Preparation method and catalytic application of antimony trioxide with porous structure
By constructing a porous antimony trioxide structure, and employing montmorillonite combined with carbon nanotubes, lanthanum oxide composite modification, and a multi-level pore design, the problems of small specific surface area and poor catalytic stability of traditional antimony trioxide were solved, achieving highly efficient catalytic performance and improved stability.
Patent Information
- Application Number
- CN202511519768.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-23
- Publication Date
- 2026-01-13
AI Technical Summary
Traditional antimony trioxide is mostly solid particles or dense structures, which have small specific surface area, insufficient exposure of active sites, and low mass transfer efficiency, limiting its full catalytic performance. Furthermore, porous antimony trioxide generally has poor catalytic activity and poor catalytic stability under long-term use.
A porous antimony trioxide structure was constructed using a dual emulsion template method. The specific surface area was increased by pretreatment with montmorillonite. Montmorillonite was then combined with carbon nanotubes and lanthanum oxide to form a composite support. Combined with kaolinite, titanium dioxide and mullite whiskers, a hierarchical pore structure was formed to improve mechanical strength and mass transfer efficiency. Furthermore, catalytic activity was enhanced by doping with lanthanum oxide.
It significantly increases the specific surface area and number of active sites of antimony trioxide, shortens the reactant diffusion path, enhances the redox ability and photocatalytic efficiency of the catalyst, and improves the structural stability and catalytic stability of the material.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of antimony trioxide technology, specifically to a method for preparing porous antimony trioxide and its catalytic application. Background Technology
[0002] Antimony trioxide (Sb₂O₃), as an important inorganic functional material, possesses unique redox properties and surface activity, and is widely used in flame retardants, pigments, catalysts, and other fields. In the field of catalysis, antimony trioxide can be used in various scenarios such as polyester synthesis, petroleum refining, and organic synthesis. For example, it serves as a core catalyst in the PET polycondensation reaction, accelerating the transesterification process by activating reaction intermediates; and in the ammonia oxidation reaction, it can regulate the reaction pathway and reduce the formation of byproducts.
[0003] However, antimony trioxide prepared by traditional methods is mostly in the form of solid particles or dense structures, which suffer from defects such as small specific surface area, insufficient exposure of active sites, and low mass transfer efficiency, severely limiting its catalytic performance. To solve this problem, the development of porous antimony trioxide has become a research hotspot. Porous structures can increase the number of active sites by increasing the specific surface area, while the pore structure can promote the diffusion and transport of reactants and products.
[0004] Currently, porous antimony trioxide exhibits generally poor catalytic properties. With long-term catalytic activity and repeated use, the catalytic stability of the product deteriorates significantly, limiting its utilization efficiency. Based on this, the present invention further improves upon this by providing a method for preparing porous antimony trioxide and its catalytic application. Summary of the Invention
[0005] In view of the deficiencies of the prior art, the purpose of this invention is to provide a method for preparing porous antimony trioxide and its catalytic application, so as to solve the problems mentioned in the background art.
[0006] The present invention solves the technical problem by adopting the following technical solution: This invention provides a method for preparing porous antimony trioxide, comprising the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 5-8 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
[0007] Preferably, the method for preparing the antimony trioxide matrix is as follows: S1, Oil phase preparation: Weigh 2-3 parts of Span-80 and add it to 40-45 parts of white oil. Stir at 60-65℃ for 20-30 minutes until completely dissolved to obtain the oil phase. S2, P / O emulsion preparation: Weigh 4-6 parts of antimony glycol and dissolve it in 30-35 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 10-20 min to form a P / O emulsion; S3, Preparation of dual emulsion: Weigh 3-5 parts of Tween-80 and add it to 80-100 parts of deionized water. After stirring and dissolving, add 0.1-0.2 parts of sodium dihydrogen phosphate to adjust the pH to 5.0-55 to obtain the aqueous phase. Slowly add the P / O emulsion dropwise to the aqueous phase. First, stir at a high speed of 12000 r / min for 120-130 s, and then stir at a low speed of 30-40 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: Let the emulsion stand for 30-35 min, centrifuge at 8000 r / min for 10-15 min to collect the precipitate, wash with anhydrous ethanol and deionized water alternately 4-6 times, vacuum dry at 70-75℃ for 10-12 h, then calcine at 500-550℃ for 2-4 h with a heating rate of 2-4℃ / min, and obtain antimony trioxide matrix after cooling.
