image of the catalytic packing material, in which... Figure 10 In Figure a, the optical image of the catalytic packing material prepared in Example 1 is shown, and in Figure b, the optical image of the catalytic packing material prepared in Comparative Example 1 is shown.

[0060] Figure 11 This is a schematic diagram of the electrochemically enhanced ozone reaction device in the embodiment. Detailed Implementation

[0061] The present invention will be further described below with reference to specific embodiments, but the essence of the present invention is not limited to the embodiments described below. Unless otherwise specified, the methods described are conventional methods, and the materials described are available from publicly available commercial sources unless otherwise specified. Those skilled in the art should know that any simple modifications or substitutions based on the essence of the present invention fall within the scope of protection claimed by the present invention.

[0062] The specific technical solution of the present invention is as follows:

[0063] 1. Preparation of carbon-encapsulated high-entropy perovskite composite materials:

[0064] Add the water-soluble carbon precursor to a beaker containing deionized water and stir to obtain solution A;

[0065] La salt and seven transition metal salts were added to water in a 1:1 molar ratio and stirred to obtain a metal salt mixture; the seven transition metal salts were added in equal amounts.

[0066] The La salts and transition metal salts are nitrates, sulfates, or their crystalline forms, respectively. Specifically, the La salt is La(NO3)3·6H2O, and the transition metal salts are Al2(SO4)3·18H2O, Mn(NO3)2·4H2O, Fe(NO3)3·9H2O, Co(NO3)3·6H2O, Ni(NO3)3·6H2O, Cu(NO3)2·3H2O, and ZnSO4·7H2O.

[0067] Solution A was mixed with the metal salt mixture at a volume ratio of 1:1 and transferred to a hydrothermal high-pressure reactor. The mixture was then hydrothermally reacted at 180–220 °C for 10–12 h. The mixture was cooled to room temperature, and the precipitate was collected. It was then washed three times with deionized water and anhydrous ethanol, and freeze-dried at -20 °C. Finally, it was ground to a fineness of 100–300 mesh.

[0068] Under nitrogen protection, the grinding product is heated to 200-250℃ at a heating rate of 1-3℃ / min, and then heated to 600-800℃ at a heating rate of 4-6℃ / min, and held for 4-6 hours. After cooling, carbon-encapsulated high-entropy perovskite composite material is obtained.

[0069] 2. Preparation of catalytic packing material:

[0070] Weigh out the carbon-encapsulated high-entropy perovskite composite material, binder, and carbon-based support prepared above, mix them, add water, stir, and press into granules. Then dry the granules at 60-70℃ for 10-12 hours, and then calcine them at 700-900℃ for 2-4 hours to obtain the catalytic filler.

[0071] Testing revealed that the catalytic packing material has a diameter of 1.5–2.0 cm and a specific gravity of 2–5 g / cm³. 3 The crushing strength is 20-50 N.

[0072] The carbon-encapsulated high-entropy perovskite composite material has a mass ratio of 5-10%, the binder has a mass ratio of 10-15%, and the carbon-based carrier is the remainder.

[0073] 3. Electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater:

[0074] S21. Anode plates and cathode plates are placed on both sides of the reaction zone of the electrochemically enhanced ozone reactor to form catalytic electrodes, and connected to an external power source. The aforementioned catalytic packing material is then filled between the anode and cathode plates as an intermediate electrode, wherein the amount of catalytic packing material added is 5-50 g / L of the reactor volume; and the catalytic packing material is driven to rotate between the anode and cathode plates, together forming a three-dimensional rotating electrode system.

[0075] S22. Pump the high-salt wastewater to be treated into the above reactor;

[0076] S23. Ozone is introduced into the reactor at a flow rate of 0.1–1.0 g / min, while a DC power supply is turned on to carry out the electrochemical reaction; wherein the voltage of the DC power supply is 1.8–2.8 V and the current density is 50–100 mA / cm².

[0077] S24. After the ozone catalytic oxidation process and the electrochemical reduction process work synergistically for 30 to 90 minutes, organic matter in the wastewater is removed.

[0078] The anode plate in the reactor uses boron-doped diamond thin film electrodes or composite electrodes of titanium-based noble metals and transition metal oxides; the cathode plate uses graphite, graphene, iron electrodes or stainless steel electrodes.

