High-salt-resistant hydrophobic surface type ozone composite catalytic material, and preparation method and application thereof

Abstract

The application discloses a high-salt-resistant hydrophobic surface type ozone composite catalytic material and a preparation method and application thereof, and belongs to the technical field of catalytic material preparation.The method is characterized by mixing triflate of at least one metal in iron, manganese, copper, cerium and lanthanum, PVDF and a pore-forming agent, loading on the surface of ceramic particles and preparing by high-temperature annealing.The application uses PVDF to construct a hydrophobic limited space, repels salt ions and enriches organic pollutants, and effectively overcomes the competitive adsorption and free radical quenching effect in high-salt wastewater by combining the high activity of triflate.The material can still maintain high-efficiency catalytic performance in a high-salt environment, and significantly improves the ozone utilization rate and the degradation efficiency of organic pollutants.

Description

Technical Field

[0001] This invention belongs to the field of catalytic material preparation technology, and particularly relates to a high-salt-resistant hydrophobic surface ozone composite catalytic material, its preparation method and application. Background Technology

[0002] Ozone catalytic oxidation technology is widely used in the advanced treatment stages of landfill leachate, pharmaceutical wastewater, and industrial park wastewater. Through the adsorption and enrichment, synergistic activation, and catalytic activation of the catalyst, it can significantly improve COD removal rate and ozone utilization rate. Chinese patent CN 222312867 U discloses an ozone catalytic oxidation plate catalyst that enhances gas-liquid (ozone-wastewater) two-phase mass transfer and diffusion, allowing ozone to penetrate the permeable membrane and contact the catalyst plate and wastewater liquid membrane for catalytic oxidation. This achieves a confined reaction of ozone catalytic oxidation, effectively improving the gas-liquid-solid three-phase contact and significantly enhancing the removal efficiency of recalcitrant substances and ozone utilization rate. However, this patent achieves this through structural improvements to the plate catalyst plate, permeable membrane, and separator. Chinese patent CN 120618485A discloses an ozone catalyst supported on metal oxides and its application. It uses porous ceramics as a support, utilizing the synergistic effect between the support and active components to improve oxidation reaction efficiency while maintaining high catalyst activity. Chinese patent CN119080205 A discloses an ozone catalytic oxidation wastewater treatment device and method, including a pretreatment unit and a catalytic reactor. The catalytic reactor is filled with a catalyst, which is a cylindrical molecular sieve support. The active components include one or more oxides of Fe, Ru, Mn, Cu, Ni, Zn, Co, Ce, and La, effectively improving the mass transfer efficiency between them. Recalcitrant pollutants adsorbed in the catalyst and in the wastewater are mineralized and decomposed. Chinese patent CN111375424A discloses a method for preparing and applying a supported polymetallic oxide catalytic ozone oxidation catalyst, particularly a method for preparing a supported polymetallic oxide catalytic ozone oxidation catalyst using manganese, copper, and cerium as catalytic active components. However, the above-mentioned catalytic materials all employ the traditional "impregnation-calcination" method, directly loading metal oxides or salts onto the surface of a porous support, forming a layered structure with a clear boundary between the active components and the support. This structure is easily interfered with by competitive adsorption of salt ions in high-salinity wastewater, leading to a decrease in catalyst activity. Furthermore, the above patents only focus on improving ozone mass transfer efficiency, without overcoming the problem of ineffective ozone decomposition in high-salt wastewater. They also have limited improvement on the oxidative degradation efficiency of organic matter in high-salt wastewater and have not effectively optimized the process to address the interference of salt ions. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention proposes a high-salt-resistant hydrophobic surface-type ozone composite catalyst material, its preparation method, and its applications. This invention enhances the adsorption and enrichment of organic pollutants at the hydrophobic interface by constructing a hydrophobic confined space, and couples ozone catalytic oxidation within the hydrophobic confined pore space. This hydrophobic confined pore space not only facilitates the adsorption and enrichment of organic pollutants but also reduces the interference of salt on the oxidation reaction, ultimately resulting in a high-salt-resistant hydrophobic surface-type ozone composite catalyst material.