[0008] Preferably, the stirring speed of the stirring process is 450-550 r / min, and the stirring time is 1 hour.
[0009] Preferably, the preparation method of the montmorillonite carrier is as follows: S01: Heat montmorillonite at 210-230℃ for 5-10 min, then raise the temperature to 350℃ at a rate of 2-5℃ / min, hold for 1 h, and then air cool to room temperature; S02: Prepare a 5-8% (w / w) dopamine hydrochloride solution; mix 2-5 parts of dopamine hydrochloride solution, 1-3 parts of sodium lignosulfonate, 3-5 parts of carbon nanotubes, and 1-2 parts of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:(11-14). After ultrasonic treatment, the montmorillonite compound loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:(3-5). After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
[0010] Preferably, the ultrasonic power of the ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour; the ball milling treatment lasts for 2 hours with a ball milling speed of 1000-1500 r / min.
[0011] Preferably, the preparation method of the feed material is as follows: S03a: 3-5 parts of kaolin, 2-5 parts of titanium dioxide and 1-3 parts of mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 2-5 parts of sodium carboxymethyl cellulose, 5-8 parts of sodium dodecylbenzene sulfonate solution and 1-3 parts of phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8, with an ultrasonic power of 350-400W for 1 hour. After ultrasonication, the mixture was filtered and dried to obtain the feed material.
[0012] Preferably, the sintering temperature of the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.
[0013] Preferably, the pH value of the phosphate buffer solution is 5.5-6.5; and the mass fraction of the sodium dodecylbenzenesulfonate solution is 8-12%.
[0014] The present invention also provides a method for preparing porous antimony trioxide and its application in catalytic degradation.
[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention employs a dual emulsion template method to construct the antimony trioxide matrix, while simultaneously pretreating it with montmorillonite: preheating at 210-230℃ to break the interlayer water, followed by heating to 350℃ and holding for 1 hour, thermal expansion exfoliates the interlayer structure, increasing the specific surface area and exposing more active sites; dopamine / carbon nanotube composite modification: dopamine hydrochloride self-polymerizes under weakly alkaline conditions to form a polydopamine (PDA) coating layer, anchoring carbon nanotubes (CNTs) through π-π stacking and electrostatic interactions, while lanthanum oxide (La2O3) nanoparticles are embedded in the interlayer, forming a "montmorillonite-PDA-CNTs-La2O3" composite carrier. This design enhances the carrier's conductivity (CNTs), adsorption capacity (PDA), and acidic site density (La2O3); synergistic enhancement with added materials: sintered kaolin, titanium dioxide (TiO2), and mullite whiskers are processed with sodium carboxymethyl cellulose / Sodium dodecylbenzenesulfonate, after treatment, is uniformly loaded onto the surface of montmorillonite via ultrasonic dispersion to form a hierarchical porous structure, further enhancing mechanical strength and mass transfer efficiency. Hierarchical pore design: Micron-sized macropores (50-200 nm in diameter) formed by a double emulsion template method are combined with interlayer mesopores (2-5 nm) in montmorillonite and micropores (<2 nm) in TiO2 / kaolinite to construct a three-dimensional mass transfer network, shortening the reactant diffusion path; Lanthanum oxide synergistic catalysis: La... 3⁺ Doping introduces Lewis acidic sites, promoting the adsorption of organic pollutants and the breaking of C-C bonds; simultaneously, it enhances the redox ability of Sb₂O₃ through electron transfer, accelerating the separation of photogenerated carriers; Carbon nanotube conductive network: CNTs serve as electron transport channels, reducing charge recombination rate and improving photocatalytic efficiency; Montmorillonite carrier anchoring: Sb₂O₃ nanoparticles (50-100 nm) are uniformly dispersed on the montmorillonite surface through ball milling, and interlayer forces (such as electrostatic adsorption and hydrogen bonding) inhibit particle agglomeration; Mullite whisker support: Mullite whiskers (aspect ratio 5-10) in the sintered body form a physical framework, improving the structural stability of the material under high temperature or strong acid and alkali environments. Detailed Implementation
[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0017] This embodiment describes a method for preparing porous antimony trioxide, comprising the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 5-8 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
[0018] The method for preparing the antimony trioxide matrix in this embodiment is as follows: S1, Oil phase preparation: Weigh 2-3 parts of Span-80 and add it to 40-45 parts of white oil. Stir at 60-65℃ for 20-30 minutes until completely dissolved to obtain the oil phase. S2, P / O emulsion preparation: Weigh 4-6 parts of antimony glycol and dissolve it in 30-35 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 10-20 min to form a P / O emulsion; S3, Preparation of dual emulsion: Weigh 3-5 parts of Tween-80 and add it to 80-100 parts of deionized water. After stirring and dissolving, add 0.1-0.2 parts of sodium dihydrogen phosphate to adjust the pH to 5.0-55 to obtain the aqueous phase. Slowly add the P / O emulsion dropwise to the aqueous phase. First, stir at a high speed of 12000 r / min for 120-130 s, and then stir at a low speed of 30-40 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: Let the emulsion stand for 30-35 min, centrifuge at 8000 r / min for 10-15 min to collect the precipitate, wash with anhydrous ethanol and deionized water alternately 4-6 times, vacuum dry at 70-75℃ for 10-12 h, then calcine at 500-550℃ for 2-4 h with a heating rate of 2-4℃ / min, and obtain antimony trioxide matrix after cooling.