[0079] The anode plate and cathode plate are symmetrically arranged in the reaction zone of the reactor, with a spacing of 3-5 cm between them, for filling with catalytic packing material;

[0080] The TDS (total dissolved solids) in the high-salt wastewater is 5000-500000 mg / L, and the pH value of the high-salt wastewater is 3-11.

[0081] This invention appendix Figure 1-10 :

[0082] SEM images are used to characterize the morphology of materials using scanning electron microscopy.

[0083] TEM images are images that characterize the microstructure of materials using transmission electron microscopy.

[0084] The EDS image was obtained using an energy dispersive spectrometer.

[0085] The XRD pattern was obtained using an X-ray diffractometer.

[0086] The XPS full spectrum was obtained using an X-ray photoelectron spectrometer.

[0087] The Raman spectrum was obtained using a Raman spectrometer.

[0088] The FT-IR image was obtained using a Fourier transform infrared spectrometer.

[0089] The optical image was taken using an optical microscope.

[0090] Example 1:

[0091] Preparation of carbon-encapsulated high-entropy perovskite composite materials:

[0092] S11. Add 0.2g of starch to 50mL of pure water and stir to obtain solution A;

[0093] S12. Weigh 3.03g of La(NO3)3·6H2O, 0.67g of Al2(SO4)3·18H2O, 0.25g of Mn(NO3)2·4H2O, 0.41g of Fe(NO3)3·9H2O, 0.29g of Co(NO3)3·6H2O, 0.29g of Ni(NO3)3·6H2O, 0.24g of Cu(NO3)2·3H2O, and 0.29g of ZnSO4·7H2O, add them to 1L of water and stir for 30min, magnetically stir for 30min, and then ultrasonically disperse for 30min to obtain solution B;

[0094] S13. Slowly add solution A to solution B (volume ratio 1:1) and stir to mix. Then transfer the mixture to a hydrothermal high-pressure reactor made of polytetrafluoroethylene (PTFE) and react at 200°C for 10 hours. Cool to room temperature and collect the precipitate, then wash it three times repeatedly with deionized water and anhydrous ethanol. Then freeze-dry it at -20°C for 12 hours. Finally, grind it to 100 mesh to ensure it is fully heated during calcination, allowing the residual carbon precursor and nitrate ions to decompose.

[0095] S14. The ground product is then placed in a muffle furnace for calcination, with nitrogen protection throughout the process to prevent decomposition of the carbon skeleton. The temperature is first increased from room temperature to 200℃ at a rate of 1℃ / min. Then, it is increased to 700℃ at a rate of 5℃ / min and held at that temperature for 4 hours. After cooling, a carbon-encapsulated high-entropy perovskite composite material is obtained, with the molecular formula La(Cu). 0.29 Mn 0.12 Al 0.15 Fe 0.11 Co 0.11 Ni 0.09 Zn 0.13 )O3 / C.

[0096] Its SEM microstructure is as follows Figure 1 As shown in Figure ab, the carbon-encapsulated high-entropy perovskite composite material prepared in this embodiment is formed by a carbon skeleton.

[0097] like Figure 2 Figures ab show TEM images of different sizes, indicating that it has a core-shell structure, that is, high-entropy perovskite particles are wrapped by a carbon framework, and the coating layer is of uniform thickness; and high-resolution TEM shows high-entropy lattice fringes.

[0098] like Figure 3 The EDS diagram shows that La and Al are present in this carbon-encapsulated high-entropy perovskite composite material. 、 Mn 、 Fe 、 Co 、 Ni, Cu 、The uniform distribution of Zn metal and carbon elements proves that carbon was successfully introduced and uniformly encapsulated in the high-entropy perovskite composite material.

[0099] Figure 4 The images show the XRD patterns of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1. Figure 4 The typical perovskite crystal diffraction peaks are shown, indicating that the carbon-encapsulated high-entropy perovskite composite material and the high-entropy perovskite composite material alone in Comparative Example 1 have similar crystal plane characteristics.

[0100] Figure 5 XPS full spectra of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1. Compared with Comparative Example 1, the binding energy of the metal elements in Example 1 may have undergone a slight shift due to carbon encapsulation, indicating electronic interactions.

[0101] Figure 6 The images show the Raman spectra of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1. The figures show that the carbon-encapsulated high-entropy perovskite composite material prepared in this example exhibits obvious D and G peaks, indicating that graphitization defects occurred in the carbon framework after calcination.

