An AgIO 4 / CeO 2 Composite catalyst and its preparation method and application
By using AgIO4/CeO2 composite catalyst and electron beam irradiation, the problem of low degradation efficiency of high concentration organic pollutants in sewage in the prior art is solved, and efficient and economical sewage treatment effect is achieved.
Patent Information
- Application Number
- CN202311285116.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-28
- Publication Date
- 2025-04-04
AI Technical Summary
When existing electron beam irradiation technology degrades high concentrations of organic pollutants in wastewater, the degradation efficiency and poor effect are low, resulting in high treatment costs and application challenges.
AgIO4/CeO2 composite catalyst is used to improve the degradation efficiency and reaction rate of organic pollutants in wastewater through synergistic effects with electron beams. The particle size of the catalyst is 10 nm to 100 μm, and AgIO4 and CeO2 form dual active sites to enhance the catalytic effect.
It significantly improves the mineralization efficiency and reaction rate of electron beam irradiation, reduces treatment costs, maintains the stability and recyclability of the catalyst, and is suitable for the purification of water bodies such as industrial wastewater and urban sewage.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of sewage treatment, and specifically relates to an AgIO4 / CeO2 composite catalyst and a preparation method and application thereof. Background Art
[0002] In the process of urbanization, some industries, such as coal chemical industry, printing and dyeing, pharmaceuticals, electronics, metallurgy and pulp, emit a large amount of high-concentration, difficult-to-degrade organic pollutants every year, posing a serious threat to the environment and human health. my country's daily sewage treatment scale has exceeded 200 million tons, ranking first in the world. However, traditional sewage treatment technology has bottlenecks, making it difficult to efficiently, quickly and economically remove high-concentration organic pollutants in sewage.
[0003] Electron beam irradiation is a new type of wastewater treatment technology that has been widely used and received much attention. Electron beam irradiation generates hydroxyl radicals to achieve rapid degradation of organic pollutants, and is an efficient method for industrial wastewater treatment and purification. Compared with traditional biochemical, physical and chemical treatment methods, electron beam irradiation has higher treatment efficiency and shorter treatment cycle, and does not require the addition of additional chemicals. Therefore, under the goal of achieving zero emissions and wastewater reuse, electron beam irradiation technology has become one of the important directions for improving current wastewater treatment technology. Summary of the invention
[0004] The present invention is based on the inventor's discovery and understanding of the following facts and problems:
[0005] The advantage of electron beam irradiation technology is that it can directly degrade organic pollutants, achieve sewage purification and wastewater resource utilization. This technology can effectively remove various difficult-to-degrade, high-concentration organic pollutants, such as agricultural organic matter, petroleum hydrocarbons, dyes, nitrosamines, cyanides, etc., and is suitable for various industrial wastewater, urban sewage, rural domestic sewage, insecticides, pesticides and other water bodies. However, the existing electron beam irradiation technology often has the problems of low degradation efficiency and poor degradation effect, resulting in high treatment costs, and still faces great challenges in application.
[0006] The present invention aims to solve one of the technical problems in the related art to at least a certain extent. To this end, the embodiment of the present invention proposes an AgIO4 / CeO2 composite catalyst, which can cooperate with the irradiation of electron beams to degrade organic pollutants in sewage, improve the mineralization efficiency and reaction rate of electron beam irradiation, and has good application prospects.
[0007] The AgIO4 / CeO2 composite catalyst of the embodiment of the present invention has a particle size of 10 nm to 100 μm.
[0008] The advantages and technical effects brought by the AgIO4 / CeO2 composite catalyst of the embodiment of the present invention are as follows: 1. In the embodiment of the present invention, AgIO4 and CeO2 can form dual active sites, which play a synergistic role and can achieve multivalent state conversion by gaining and losing electrons, so that the composite catalyst has a good catalytic effect; 2. In the embodiment of the present invention, the composite catalyst has efficient adsorption and catalytic capabilities, and can cooperate with the irradiation of electron beams to degrade organic pollutants in sewage, thereby improving the mineralization efficiency and reaction rate of electron beam irradiation, reducing treatment costs, and facilitating the promotion and application of electron beam irradiation technology; 3. In the embodiment of the present invention, the composite catalyst can maintain high stability and recyclability under irradiation, has good economy and will not cause secondary pollution, and has good application prospects.
[0009] In some embodiments, the loading amount of AgIO4 in the composite catalyst is 1 to 30 wt%.