[0019] In this embodiment, the stirring speed is 450-550 r / min, and the stirring time is 1 hour.
[0020] The preparation method of the montmorillonite carrier in this embodiment is as follows: S01: Heat montmorillonite at 210-230℃ for 5-10 min, then raise the temperature to 350℃ at a rate of 2-5℃ / min, hold for 1 h, and then air cool to room temperature; S02: Prepare a 5-8% (w / w) dopamine hydrochloride solution; mix 2-5 parts of dopamine hydrochloride solution, 1-3 parts of sodium lignosulfonate, 3-5 parts of carbon nanotubes, and 1-2 parts of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:(11-14). After ultrasonic treatment, the montmorillonite compound loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:(3-5). After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
[0021] In this embodiment, the ultrasonic power for ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour; the ball milling treatment lasts for 2 hours with a ball milling speed of 1000-1500 r / min.
[0022] The preparation method of the feed material in this embodiment is as follows: S03a: 3-5 parts of kaolin, 2-5 parts of titanium dioxide and 1-3 parts of mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 2-5 parts of sodium carboxymethyl cellulose, 5-8 parts of sodium dodecylbenzene sulfonate solution and 1-3 parts of phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8, with an ultrasonic power of 350-400W for 1 hour. After ultrasonication, the mixture was filtered and dried to obtain the feed material.
[0023] In this embodiment, the sintering temperature for the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.
[0024] The pH value of the phosphate buffer solution in this embodiment is 5.5-6.5; the mass fraction of the sodium dodecylbenzenesulfonate solution is 8-12%.
[0025] This embodiment describes the application of a method for preparing porous antimony trioxide in catalytic degradation.
[0026] Example 1. This embodiment describes a method for preparing porous antimony trioxide, comprising the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 5 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
[0027] The method for preparing the antimony trioxide matrix in this embodiment is as follows: S1, Oil phase preparation: Weigh 2 parts of Span-80 and add it to 40 parts of white oil. Stir at 60°C for 20 minutes until completely dissolved to obtain the oil phase; S2, P / O emulsion preparation: Weigh 4 parts of antimony glycol and dissolve it in 30 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 10 min to form a P / O emulsion. S3, Preparation of dual emulsion: Weigh 3 parts of Tween-80 and add it to 80 parts of deionized water. After stirring and dissolving, add 0.1 parts of sodium dihydrogen phosphate to adjust the pH to 5.0 to obtain the aqueous phase. Slowly add the P / O emulsion dropwise to the aqueous phase. First, stir at a high speed of 12000 r / min for 120 s, and then stir at a low speed of 30 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: The emulsion was allowed to stand for 30 min, centrifuged at 8000 r / min for 10 min to collect the precipitate, washed 4 times alternately with anhydrous ethanol and deionized water, dried under vacuum at 70℃ for 10 h, and then calcined at 500℃ for 2 h with a heating rate of 2℃ / min. After cooling, the antimony trioxide matrix was obtained.
[0028] In this embodiment, the stirring speed is 450 r / min, and the stirring time is 1 h.
[0029] The preparation method of the montmorillonite carrier in this embodiment is as follows: S01: Heat-treat montmorillonite at 210℃ for 5 min, then raise the temperature to 350℃ at a rate of 2℃ / min, hold for 1 h, and then air-cool to room temperature; S02: Prepare a 5% (w / w) dopamine hydrochloride solution; mix 2 parts of dopamine hydrochloride solution, 1 part of sodium lignosulfonate, 3 parts of carbon nanotubes and 1 part of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:11. After ultrasonic treatment, the montmorillonite remixed loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:3. After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
[0030] In this embodiment, the ultrasonic power for ultrasonic treatment is 350W, and the ultrasonic treatment lasts for 1 hour; the ball milling treatment lasts for 2 hours at a ball milling speed of 1000 r / min.