[0102] Figure 7 The figures show the FT-IR spectra of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1. The figures show no significant difference in the infrared characteristic peaks between the carbon-encapsulated high-entropy perovskite composite material and the high-entropy perovskite composite material. Multiple metal elements characteristic of high-entropy perovskite are present, and the peak sizes do not change significantly, indicating that carbon encapsulation has a relatively small impact on high-entropy perovskite.

[0103] Figure 8 The electrochemical performance curves of the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 and the high-entropy perovskite composite material prepared in Comparative Example 1 are shown; wherein Figure 8 In Figure 1, a represents the cyclic voltammetry curve (CV) and b represents the impedance diagram. From the figures, it can be seen that the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1 has a lower impedance compared to the high-entropy perovskite catalyst alone, indicating that the carbon-encapsulated framework can enhance the conductivity of the material.

[0104] Preparation of catalytic packing material:

[0105] Weigh 2.5g of the carbon-coated perovskite composite material prepared above, 40g of coal powder, and 7.5g of red kaolin (iron content 3-5%), then add water, mix, and press into granules. The granules are then vacuum-dried at 60℃ for 12h. Finally, they are calcined at 800℃ for 2h to obtain the catalytic filler. Its optical photograph is shown in Figure 10a; it has a small particle size and a darker color due to carbon encapsulation.

[0106] The catalytic packing material was measured to have a crush strength of 40 N, a diameter of 1.5 cm, and a specific gravity of 3.5 g / cm³. 3 .

[0107] The red clay selected in this embodiment contains self-adhesive silicon and aluminum, as well as catalytically active elements such as iron, magnesium, and titanium, with iron primarily existing as Fe₂O₃. Its specific material composition is shown in Table 1 below, and its ESD is as follows: Figure 9 As shown.

[0108] Table 1. Proportion of elements in red clay

[0109]

[0110] Electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater:

[0111] The above-prepared catalytic packing material is used in a method for electrochemical synergistic ozone treatment of organic matter in high-salt wastewater, which includes the following steps:

[0112] S21. Anode plates and cathode plates are placed on both sides of the reaction zone of the electrochemically enhanced ozone reactor to form catalytic electrodes, and connected to an external power source. The aforementioned catalytic packing material is then filled between the anode plates and cathode plates as an intermediate electrode, wherein the amount of catalytic packing material added is 10 g / L of the reactor volume; and the catalytic packing material is driven to rotate between the anode plates and cathode plates, together forming a three-dimensional rotating electrode system.

[0113] S22. The high-salt wastewater to be treated is pumped into the above reactor; the high-salt wastewater is wastewater produced from the pharmaceutical intermediate sucralose, wherein the wastewater quality is as follows: chloride ion content 9700 mg / L, COD concentration 25700 mg / L, TDS 27370 mg / L, and pH value 6.0.

[0114] S23. Introduce ozone into the reactor at a flow rate of 0.1 g / min, and simultaneously turn on the DC power supply to carry out the electrochemical reaction. The DC power supply has a voltage of 2.8 V and a current density of 100 mA / cm².

[0115] S24. After 90 minutes of synergistic action between ozone catalytic oxidation and electrochemical reduction, organic matter in wastewater is removed.

[0116] The effluent from the reactor outlet was tested, and its COD concentration was 1150 mg / L, chloride ion concentration decreased to 6200 mg / L, and TDS concentration decreased to 19500 mg / L.

[0117] This demonstrates that the electrochemical performance enhancement of the ozone reaction in this invention can effectively degrade organic matter in high-salt water, achieving a COD removal rate of 95.5%.

[0118] The chloride ion concentration was determined by ion chromatography, the TDS concentration was determined by drying at 150℃, and the COD concentration was determined by rapid digestion.

[0119] The electrochemically enhanced ozone reactor used in the above method is a combination of an existing electrochemical reactor and an ozone oxidation reactor, and its structure is as follows: Figure 11 As shown, the electrochemically enhanced ozone reaction device includes a reactor 1, with a reaction zone 11 in the middle inside the reactor. An anode plate 2 and a cathode plate 3 are symmetrically arranged on both sides of the reaction zone 11, with a spacing of 3-5 cm between them. Catalytic packing material 6 is filled between the anode and cathode plates; specifically, a grid plate can be fixed inside the reactor 1 to support the catalytic packing material. The anode plate 2 and cathode plate 3 are respectively connected to the positive and negative terminals of an external power supply 4. An ozone inlet pipe 14 is connected to the bottom of the reactor 1, and an inlet 12 and an outlet 13 are provided.