[0004] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material includes the following steps: (1) The metal oxide is mixed with trifluoromethanesulfonic acid and reacted, and then post-processed to obtain trifluoromethanesulfonate containing water of crystallization; The metal oxide is selected from one or more of iron, manganese, copper, cerium and lanthanum; (2) Dissolve PVDF (polyvinylidene fluoride) powder in an organic solvent, add the trifluoromethanesulfonate containing water of crystallization and the pore-forming agent, and then heat and ultrasonically disperse the solution to obtain a PVDF composite solution. (3) The particulate carrier is pretreated and mixed with the film material and the PVDF composite solution, and then loaded onto the surface of the particulate carrier; (4) Remove the solvent and then anneal to finally obtain the high-salt resistant hydrophobic surface ozone composite catalyst.

[0005] In existing technologies, Cl in high-salinity wastewater - SO4 2- CO3 2- Anions pose a serious challenge to the catalytic oxidation of ozone, with interference mechanisms mainly manifested as a dual effect of "competitive adsorption" and "free radical quenching." Salt ions can seize the active sites of the catalyst, hindering effective contact between ozone and active components, leading to ineffective ozone decomposition; simultaneously, Cl... -Plasma readily consumes hydroxyl radicals (・OH) generated from ozone decomposition, producing less reactive chlorine radicals that significantly weaken the system's oxidative degradation capacity. Existing technologies primarily focus on improving mass transfer efficiency, lacking specific designs to address the dual interference of salt ions, thus limiting catalytic performance in high-salt environments. To address these shortcomings, this invention innovatively proposes a synergistic solution of "hydrophobic confined space construction + targeted design of active components." A low-surface-energy hydrophobic layer is constructed using PVDF, repelling hydrophilic salt ions based on the "like dissolves like" principle. Simultaneously, confined channels selectively enrich hydrophobic organic pollutants, significantly increasing the probability of reaction collisions. Combined with trifluoromethanesulfonates of Fe, Mn, Cu, Ce, and La as active components, this system, through a triple synergistic mechanism of "hydrophobic repulsion of salt ions, confined enrichment of pollutants, and activation of ozone by highly active components," fundamentally blocks the interference of salt ions, effectively overcoming the application bottleneck of existing technologies in high-salt environments.

[0006] Optionally, the metal oxide is a mixture of CuO, MnO2 and La2O3, a mixture of CeO2 and La2O3, or a mixture of Fe2O3, CeO2 and La2O3.

[0007] This invention has experimentally demonstrated that, since the decomposition of ozone into oxygen or highly reactive hydroxyl radicals (·OH) involves electron transfer, the composite of the aforementioned metal oxides can promote electron transfer. For example, the cerium element in cerium dioxide (CeO2) can be incorporated into the CeO2 matrix. 3+ and Ce 4+ The cyclical movement between two valence states allows for rapid electron transfer, effectively promoting the decomposition of ozone molecules and increasing the decomposition rate several times over. Secondly, it creates more active sites: combining metal ions of different radii (such as lanthanides and transition metals) forms "lattice defects" (such as oxygen vacancies) in the catalyst's crystal structure. These defects are active sites; the more active sites there are, the more ozone molecules can participate in the reaction simultaneously, thus increasing catalytic efficiency. Furthermore, combining different metal oxides can form highly efficient catalytic systems. Utilizing the synergistic effect between different metal oxides can yield performance superior to that of a single component.

[0008] Optionally, the molar ratio of the metal oxide to trifluoromethanesulfonic acid is 10:(1-2).

[0009] Optionally, the loading process in step (3) includes the following steps: pre-mixing the pre-treated granular carrier with the film material and PVDF composite solution, and loading the resulting mixture onto the surface of the pre-treated granular carrier using a granulator.

[0010] Furthermore, the granulator is selected from a disc granulator.

[0011] Optionally, the organic solvent is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, or N,N-dimethylacetamide; Optionally, the pore-forming agent is selected from polyvinylpyrrolidone or polyethylene glycol. Using polyvinylpyrrolidone or polyethylene glycol as a pore-forming agent can significantly increase the specific surface area of ​​the catalyst, ensuring that active molecules can smoothly enter the active sites and preventing aggregation.

[0012] Optionally, in step (2), the concentration of PVDF in the solution obtained after dissolving PVDF in an organic solvent is 5-15 wt%. Within this range, the catalyst can be guaranteed to have good hydrophobic properties.

[0013] Optionally, the concentration of trifluoromethanesulfonate in the PVDF composite solution is 1-20 wt%. Within this range, a good loading of active ingredients can be ensured for the catalyst.