[0031] The preparation method of the feed material in this embodiment is as follows: S03a: 3 parts kaolin, 2 parts titanium dioxide and 1 part mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 2 parts sodium carboxymethyl cellulose, 5 parts sodium dodecylbenzene sulfonate solution and 1 part phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8, with an ultrasonic power of 350 W for 1 hour. After ultrasonication, the mixture was filtered and dried to obtain the feed material.
[0032] In this embodiment, the sintering temperature for the blending sintering process is 300°C, and the sintering time is 1 hour.
[0033] The pH value of the phosphate buffer solution in this embodiment is 5.5; the mass fraction of the sodium dodecylbenzenesulfonate solution is 8%.
[0034] This embodiment describes the application of a method for preparing porous antimony trioxide in catalytic degradation.
[0035] Example 2. This embodiment describes a method for preparing porous antimony trioxide, comprising the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 8 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
[0036] The method for preparing the antimony trioxide matrix in this embodiment is as follows: S1, Oil phase preparation: Weigh 3 parts of Span-80 and add it to 45 parts of white oil. Stir at 65°C for 30 minutes until completely dissolved to obtain the oil phase; S2, P / O emulsion preparation: Weigh 6 parts of antimony glycol and dissolve it in 35 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 20 min to form a P / O emulsion. S3, Preparation of dual emulsion: Weigh 5 parts of Tween-80 and add it to 100 parts of deionized water. After stirring and dissolving, add 0.2 parts of sodium dihydrogen phosphate to adjust the pH to 5.5 to obtain the aqueous phase. Slowly add the P / O emulsion to the aqueous phase. First, stir at a high speed of 12000 r / min for 130 s, and then stir at a low speed of 40 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: The emulsion was allowed to stand for 35 min, centrifuged at 8000 r / min for 15 min to collect the precipitate, washed 6 times alternately with anhydrous ethanol and deionized water, dried under vacuum at 75℃ for 12 h, and then calcined at 550℃ for 4 h at a heating rate of 4℃ / min. After cooling, the antimony trioxide matrix was obtained.
[0037] In this embodiment, the stirring speed is 550 r / min, and the stirring time is 1 h.
[0038] The preparation method of the montmorillonite carrier in this embodiment is as follows: S01: Heat-treat montmorillonite at 230℃ for 10 min, then raise the temperature to 350℃ at a rate of 5℃ / min, hold for 1 h, and then air-cool to room temperature; S02: Prepare an 8% (w / w) dopamine hydrochloride solution; mix 5 parts of dopamine hydrochloride solution, 3 parts of sodium lignosulfonate, 5 parts of carbon nanotubes and 2 parts of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:14. After ultrasonic treatment, the montmorillonite compound loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:5. After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
[0039] In this embodiment, the ultrasonic power for ultrasonic treatment is 400W, and the ultrasonic treatment lasts for 1 hour; the ball milling treatment lasts for 2 hours at a ball milling speed of 1500 r / min.
[0040] The preparation method of the feed material in this embodiment is as follows: S03a: 5 parts kaolin, 5 parts titanium dioxide and 3 parts mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 5 parts sodium carboxymethyl cellulose, 8 parts sodium dodecylbenzene sulfonate solution and 3 parts phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8 with an ultrasonic power of 400W for 1 hour. After ultrasonic treatment, the mixture was filtered and dried to obtain the feed material.
[0041] In this embodiment, the sintering temperature for the blending sintering process is 350°C, and the sintering time is 1 hour.
[0042] The pH value of the phosphate buffer solution in this embodiment is 6.5; the mass fraction of the sodium dodecylbenzenesulfonate solution is 12%.
[0043] This embodiment describes the application of a method for preparing porous antimony trioxide in catalytic degradation.