[0120] This invention uses mechanical or hydraulic power to drive the catalytic packing material to rotate within the reaction zone, thereby increasing the contact area between the wastewater and the catalytic packing material, and thus enhancing the removal efficiency of organic matter. Specifically, a stirrer is installed inside the reactor. One end of the stirrer is connected to a motor located outside the reactor, and the other end is connected to stirring blades located inside the reactor. The rotation of the stirrer creates a strong water flow, causing the catalytic packing particles to rotate accordingly.

[0121] A water distributor 5 can also be installed below the reaction zone of the reactor (e.g., Figure 11 As shown, external sewage or sewage from inside the reactor is pumped out and pressurized by an external circulation pump, and then sprayed at high speed from the nozzle on the distributor 5 into the reaction zone 11, causing the catalytic packing 6 to rotate accordingly. This increases the contact area between the sewage and the catalytic packing, thereby increasing the removal of organic matter.

[0122] In addition, the exhaust port at the top of reactor 1 is used to discharge exhaust gas. At the same time, the exhaust gas can also be introduced into the bottom of the reaction zone through exhaust gas pipe 7 to cause the catalytic packing 6 to move.

[0123] The anode plate 2 is a boron-doped diamond thin-film electrode or a composite electrode of titanium-based noble metals and transition metal oxides; the cathode plate 3 is a graphite, graphene, iron, or stainless steel electrode. For illustrative purposes, in this embodiment, the anode plate 2 is a boron-doped diamond thin-film electrode, and the cathode plate 3 is a graphite electrode. Of course, other electrodes are also applicable to this application and will not be elaborated upon here.

[0124] Example 2:

[0125] Preparation of carbon-encapsulated high-entropy perovskite composite materials:

[0126] S11. Add 0.2g of citric acid to 50mL of pure water and stir to obtain solution A;

[0127] S12. Weigh 3.03g of La(NO3)3·6H2O, 0.34g of Al2(SO4)3·18H2O, 0.38g of Mn(NO3)2·4H2O, 0.2g of Fe(NO3)3·9H2O, 0.44g of Co(NO3)3·6H2O, 0.15g of Ni(NO3)3·6H2O, 0.36g of Cu(NO3)2·3H2O, and 0.29g of ZnSO4·7H2O, add them to 1L of water, magnetically stir for 30min, and then ultrasonically disperse for 30min to obtain solution B.

[0128] S13. Slowly add solution A to solution B (volume ratio 1:1) and stir to mix. Then transfer the mixture to a hydrothermal high-pressure reactor made of polytetrafluoroethylene (PTFE) and react at 220°C for 8 hours. Cool to room temperature and collect the precipitate, then wash it three times repeatedly with deionized water and anhydrous ethanol. Then freeze-dry it at -20°C for 12 hours. Finally, grind it to 100 mesh to ensure it is fully heated during calcination, allowing the residual carbon precursor and nitrate ions to decompose.

[0129] S14. The ground product is then placed in a muffle furnace for calcination, with nitrogen protection throughout the process to prevent decomposition of the carbon skeleton. The temperature is first increased from room temperature to 220℃ at a rate of 2℃ / min. Then, it is increased to 600℃ at a rate of 4℃ / min and held at that temperature for 6 hours. After cooling, a carbon-encapsulated high-entropy perovskite composite material is obtained, with the molecular formula La(Cu). 0.30 Mn 0.12 Al 0.08 Fe 0.13 Co 0.11 Ni 0.12 Zn 0.14 )O3 / C.

[0130] Preparation of catalytic packing material:

[0131] Weigh 5g of the carbon-coated perovskite composite material prepared above, 40g of biomass carbon, and 5g of red kaolin (composition same as in Example 1), add water, mix, and press into granules. Then, place the granules under vacuum drying at 60°C for 12 hours. Calcine at 700°C under nitrogen for 4 hours to obtain the catalytic filler.

[0132] The catalytic packing material was measured to have a crush strength of 20 N and a specific gravity of 2 g / cm³. 3 .