[0014] Optionally, the concentration of the pore-forming agent in the PVDF composite solution is 5-20 wt%. By adjusting the amount of pore-forming agent added, the pore size and number of pores can be controlled, thereby optimizing the specific surface area of ​​the catalyst.

[0015] Optionally, in step (3), the particulate carrier is selected from ceramic spherical particles; as a specific example, the ceramic spherical particles are selected from α-alumina ceramic spheres, cordierite ceramic spheres or zirconia ceramic spheres.

[0016] As an example, the film material is selected from epoxy resin, phenolic resin or polyurethane resin.

[0017] As an example, the particle size of the ceramic spherical particles is 1.5-4 mm.

[0018] Optionally, in step (4), the drying temperature is 80-110℃ and the drying time is 10-30 min; The annealing temperature is 120-150℃.

[0019] A hydrophobic surface-type ozone composite catalytic material resistant to high salt content was prepared by the above-described preparation method.

[0020] The high-salt-resistant hydrophobic surface ozone composite catalytic material prepared by this invention can be applied to the field of degrading pollutants in various types of wastewater through ozone catalytic oxidation reaction.

[0021] Optionally, a specific application could be the degradation treatment of organic pollutant wastewater; for example, organic wastewater containing phenol or tetracycline hydrochloride. The composite catalytic material prepared by this invention is particularly applicable to the treatment of high-salinity wastewater, for example, wastewater with a salt content of 5%-10%.

[0022] Compared with the prior art, the present invention has the following advantages and technical effects: 1. The membrane performance is more stable. The present invention uses organic salt to achieve a "completely fused uniform membrane layer", which avoids the problems of "interlayer separation and interface performance degradation" that are prone to occur in the "layered structure" in the prior art. The membrane layer (hydrophobic surface ozone composite catalyst material) prepared by the present invention has stronger structural integrity and functional sustainability.

[0023] 2. The present invention has lower operating costs and the catalytic function of the uniform membrane layer does not require "aeration" to trigger, which eliminates the need for investment in aeration equipment and aeration energy consumption that may be required in the prior art, simplifies the operation process in practical applications, and reduces operating costs.

[0024] 3. Existing layered nitrates and PVDF cannot be tightly bound together and are prone to detachment and interference; the catalyst is encapsulated inside, resulting in low catalytic efficiency. In contrast, the composite catalytic material of this invention has an integrated structure, is not easily detached, resists interference, allows direct contact, and achieves high catalytic efficiency. Detailed Implementation

[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0026] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0027] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0028] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0029] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0030] This invention discloses a method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material, comprising the following steps: (1) Preparation of trifluoromethanesulfonate: One or more of the oxides of Fe, Mn, Cu, Ce and La are mixed with trifluoromethanesulfonic acid at a molar ratio of 10:(1-2), and the mixture is stirred at 60-80℃ for 6-12 hours. After filtering to remove unreacted metal oxides, the solution is concentrated and cooled to precipitate crystals, thus obtaining trifluoromethanesulfonate containing water of crystallization. (2) Preparation of PVDF film solution: Dissolve PVDF powder in a solvent (such as N,N-dimethylformamide DMF, N-methylpyrrolidone NMP, N,N-dimethylacetamide) to prepare a 5-15 wt% solution, then add trifluoromethanesulfonate and pore-forming agent (such as polyvinylpyrrolidone PVP, polyethylene glycol PEG), heat to 50-80℃ to accelerate dissolution, and obtain PVDF composite solution; In the PVDF composite solution, the concentration of the pore-forming agent is 5-20 wt%, and the concentration of trifluoromethanesulfonate is 1-20 wt%; ultrasonic treatment for 10-30 minutes is required for homogenization. (3) Loading onto ceramic spherical particles or other particles: The ceramic particles are initially mixed with the film material (such as resin, adhesive) and PVDF composite solution, and the film material is initially loaded onto the particle surface by a disc granulator or the like.

[0031] (4) Stable molding: The particles loaded with the adhesive film are first dried at 80-110℃ for 10-30 min to remove residual solvent, and finally annealed at high temperature (120-150℃) to improve crystallinity and form a particulate ozone composite catalyst material with high salt resistance and hydrophobic surface.

[0032] The present invention also discloses a high-salt-resistant hydrophobic surface ozone composite catalyst material prepared by the above method.