[0044] Example 3. This embodiment describes a method for preparing porous antimony trioxide, comprising the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 6.5 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
[0045] The method for preparing the antimony trioxide matrix in this embodiment is as follows: S1, Oil phase preparation: Weigh 2.5 parts of Span-80 and add it to 42.5 parts of white oil. Stir at 62°C for 25 minutes until completely dissolved to obtain the oil phase; S2, P / O emulsion preparation: Weigh 5 parts of antimony glycol and dissolve it in 32.5 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 15 min to form a P / O emulsion. S3, Preparation of dual emulsion: Weigh 4 parts of Tween-80 and add it to 90 parts of deionized water. After stirring and dissolving, add 0.15 parts of sodium dihydrogen phosphate to adjust the pH to 5.2 to obtain the aqueous phase. Slowly add the P / O emulsion dropwise to the aqueous phase. First, stir at a high speed of 12000 r / min for 125 s, and then stir at a low speed of 35 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: The emulsion was allowed to stand for 32 min, centrifuged at 8000 r / min for 12.5 min to collect the precipitate, washed 5 times alternately with anhydrous ethanol and deionized water, dried under vacuum at 72℃ for 11 h, and then calcined at 525℃ for 3 h at a heating rate of 3℃ / min. After cooling, antimony trioxide matrix was obtained.
[0046] In this embodiment, the stirring speed is 500 r / min, and the stirring time is 1 h.
[0047] The preparation method of the montmorillonite carrier in this embodiment is as follows: S01: Heat-treat montmorillonite at 220℃ for 7.5 min, then raise the temperature to 350℃ at a rate of 3.5℃ / min, hold for 1 h, and then air-cool to room temperature; S02: Prepare a 6.5% (w / w) dopamine hydrochloride solution; mix 3.5 parts of dopamine hydrochloride solution, 2 parts of sodium lignosulfonate, 4 parts of carbon nanotubes and 1.5 parts of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:13. After ultrasonic treatment, the montmorillonite compound loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:4. After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
[0048] In this embodiment, the ultrasonic power for ultrasonic treatment is 375W, and the ultrasonic treatment lasts for 1 hour; the ball milling treatment lasts for 2 hours at a ball milling speed of 1250 r / min.
[0049] The preparation method of the feed material in this embodiment is as follows: S03a: 4 parts kaolin, 3.5 parts titanium dioxide and 2 parts mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 3.5 parts sodium carboxymethyl cellulose, 6.5 parts sodium dodecylbenzene sulfonate solution and 2 parts phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8 with an ultrasonic power of 370W for 1 hour. After ultrasonic treatment, the mixture was filtered and dried to obtain the feed material.
[0050] In this embodiment, the sintering temperature for the blending sintering process is 325°C, and the sintering time is 1 hour.
[0051] The pH value of the phosphate buffer solution in this embodiment is 6.0; the mass fraction of the sodium dodecylbenzenesulfonate solution is 10%.
[0052] This embodiment describes the application of a method for preparing porous antimony trioxide in catalytic degradation.
[0053] Comparative Example 1. Unlike Example 3, no montmorillonite carrier was added.
[0054] Comparative Example 2. Unlike Example 3, no loading liquid treatment was used in the preparation of the montmorillonite loading agent.
[0055] Comparative Example 3. Unlike Example 3, no carbon nanotubes or lanthanum oxide were added to the carrier solution.
[0056] Comparative Example 4. Unlike Example 3, no additive treatment was used in the preparation of the montmorillonite carrier.
[0057] Comparative Example 5. Unlike Example 3, no sintered material was added during the preparation of the feed material.
[0058] Comparative Example 6. Unlike Example 3, no kaolin or titanium dioxide was added to the sintered body.
[0059] The product performance was tested in Examples 1-3 and Comparative Examples 1-6, using the test product as a photocatalyst to degrade simulated Rhodamine B wastewater (initial concentration 100 mg / L). Reaction conditions: catalyst dosage 1.0 g / L, visible light source (500 W xenon lamp), reaction temperature 25℃, stirring rate 400 r / min. The test results are as follows: From Examples 1-3 and Comparative Examples 1-6, it can be seen that the product of the present invention has a long-term degradation rate and excellent degradation performance stability. At the same time, the performance of the product tends to deteriorate when no montmorillonite carrier is added, no carrier liquid treatment is used in the preparation of the montmorillonite carrier, no carbon nanotubes and lanthanum oxide are added to the carrier liquid, no feedstock treatment is used in the preparation of the montmorillonite carrier, no sintered body is added in the preparation of the feedstock, and no kaolin and titanium dioxide are added to the sintered body. Only the product raw materials obtained by the method of the present invention have the most significant performance effect.