[0133] Electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater:

[0134] The catalytic packing material prepared above was applied in an electrochemically enhanced ozone reactor to degrade high-salt, high-COD nitrophenol production wastewater. The wastewater had a chloride ion content of 4500 mg / L, a COD concentration of 75000 mg / L, a TDS of 45370 mg / L, and a pH of 8.5. The catalyst dosage was 20 g / L, the ozone dosage was 1.0 g / min, and the current density was 80 mA / cm². 2 The external power supply has a constant voltage of 2.2V. The reaction time is 60 minutes.

[0135] The removal method was the same as in Example 1. The effluent was tested, and the COD concentration was 3350 mg / L, while the chloride ion concentration decreased to 2100 mg / L. This demonstrates the good application potential of this carbon-encapsulated high-entropy perovskite catalyst for high-salt, high-organic-content wastewater.

[0136] Example 3:

[0137] Preparation of carbon-encapsulated high-entropy perovskite composite materials:

[0138] S11. Add 0.2g of glucose to 50mL of pure water and stir to obtain solution A;

[0139] S12. Weigh 3.03g of La(NO3)3·6H2O, 0.67g of Al2(SO4)3·18H2O, 0.25g of Mn(NO3)2·4H2O, 0.41g of Fe(NO3)3·9H2O, 0.29g of Co(NO3)3·6H2O, 0.29g of Ni(NO3)3·6H2O, 0.24g of Cu(NO3)2·3H2O, and 0.29g of ZnSO4·7H2O, add them to 1L of water, magnetically stir for 30min, and then ultrasonically disperse for 30min to obtain solution B.

[0140] S13. Slowly add solution A to solution B (volume ratio 1:1) and stir to mix. Then transfer the mixture to a hydrothermal high-pressure reactor made of polytetrafluoroethylene (PTFE) and react at 180°C for 12 hours. Cool to room temperature and collect the precipitate, then wash it three times repeatedly with deionized water and anhydrous ethanol. Then freeze-dry it at -20°C for 12 hours. Finally, grind it to 200 mesh to ensure it is fully heated during calcination, allowing the residual carbon precursor and nitrate ions to decompose.

[0141] S14. The ground product is then placed in a muffle furnace for calcination, with nitrogen protection throughout the process to prevent decomposition of the carbon skeleton. The temperature is first increased from room temperature to 250°C at a rate of 3°C / min. Then, it is increased to 800°C at a rate of 6°C / min and held at that temperature for 5 hours. After cooling, a carbon-encapsulated high-entropy perovskite composite material is obtained.

[0142] Preparation of catalytic packing material:

[0143] Weigh 5g of the carbon-coated perovskite composite material prepared above, 37.5g of coal coke powder, and 7.5g of red kaolin (composition same as in Example 1), add water, mix, and press into granules. Then, place the granules under vacuum drying at 70℃ for 10h. Finally, calcine at 900℃ under nitrogen for 2h to obtain the catalytic filler.

[0144] The catalytic packing material was measured to have a crush strength of 30 N and a specific gravity of 3 g / cm³. 3 .

[0145] Electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater:

[0146] The catalytic packing material prepared above was applied in an electrochemically enhanced ozone reactor to degrade reverse osmosis concentrate wastewater from the coal chemical industry, using the same method as in Example 1.

[0147] In this embodiment, the wastewater quality was as follows: chloride ion content 280 mg / L, COD concentration 150 mg / L, TDS 380 mg / L, and pH value 6.5. The catalyst dosage was 5 g / L, the ozone dosage was 0.1 g / min, and the current density was 50 mA / cm². 2 The external power supply has a constant voltage of 1.8V. The reaction time is 30 minutes.

[0148] The effluent was tested, and its COD concentration was 25 mg / L, while the chloride ion concentration decreased to 120 mg / L. This demonstrates that the carbon-encapsulated high-entropy perovskite catalyst has high application potential for treating organic matter in high-salt reverse osmosis concentrate.

[0149] Comparative Example 1:

[0150] Same as Example 1, except that:

[0151] Preparation of high-entropy perovskite composite materials:

[0152] Weigh 3.03g of La(NO3)3·6H2O, 0.67g of Al2(SO4)3·18H2O, 0.25g of Mn(NO3)2·4H2O, 0.41g of Fe(NO3)3·9H2O, 0.29g of Co(NO3)3·6H2O, 0.29g of Ni(NO3)3·6H2O, 0.24g of Cu(NO3)2·3H2O, and 0.29g of ZnSO4·7H2O and add them to 1L of water. Stir magnetically for 30min, then sonicate for 30min to obtain a solution.