[0033] 1. Analysis of the core issues of salt ion interference Cl in high-salinity wastewater - SO4 2- CO3 2- The interference of anions on the ozone catalytic oxidation reaction is mainly manifested in two aspects: (1) Competitive adsorption: Salt ions easily compete with organic pollutants for active sites of catalysts, resulting in ozone being unable to effectively contact the active components, thus causing ineffective decomposition and reducing ozone utilization; (2) Free radical quenching: Salt ions (especially Cl) - It reacts with hydroxyl radicals (・OH) generated by ozone decomposition, consuming ・OH and generating less reactive chlorine radicals, which greatly weakens the oxidative degradation ability.

[0034] Existing technologies only improve mass transfer efficiency by optimizing the carrier structure or the combination of active components, without designing solutions for the dual interference mechanism of "competitive adsorption + free radical quenching" of salt ions, resulting in limited catalytic performance in high-salt environments.

[0035] 2. The core mechanism of salt tolerance optimization in this invention This invention reduces salt ion interference at its source through a synergistic approach of "hydrophobic confined space construction + targeted design of active components." The specific principle is as follows: Salt ion repulsion effect at hydrophobic interfaces: PVDF (polyvinylidene fluoride), as a hydrophobic substrate, has fluorine atoms in its molecular structure with extremely high electronegativity, causing a low surface energy hydrophobic layer to form on the catalyst surface. According to the principle of "like dissolves like," hydrophilic salt ions (such as Cl-) repel each other. - Na + It is difficult for it to adsorb at the hydrophobic interface and it is excluded from the confined space, thus avoiding the competition of salt ions for the active site. Confined space for pollutant enrichment: Hydrophobic confined channels have strong adsorption selectivity for hydrophobic organic pollutants (such as phenol and tetracycline hydrochloride), which can form a high concentration area of ​​pollutants around the catalytic active site, significantly increasing the probability of collision between ozone and pollutants and compensating for the reaction kinetic disadvantages under high salinity conditions. The activity enhancement effect of trifluoromethanesulfonates: Trifluoromethanesulfonates of Fe, Mn, Cu, Ce or La, as active components, have a high degree of ionization and uniformly dispersed catalytic active centers. When they work synergistically with the hydrophobic layer of PVDF, they can efficiently activate ozone to generate OH. Moreover, the affinity of these active components for salt ions is much lower than that of traditional metal oxides, which further reduces the inhibition of catalytic activity by salt ions.

[0036] In summary, this invention achieves the technical goal of "reducing salt interference and improving degradation efficiency" through the triple synergy of "hydrophobic repulsion of salt ions + confined enrichment of pollutants + activation of ozone by highly active components", thus overcoming the core defects of existing technologies.

[0037] The present invention also discloses that the high-salt-resistant hydrophobic surface ozone composite catalytic material prepared above can be applied to the field of degrading pollutants in various types of wastewater through ozone catalytic oxidation reaction.

[0038] In optional embodiments, the specific application can be the degradation treatment of organic pollutant wastewater; for example, organic wastewater containing phenol or tetracycline hydrochloride. The composite catalytic material prepared by this invention can be particularly applied to the treatment of high-salinity wastewater, for example, wastewater with a salt content of 5%-10%.

[0039] All raw materials used in this invention were purchased from the market.

[0040] The technical solution of the present invention will be further described below through embodiments.

[0041] Example 1 A method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material includes the following steps: (1) Preparation of trifluoromethanesulfonate: Weigh CuO, MnO2 and La2O3 (mass ratio 0.2:0.1:1), mix with trifluoromethanesulfonic acid at a molar ratio of 10:1, stir and react at 60°C for 12 hours, filter to remove unreacted metal oxides, concentrate the solution and cool to precipitate crystals, and obtain trifluoromethanesulfonate containing water of crystallization.

[0042] (2) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N,N-dimethylformamide DMF to prepare a 5wt% solution, then add trifluoromethanesulfonate (Cu, Mn and La) containing water of crystallization and pore-forming agent polyvinylpyrrolidone PVP, heat to 50℃ to accelerate dissolution, and then sonicate for 30 min to mix evenly to obtain PVDF composite solution.

[0043] The concentration of trifluoromethanesulfonates (Cu, Mn and La) containing water of crystallization was 1 wt%, and the concentration of the pore-forming agent polyvinylpyrrolidone (PVP) was 10 wt%.