[0060] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
[0061] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A method for producing a porous structure of antimony trioxide, characterized by, Includes the following steps: Antimony trioxide matrix was added to montmorillonite carrier at a ratio of 5-8 times the total amount of antimony trioxide matrix and stirred. After stirring, the mixture was filtered and dried to obtain the porous antimony trioxide structure of the present invention.
2. The method for preparing porous antimony trioxide according to claim 1, characterized in that, The preparation method of the antimony trioxide matrix is as follows: S1, Oil phase preparation: Weigh 2-3 parts of Span-80 and add it to 40-45 parts of white oil. Stir at 60-65℃ for 20-30 minutes until completely dissolved to obtain the oil phase. S2, P / O emulsion preparation: Weigh 4-6 parts of antimony glycol and dissolve it in 30-35 parts of polyol phase (dipropylene glycol: ethylene glycol = 2:1, mass ratio), stir until completely dissolved to obtain a precursor solution; add the precursor solution to the above oil phase and stir at 10000 r / min for 10-20 min to form a P / O emulsion; S3, Preparation of dual emulsion: Weigh 3-5 parts of Tween-80 and add it to 80-100 parts of deionized water. After stirring and dissolving, add 0.1-0.2 parts of sodium dihydrogen phosphate to adjust the pH to 5.0-5.5 to obtain the aqueous phase. Slowly add the P / O emulsion dropwise to the aqueous phase. First, stir at a high speed of 12000 r / min for 120-130 s, and then stir at a low speed of 30-40 r / min for 1 h to form a P / O / O dual emulsion. S4, Post-treatment: Let the emulsion stand for 30-35 min, centrifuge at 8000 r / min for 10-15 min to collect the precipitate, wash with anhydrous ethanol and deionized water alternately 4-6 times, vacuum dry at 70-75℃ for 10-12 h, then calcine at 500-550℃ for 2-4 h with a heating rate of 2-4℃ / min, and obtain antimony trioxide matrix after cooling.
3. The method for preparing porous antimony trioxide according to claim 1, characterized in that, The stirring speed for the stirring process is 450-550 r / min, and the stirring time is 1 hour.
4. The method for preparing porous antimony trioxide according to claim 1, characterized in that, The preparation method of the montmorillonite carrier is as follows: S01: Heat montmorillonite at 210-230℃ for 5-10 min, then raise the temperature to 350℃ at a rate of 2-5℃ / min, hold for 1 h, and then air cool to room temperature; S02: Prepare a 5-8% (w / w) dopamine hydrochloride solution; mix 2-5 parts of dopamine hydrochloride solution, 1-3 parts of sodium lignosulfonate, 3-5 parts of carbon nanotubes, and 1-2 parts of lanthanum oxide thoroughly to obtain the carrier solution; S03: The montmorillonite product and loading liquid of S01 are ultrasonically treated at a weight ratio of 5:(11-14). After ultrasonic treatment, the montmorillonite compound loading agent is obtained. Montmorillonite mixed loading agent and loading material were ball-milled at a weight ratio of 7:(3-5). After ball milling, the mixture was filtered and dried to obtain montmorillonite loading agent.
5. The method for preparing porous antimony trioxide according to claim 4, characterized in that, The ultrasonic power of the ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour.
6. The method for preparing porous antimony trioxide according to claim 4, characterized in that, The ball milling process is carried out at a speed of 1000-1500 r / min for 2 hours.
7. The method for preparing porous antimony trioxide according to claim 4, characterized in that, The preparation method of the feed material is as follows: S03a: 3-5 parts of kaolin, 2-5 parts of titanium dioxide and 1-3 parts of mullite whiskers are blended and sintered. After sintering, a sintered body is obtained. S03b: Mix 2-5 parts of sodium carboxymethyl cellulose, 5-8 parts of sodium dodecylbenzene sulfonate solution and 1-3 parts of phosphate buffer solution thoroughly to obtain the treatment solution; The sintered body and the treatment liquid were ultrasonically treated at a weight ratio of 5:8, with an ultrasonic power of 350-400W for 1 hour. After ultrasonication, the mixture was filtered and dried to obtain the feed material.
8. The method for preparing porous antimony trioxide according to claim 7, characterized in that, The sintering temperature for the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.
9. The method for preparing porous antimony trioxide according to claim 7, characterized in that, The pH value of the phosphate buffer solution is 5.5-6.5; the mass fraction of the sodium dodecylbenzenesulfonate solution is 8-12%.
10. The application of the method for preparing porous antimony trioxide according to claim 1 in catalytic degradation.