[0153] The above solution was transferred to a hydrothermal high-pressure reactor made of polytetrafluoroethylene and reacted at 200°C for 10 hours. After cooling to room temperature, the precipitate was collected and washed three times repeatedly with deionized water and anhydrous ethanol. It was then freeze-dried at -20°C for 12 hours. Finally, it was ground to 100 mesh to ensure sufficient heating during calcination, allowing the residual carbon precursor and nitrate ions to decompose thermally.

[0154] The ground product was then placed in a muffle furnace for calcination, with nitrogen protection throughout the process to prevent decomposition of the carbon skeleton. The temperature was first increased from room temperature to 200℃ at a rate of 1℃ / min, then increased to 700℃ at a rate of 5℃ / min and held at that temperature for 4 hours. After cooling, a high-entropy perovskite composite material with the molecular formula La(Cu) was obtained. 0.25 Mn 0.15 Al 0.16 Fe 0.13 Co 0.12 Ni 0.09 Zn 0.12 )O3.

[0155] Its SEM microstructure is as follows Figure 1 As shown in the middle CD, it can be seen that the prepared high-entropy perovskite composite material is not encapsulated by a carbon framework.

[0156] Its XRD pattern is as follows Figure 4 As shown, the XPS full spectrum is as follows: Figure 5 As shown, the FT-IR plot is as follows Figure 7 As shown. From Figure 4 , Figure 5 , Figure 7 The comparison shows that the high-entropy perovskite composite material is similar to the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1.

[0157] from Figure 6The Raman spectra show that the pure high-entropy perovskite composite material lacks D and G peaks, indicating the absence of carbon defects. This is one of the reasons for the significant performance difference compared to the carbon-encapsulated high-entropy perovskite composite material prepared in Example 1.

[0158] Preparation of catalytic packing material:

[0159] 2.5g of the perovskite composite material prepared above, 40g of coal powder, and 7.5g of red kaolin (composition same as in Example 1) were weighed out, and then water was added and mixed before being pressed into granules. The granules were then vacuum dried at 60℃ for 12h. They were then calcined at 800℃ for 2h to obtain the catalytic filler. Its optical photograph is shown in Figure 10b; it is lighter in color due to the lack of carbon encapsulation. The catalytic filler was measured to have a compressive strength of 40N and a specific gravity of 3.5g / cm³. 3 .

[0160] Electrochemical synergistic ozone treatment of organic matter in high-salinity wastewater:

[0161] Same as in Example 1,

[0162] The COD concentration of the effluent was measured to be 5560 mg / L, with a COD removal rate of 78.36%. This indicates that the carbon skeleton in the carbon-encapsulated perovskite composite material has a significant impact on the catalytic performance of the catalytic packing material during preparation. Due to the absence of the carbon skeleton, electron transfer at the interface with the high-entropy metal is limited, reducing the degradation efficiency of organic matter in high-salt wastewater.

[0163] Comparative Example 2:

[0164] Similar to Example 1, the main difference is that no carbon is added to encapsulate the high-entropy perovskite composite material; only ozone and electrochemistry are used to degrade the organic matter.

[0165] The effluent was tested and found to have a chloride ion concentration of 5560 mg / L, a COD concentration of 9800 mg / L, and a COD removal rate of 61.87%.

[0166] Comparative Example 3:

[0167] Same as Example 1, except that the DC power supply voltage is 1.0V in the electrochemical synergistic ozone treatment of organic matter in high-salt wastewater.

[0168] That is, in the electrochemically enhanced ozone reaction device of Comparative Example 3, the DC power supply voltage is 1.0V and the current density is 20mA / cm². 2 .

[0169] The COD concentration of the effluent was measured to be 13500 mg / L, with a COD removal rate of 47.47%. This is mainly because the current density decreases under low voltage, weakening electron conduction; simultaneously, the high chloride ion content in the wastewater deactivates free radicals. Therefore, voltage has a significant impact on the removal efficiency of organic matter in high-salinity wastewater.

[0170] Comparative Example 4:

[0171] Same as Example 1, except that the catalyst packing is different. In the method of electrochemical synergistic ozone treatment of organic matter in high-salt wastewater, the catalyst packing in Comparative Example 3 is MnO2.