[0044] (3) Loading onto ceramic spherical particles: Select α-alumina ceramic balls (particle size 2-3mm), first place the α-alumina ceramic balls in a 110℃ oven for pretreatment and drying for 2 hours to remove surface adsorbed water; the adhesive film material is epoxy resin, which accounts for 6% of the mass of ceramic particles.

[0045] Take 100g of pretreated α-alumina ceramic balls, add 6g of epoxy resin E-51 and 20g of PVDF composite solution prepared in step (2), stir for 10 min to make the materials initially mixed evenly, and then put them into a disc granulator (speed 35r / min) for 18 min to make the film material and PVDF composite solution evenly coat the surface of the ceramic particles to form a preliminary loading layer. After loading, the particle size is controlled at 2.5-3.5mm (the loading amount is 26g of film material and PVDF composite solution per 100g of ceramic particles).

[0046] (4) Stabilization and molding: The particles of the loaded film obtained in step (3) are first dried at 80°C for 30 min to remove residual solvent, and finally annealed at 120°C to improve crystallinity, forming a particle body (catalytic material) of a hydrophobic surface ozone composite catalyst resistant to high salt.

[0047] Effect test: The simulated wastewater contained 100 mg / L phenol and 10% sodium chloride (mass concentration). The dosage of the catalyst material prepared in Example 1 was 100 g / L, the ozone dosage was 400 mg / (L·h), the reaction temperature was 25℃, and the solution pH was 7.0. Using this catalyst material to oxidize 100 mg / L phenol for 3 min, the removal rate increased from 13% to 58% compared with the blank group that only added ozone and did not add catalyst material, showing a significant improvement.

[0048] Example 2 A method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material includes the following steps: (1) Preparation of trifluoromethanesulfonate: Weigh CeO2 and La2O3 (mass ratio 1:1), mix them with trifluoromethanesulfonic acid at a molar ratio of 10:2, stir and react at 80°C for 6 hours, filter to remove unreacted metal oxides, concentrate the solution and cool to precipitate crystals, and obtain trifluoromethanesulfonate containing water of crystallization.

[0049] (2) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N-methylpyrrolidone (NMP) to prepare a 10wt% solution, then add trifluoromethanesulfonate (Ce and La) and pore-forming agent polyvinylpyrrolidone (PVP); heat to 70℃ to accelerate dissolution, and then sonicate for 15 min to mix evenly to obtain PVDF composite solution.

[0050] The concentration of trifluoromethanesulfonates (Ce and La) was 10 wt%; the concentration of the pore-forming agent polyvinylpyrrolidone (PVP) was 5 wt%.

[0051] (3) Loading onto ceramic spherical particles: Select cordierite ceramic balls (particle size 1.5-2mm), first place the cordierite ceramic balls in an oven at 105℃ and dry for 3 hours to remove surface adsorbed water; Take 100g of pretreated cordierite ceramic balls, add 5g of phenolic resin PF-2123 and 22g of PVDF composite solution prepared in step (2), stir for 15 min to fully mix the materials, and then put them into a disc granulator (30r / min) for 20 min to make the film material and PVDF composite solution uniformly coat the surface of the ceramic particles. After loading, the particle size is controlled at 1.8-2.3mm (the loading amount is 27g of film material and PVDF composite solution per 100g ceramic particles).

[0052] (4) Stabilizing and molding: The particles of the loaded film obtained in step (3) are first dried at 100℃ for 20 min to remove residual solvent, and finally annealed at high temperature at 145℃ to improve crystallinity, forming a particle body (catalytic material) of a hydrophobic surface ozone composite catalyst resistant to high salt.

[0053] Effect test: In a 5% sodium chloride solution, the dosage of the catalyst material prepared in Example 2 was 100 g / L, the ozone dosage was 400 mg / (L·h), the reaction temperature was 25°C, the solution pH was 7.0, and the ozone oxidation was carried out for 4 min. Using this composite catalyst material to treat 100 mg / L phenol, compared with the blank group with only ozone added and no catalyst material added, the removal efficiency increased from 16% to 65%, which significantly improved the removal efficiency.

[0054] Example 3 A method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material includes the following steps: (1) Preparation of trifluoromethanesulfonate: Weigh Fe2O3, CeO2 and La2O3 (mass ratio 1:1:1), mix with trifluoromethanesulfonic acid at a molar ratio of 10:1.5, stir and react at 70°C for 10 hours, filter to remove unreacted metal oxides, concentrate the solution and cool to precipitate crystals, and obtain trifluoromethanesulfonate containing water of crystallization.