[0172] The concentration of chloride ions in the effluent was measured to be 5800 mg / L, and the concentration of COD was 12500 mg / L, with a COD removal rate of 51.36%. This is significantly lower than the 95.5% in Example 1 and also lower than the 78.36% in Comparative Example 1. This is mainly because the catalytic performance of MnO2 is lower than that of the carbon-encapsulated high-entropy perovskite composite material.

[0173] Comparative Example 5:

[0174] Same as Example 1, except that the catalyst in the catalytic packing is different.

[0175] In Comparative Example 5, the catalyst is an activated carbon-supported composite metal. The preparation process of the activated carbon-supported composite metal is as follows:

[0176] Weigh 1g of activated carbon powder, 3.03g of La(NO3)3·6H2O, 0.67g of Al2(SO4)3·18H2O, 0.25g of Mn(NO3)2·4H2O, 0.41g of Fe(NO3)3·9H2O, 0.29g of Co(NO3)3·6H2O, 0.29g of Ni(NO3)3·6H2O, 0.24g of Cu(NO3)2·3H2O, and 0.29g of ZnSO4·7H2O, and add them to 1L of pure water. Stir magnetically for 30min, then ultrasonically disperse for 30min to obtain a solution. Transfer the solution to a hydrothermal high-pressure reactor made of polytetrafluoroethylene (PTFE) and react at 200℃ for 10h. Cool to room temperature and collect the precipitate, then wash repeatedly three times with deionized water and anhydrous ethanol. Finally, freeze-dry at -20℃ for 12h. The resulting activated carbon-supported high-entropy perovskite catalyst powder.

[0177] Catalytic packing material was prepared under the same conditions, and electrochemical synergistic ozone treatment of organic matter in high-salt wastewater was performed under the same conditions. The effluent concentration was measured to be 5300 mg / L for chloride ions and 7500 mg / L for COD, with a COD removal rate of 70.82%. This is significantly lower than the 95.5% COD removal rate in Example 1. This is mainly because the activated carbon-supported high-entropy perovskite catalyst powder in this comparative example lacks a conductive network due to the absence of a carbon framework structure. Consequently, its catalytic performance is lower than that of the carbon-encapsulated high-entropy perovskite composite material. This further illustrates that the carbon framework not only significantly influences the structural formation of the carbon-encapsulated high-entropy perovskite composite material but also affects the electronic synergy between multiple metals.

[0178] Comparative Example 6:

[0179] Similar to Example 1, the only difference is that ozone was not introduced into the reactor in the treatment of organic matter in high-salt wastewater; that is, electrochemical degradation of organic matter in wastewater was used alone.

[0180] The effluent was tested and found to have a chloride ion concentration of 5500 mg / L, a COD concentration of 18600 mg / L, and a COD removal rate of 27.63%.

[0181] This indicates that simple electrochemical catalytic oxidation has very low performance and the release efficiency of active substances is also slow.

[0182] Comparative Example 7:

[0183] Similar to Example 1, the only difference is that only ozone catalytic oxidation is used to treat the organic matter in the high-salt wastewater, without adding an anode plate and a cathode plate to form a catalytic electrode, and it is not connected to an external power source. The catalytic packing material prepared in Example 1 is also added.

[0184] The effluent concentration was measured to be 9680 mg / L, with a chloride ion removal rate of 0.21%; the COD concentration was 2650 mg / L, with a COD removal rate of 89.69%. Comparison showed that in Comparative Example 7, ozone catalytic oxidation alone reduced the removal of both organic matter and chloride ions compared to Example 1. This indicates that electrochemistry can enhance the removal rate of organic matter by ozone catalytic oxidation; that is, under electrochemical assistance, the accelerated electrons promote the redox reactions within the catalytic treatment system.

[0185] Comparative Example 8:

[0186] Same as Example 1, except that sodium-based bentonite is used as the binder instead of red kaolin in the preparation of the catalytic filler.

[0187] The effluent was tested and found to have a chloride ion concentration of 6250 mg / L, with a chloride ion removal rate of 35.57%. The COD concentration was 1850 mg / L, with a COD removal rate of 92.80%, slightly lower than the 95.5% in Example 1. This indicates that when equal masses of kaolin are used as a binder, due to its own catalytic components, it can form a synergistic effect with the carbon-encapsulated high-entropy perovskite composite material.