[0055] (2) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N,N-dimethylacetamide to prepare a 15 wt% solution, then add trifluoromethanesulfonate (Fe, Ce and La) and pore-forming agent polyethylene glycol PEG, heat to 80℃ to accelerate dissolution, and then sonicate for 10 min to mix evenly to obtain PVDF composite solution.

[0056] The concentration of trifluoromethanesulfonate (Fe, Ce and La) was 20 wt%, and the concentration of polyethylene glycol (PEG) was 20 wt%.

[0057] (3) Loading onto ceramic spherical particles: Select zirconia ceramic balls (particle size 3-4mm), first place the zirconia ceramic balls in a 120℃ oven to dry for 1.5 hours to remove surface adsorbed water; Take 100g of pretreated zirconia ceramic balls, add 8g of polyurethane resin PU-301 and 25g of PVDF composite solution prepared in step (2), stir for 20 min to mix the materials evenly, and then put them into a disc granulator (speed 40r / min) for 15 min to make the film material and PVDF composite solution completely loaded on the surface of the ceramic particles. After loading, the particle size is controlled at 3.2-4.2mm (the loading amount is 33g of film material and PVDF composite solution mixed for every 100g of ceramic particles).

[0058] (4) Stabilization and molding: The particles of the loaded film obtained in step (3) are first dried at 110°C for 10 min to remove residual solvent, and finally annealed at 150°C to improve crystallinity, forming a particle of a hydrophobic surface ozone composite catalyst material resistant to high salt.

[0059] Effect Test 1: In a 5% sodium chloride solution, the catalyst prepared in Example 3 was added at a dosage of 100 g / L, the ozone dosage was 400 mg / (L·h), the reaction temperature was 25°C, and the solution pH was 7.0. 100 mg / L phenol was subjected to ozone oxidation for 6 min. The removal rate of phenol using this catalyst increased from 23% to 89% compared to the blank group with only ozone added and no catalyst added, significantly improving the catalytic effect.

[0060] Effect Test 2: Simulated high-salt organic wastewater containing the target pollutant tetracycline hydrochloride was used as the treatment target. The salt system was NaCl, and the salt concentrations were set at 5% and 10% (mass concentration), covering the typical concentration range of high-salt wastewater. A blank group (ozone oxidation only, without catalyst) and an experimental group (the high-salt-resistant hydrophobic surface ozone composite catalyst material prepared in Example 3 of this invention) were set up. The unified reaction parameters were: catalyst dosage 100 g / L, ozone dosage 400 mg / (L·h), reaction temperature 25℃, solution pH=7.0, and a closed ozone catalytic reactor with an effective volume of 500 mL was used. Specific effect data are shown in Table 1.

[0061] Table 1 As shown in Table 1, the high-salt-tolerant hydrophobic surface ozone composite catalyst prepared in Example 3 of this invention effectively optimized the resistance to interference from salt ions. When the salt ion concentration was 5%, both the removal rate of tetracycline hydrochloride and the ozone utilization rate gradually increased with the extension of reaction time. When the salt ion concentration increased to 10%, although the removal rate of tetracycline hydrochloride and the ozone utilization rate decreased compared to the 5% concentration, they still maintained good performance. Therefore, the high-salt-tolerant hydrophobic surface ozone composite catalyst prepared in this invention can overcome the problem of ineffective ozone decomposition in high-salt wastewater, improve the oxidative degradation efficiency of organic matter in high-salt wastewater, and reduce the interference of salt on the oxidation reaction.

[0062] Comparative Example 1 A method for preparing an ozone composite catalytic material includes the following steps: (1) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N,N-dimethylformamide DMF to prepare a 5wt% solution. Add Cu(NO3)2, Mn(NO3)4 and La(NO3)3 salts in sequence (the molar ratio of Cu, Mn and La is the same as in Example 1) and pore-forming agent polyvinylpyrrolidone (PVP). Heat to 50°C to accelerate dissolution, and then sonicate for 30 min to mix evenly to obtain PVDF composite solution.

[0063] The total concentration of the three salts in the PVDF composite solution is 1 wt%, and the concentration of the pore-forming agent polyvinylpyrrolidone (PVP) is 10 wt%.