[0188] Finally, it should be noted that the above embodiments are merely preferred embodiments of the present invention and are only used to explain the present invention, not to limit the present invention. For those skilled in the art, modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Any changes, substitutions, and modifications made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A catalytic packing material, characterized in that: It is prepared from the following components in the indicated mass percentages: Carbon-encapsulated high-entropy perovskite composites contain 5-10% carbon. Adhesive 10-15%, Carbon-based support is the remainder; The carbon-encapsulated high-entropy perovskite composite material is composed of lanthanide high-entropy perovskite oxide and carbon microspheres, wherein the molecular formula of the lanthanide high-entropy perovskite oxide is La(Al) a Mn b Fe c Co d Ni e Cu f Zn g O3, where a, b, c, d, e, f, and g are all 0.01 to 1; The binder is red clay, and the mass ratio of iron in the red clay is 3-5%; The preparation steps of the carbon-encapsulated high-entropy perovskite composite material are as follows: S11. Add water-soluble carbon precursor to water and stir to obtain solution A; S12. Add La salt and transition metal salt to water at a molar ratio of 1:1 and stir to obtain a metal salt mixture. S13. Mix solution A and metal salt mixture at a volume ratio of 1:1, then carry out hydrothermal reaction, and then wash, dry and grind the resulting reaction product. S14. The ground product is calcined at high temperature to obtain a carbon-encapsulated high-entropy perovskite composite material.

2. The catalytic packing material according to claim 1, characterized in that: The carbon-based material is biochar, carbon gel, coal coke, or coal powder.

3. The catalytic packing material according to claim 1, characterized in that: The water-soluble carbon precursor is glucose, cellulose, starch, or citric acid; and / or, The transition metal salt is an Al, Mn, Fe, Co, Ni, Cu, or Zn salt; and / or, The hydrothermal reaction temperature is 180–220℃ and the time is 10–12 h.

4. The catalytic packing material according to claim 1, characterized in that: In step S13, the reaction product is washed repeatedly with pure water and ethanol 3 to 5 times, then freeze-dried and ground to 100 to 300 mesh.

5. A catalytic packing material according to claim 1, characterized in that: In step S14, the high-temperature calcination is carried out under nitrogen protection, first by raising the temperature from room temperature to 200-250°C at a rate of 1-3°C / min; then by continuing to raise the temperature to 600-800°C at a rate of 4-6°C / min; and finally by maintaining the temperature at a constant temperature for 4-8 hours.

6. A method for preparing a catalytic packing material according to any one of claims 1-5, characterized in that: Includes the following steps: Carbon-encapsulated high-entropy perovskite composite material, binder and carbon-based support are mixed in a certain mass ratio, and water is added and mixed before being pressed into granules; the granules are then dried and calcined to obtain catalytic filler.

7. The method for preparing a catalytic packing material according to claim 6, characterized in that: The drying is performed at 60–70°C for 10–12 hours, and the calcination is performed at 700–900°C for 2–4 hours; and / or, The catalytic packing has a diameter of 1.5–2.0 cm and a specific gravity of 2–5 g / cm³. 3 The crushing strength is 20-50 N.

8. The application of a catalytic packing material as described in any one of claims 1-5, characterized in that, It is applied to the electrochemical synergistic ozone treatment of organic matter in high-salt wastewater.

9. The application of the catalytic packing material according to claim 8, characterized in that, The method for electrochemically synergistically treating organic matter in high-salinity wastewater includes the following steps: S21. A catalytic packing material as described in any one of claims 1-5 is filled between the anode plate and the cathode plate in the reactor as an intermediate electrode, and the catalytic packing material is driven to rotate between the anode plate and the cathode plate to jointly form a three-dimensional rotating electrode system. S22. Pump the high-salt wastewater to be treated into the above reactor; S23. Introduce ozone into the reactor and simultaneously turn on the DC power supply to carry out the electrochemical reaction. S24. After the ozone catalytic oxidation process and the electrochemical reduction process work synergistically for 30 to 90 minutes, organic matter in the wastewater is removed.

10. The application of the catalytic packing material according to claim 9, characterized in that: The reactor is an electrochemically enhanced ozone reaction device; The catalytic packing is added at a rate of 5–50 g / L relative to the reactor volume; and / or, The ozone flow rate is 0.1–1.0 g / min; and / or, The DC power supply has a voltage of 1.8–2.8V and a current density of 50–100mA / cm².

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