[0064] (2) Loading onto ceramic spherical particles: Select α-alumina ceramic balls (particle size 2-3mm), first place the α-alumina ceramic balls in a 110℃ oven for pretreatment and drying for 2 hours to remove surface adsorbed water; Take 100g of pretreated α-alumina ceramic balls, add 6g of epoxy resin E-51 and 20g of the PVDF composite solution prepared in step (1), stir for 10 min to make the materials initially mixed evenly, and then put them into a disc granulator (speed 35r / min) for 18 min to make the film material and PVDF composite solution evenly coat the surface of the ceramic particles to form a preliminary loading layer. After loading, the particle size is controlled at 2.5-3.5mm (the loading amount is 26g of film material and PVDF composite solution per 100g ceramic particles).

[0065] (3) Stabilization and molding: The particles of the loaded film obtained in step (2) are first dried at 80°C for 30 min to remove residual solvent, and finally annealed at 120°C to improve crystallinity, forming particles of ozone composite catalyst (catalytic material).

[0066] Comparative Test: The simulated wastewater contained 100 mg / L phenol and 10% sodium chloride (mass concentration). The ozone dosage was 400 mg / (L·h), the reaction temperature was 25℃, and the solution pH was 7.0. Using the catalytic material prepared in this comparative example, with a dosage of 100 g / L, the phenol removal rate after 3 min of oxidation was 41%, which was significantly lower than the 58% phenol removal rate when using the catalytic material prepared in Example 1. It can be seen that after replacing the metal trifluoromethanesulfonate with nitrate, the catalytic activity of the prepared catalytic material decreased under high salt conditions, indicating that there is a certain synergistic effect between trifluoromethanesulfonate and the hydrophobic component PVDF.

[0067] Comparative Example 2 A method for preparing an ozone composite catalytic material includes the following steps: (1) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N-methylpyrrolidone (NMP) to prepare a 10wt% solution. Add Ce(NO3)3 and La(NO3)3 salts (the molar ratio of Ce and La is the same as in Example 2) and pore-forming agent polyvinylpyrrolidone (PVP) in sequence. Heat to 70℃ to accelerate dissolution, and then sonicate for 15 min to mix evenly to obtain PVDF composite solution.

[0068] The total concentration of the two salts in the PVDF composite solution was 10 wt%, and the concentration of the pore-forming agent polyvinylpyrrolidone (PVP) was 5 wt%.

[0069] (2) Loading onto ceramic spherical particles: Select cordierite ceramic balls (particle size 1.5-2mm), first place the cordierite ceramic balls in an oven at 105℃ for 3 hours to dry and remove surface adsorbed water; Take 100g of pretreated cordierite ceramic balls, add 5g of phenolic resin PF-2123 and 22g of PVDF composite solution prepared in step (1), stir for 15 min to make the materials fully mixed and uniform, and then put them into a disc granulator (speed 30r / min) for 20 min to make the film material and PVDF composite solution uniformly coat the surface of the ceramic particles. After loading, the particle size is controlled at 1.8-2.3mm (the loading amount is 27g of film material and PVDF composite solution per 100g ceramic particles).

[0070] (3) Stabilization and molding: The particles of the loaded film obtained in step (2) are first dried at 100℃ for 20 min to remove residual solvent, and finally annealed at high temperature at 145℃ to improve crystallinity, forming particles of ozone composite catalyst (catalytic material).

[0071] Comparative Test: In a 5% sodium chloride solution, using the catalyst prepared in this comparative example with a dosage of 100 g / L, an ozone dosage of 400 mg / (L·h), a reaction temperature of 25°C, a solution pH of 7.0, and ozone oxidation for 4 min, the phenol removal rate of the initial 100 mg / L phenol solution was 54%, significantly lower than the 65% organic matter removal rate when using the catalyst prepared in Example 2. This indicates that the triple synergy of "hydrophobic repulsion of salt ions + confined enrichment of pollutants + activation of ozone by highly active components" in Example 2 is superior to the technical effect of this comparative example.

[0072] Comparative Example 3 A method for preparing an ozone composite catalytic material includes the following steps: (1) Preparation of PVDF thin film solution: Dissolve PVDF powder in solvent N,N-dimethylacetamide to prepare a 15 wt% solution. Add Fe(NO3)3, Ce(NO3)3 and La(NO3)3 salts in sequence (the molar ratio of Fe, Ce and La is the same as in Example 3), pore-forming agent polyethylene glycol PEG, heat to 80℃ to accelerate dissolution, and then sonicate for 10 min to mix evenly to obtain PVDF composite solution.

[0073] The total concentration of the three salts in the PVDF composite solution was 20 wt%, and the concentration of polyethylene glycol (PEG) was 20 wt%.

[0074] (2) Loading onto ceramic spherical particles: Select zirconia ceramic balls (particle size 3-4mm), first place the zirconia ceramic balls in a 120℃ oven to dry for 1.5 hours to remove surface adsorbed water; Take 100g of pretreated zirconia ceramic balls, add 8g of polyurethane resin PU-301 and 25g of PVDF composite solution prepared in step (1), stir for 20 min to make the materials initially mixed evenly, and then put them into a disc granulator (speed 40r / min) for 15 min to make the film material and PVDF composite solution evenly coat the surface of the ceramic particles. After loading, the particle size is controlled at 3.2-4.2mm (the loading amount is 33g of film material and PVDF composite solution per 100g ceramic particles).

[0075] (3) Stabilization and molding: The particles of the loaded film obtained in step (2) are first dried at 110°C for 10 min to remove residual solvent, and finally annealed at 150°C to improve crystallinity and form particles of ozone composite catalyst material.

[0076] Comparative Test: The catalytic material prepared using this comparative example was placed in a 5% sodium chloride solution at a dosage of 100 g / L. The concentration of phenol in the solution was 100 mg / L, the ozone dosage was 400 mg / (L·h), the reaction temperature was 25℃, and the solution pH was 7.0. After ozone oxidation for 6 min, the phenol removal rate was 76%, which was significantly lower than the organic matter removal rate of 89% when using the catalytic material prepared in Example 3. The results indicate that the catalytic material prepared in Example 3 can effectively improve the oxidation rate of organic matter in a high-salt environment.

[0077] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-salt-resistant hydrophobic surface-type ozone composite catalytic material, characterized in that, Includes the following steps: (1) The metal oxide is mixed with trifluoromethanesulfonic acid and reacted, and then post-processed to obtain trifluoromethanesulfonate containing water of crystallization; The metal oxide is selected from at least one of iron, manganese, copper, cerium and lanthanum; (2) Dissolve PVDF powder in an organic solvent, then add the trifluoromethanesulfonate containing water of crystallization and the pore-forming agent, and then heat and ultrasonically disperse the solution to obtain a PVDF composite solution; (3) The particulate carrier is pretreated and mixed with the film material and the PVDF composite solution, and then loaded onto the surface of the particulate carrier; (4) Remove the solvent and then anneal to finally obtain the high-salt resistant hydrophobic surface ozone composite catalyst.

2. The method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, The metal oxide is selected from any one of the following three mixtures: a mixture of CuO, MnO2 and La2O3; a mixture of CeO2 and La2O3; or a mixture of Fe2O3, CeO2 and La2O3.

3. The method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, The molar ratio of the metal oxide to trifluoromethanesulfonic acid is 10:(1-2).

4. The preparation method of a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, The loading process in step (3) includes the following steps: the pretreated particulate carrier is initially mixed with the film material and PVDF composite solution, and the resulting mixture is loaded onto the surface of the pretreated particulate carrier by a granulator.

5. The method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, The organic solvent is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, or N,N-dimethylacetamide; and / or The pore-forming agent is selected from polyvinylpyrrolidone or polyethylene glycol.

6. The preparation method of a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, In step (2), the concentration of PVDF in the solution obtained after PVDF is dissolved in an organic solvent is 5-15 wt%; and / or, In the PVDF composite solution, the concentration of trifluoromethanesulfonate is 1-20 wt%; and / or, The concentration of the pore-forming agent in the PVDF composite solution is 5-20 wt%.

7. The preparation method of a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, In step (3), the particulate carrier is selected from ceramic spherical particles; and / or, The film material is selected from epoxy resin, phenolic resin or polyurethane resin.

8. The method for preparing a high-salt-resistant hydrophobic surface ozone composite catalytic material according to claim 1, characterized in that, In step (4), the drying temperature is 80-110℃, and the drying time is 10-30 min; and / or, The annealing temperature is 120-150℃.

9. A high-salt-resistant hydrophobic surface ozone composite catalyst material prepared by the preparation method according to any one of claims 1-8.

10. The application of the high-salt-resistant hydrophobic surface ozone composite catalyst material as described in claim 9 in the degradation of pollutants in wastewater.

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