[0010] The embodiment of the present invention also provides a method for preparing an AgIO4 / CeO2 composite catalyst, comprising: adding CeO2, AgNO3 and NaIO4 into water to form a sol, and drying and calcining the sol to obtain an AgIO4 / CeO2 composite catalyst.
[0011] The advantages and technical effects brought by the preparation method of the AgIO4 / CeO2 composite catalyst of the embodiment of the present invention are as follows: 1. The AgIO4 / CeO2 composite catalyst prepared by the method of the embodiment of the present invention has high adsorption and catalytic capabilities. It is added to sewage and irradiated with electron beams to effectively degrade and purify organic pollutants and other pollutants in the sewage, thereby realizing an environmentally friendly sewage treatment process; 2. The method of the embodiment of the present invention has a short process flow, is simple and easy to operate, has high production efficiency, and is easy to promote and apply in industrial production.
[0012] In some embodiments, the mass ratio of CeO2, AgNO3 and NaIO4 is (10-20): (0.3-3.68): (0.6-7.36).
[0013] In some embodiments, the drying temperature is 90-120°C and the drying time is 2-3 hours; and / or the calcination treatment comprises increasing the temperature to 400-800°C at a heating rate of 1-5°C / min and maintaining it for 2-4 hours.
[0014] In some embodiments, the method for preparing the AgIO4 / CeO2 composite catalyst further includes adding CeO2, AgNO3 and NaIO4 into water and then subjecting the water to ultrasonic treatment to form a sol.
[0015] In some embodiments, the preparation method of CeO2 includes: mixing cerium salt, anhydrous isopropyl alcohol and ammonia water to form a colloid, allowing the mixture to stand and precipitate to form a gel, and then washing, drying and grinding the gel.
[0016] In some embodiments, the mass volume ratio of the cerium salt and anhydrous isopropanol is (20g~40g): (200mL~400mL), the amount of ammonia water used is based on adjusting the pH of the system to 8~12; and / or, the stirring time to form a colloid is 6~10h, the standing precipitation time is 4~5 days, the drying temperature is 90~120°C, and the drying time is 6~8h.
[0017] The embodiment of the present invention also provides an application of the above-mentioned AgIO4 / CeO2 composite catalyst or the AgIO4 / CeO2 composite catalyst prepared by the above-mentioned preparation method in treating sewage. After the AgIO4 / CeO2 composite catalyst is added to sewage, electron beam irradiation is performed.
[0018] In some embodiments, the addition amount of the AgIO4 / CeO2 composite catalyst is 0.05-10 g / L. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 This is a transmission electron microscope (TEM) photograph of the composite catalyst prepared in Example 1 with an AgIO4 loading of 20 wt%. DETAILED DESCRIPTION
[0020] Embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.
[0021] The AgIO4 / CeO2 composite catalyst of the embodiment of the present invention has a particle size of 10 nm to 100 μm.
[0022] The AgIO4 / CeO2 composite catalyst of the embodiment of the present invention, AgIO4 and CeO2 can form a double active site, and the two play a synergistic role, and can achieve multivalent state conversion by gaining and losing electrons, so that the composite catalyst has a good catalytic effect; the composite catalyst has efficient adsorption and catalytic capabilities, and can cooperate with the irradiation of electron beams to degrade organic pollutants in sewage, thereby improving the mineralization efficiency and reaction rate of electron beam irradiation, reducing treatment costs, and facilitating the promotion and application of electron beam irradiation technology; the composite catalyst can maintain high stability and recyclability under irradiation, has good economy and will not cause secondary pollution, and has good application prospects.
[0023] In some embodiments, preferably, the loading amount of AgIO4 in the composite catalyst is 1 to 30 wt %. Further preferably, the loading amount of AgIO4 in the composite catalyst is 3 to 20 wt %.
[0024] In the embodiment of the present invention, the loading amount of AgIO4 is preferably within a suitable range, which can make the catalyst have better catalytic activity and reduce the production cost of preparing the catalyst.
[0025] The embodiment of the present invention also provides a method for preparing an AgIO4 / CeO2 composite catalyst, comprising: adding CeO2, AgNO3 and NaIO4 into water to form a sol, and drying and calcining the sol to obtain an AgIO4 / CeO2 composite catalyst.
[0026] The preparation method of the AgIO4 / CeO2 composite catalyst of the embodiment of the present invention, the prepared AgIO4 / CeO2 composite catalyst has high adsorption and catalytic ability, and is added to sewage and irradiated with electron beams to effectively degrade and purify organic pollutants and other pollutants in the sewage, thereby realizing an environmentally friendly sewage treatment process; the process flow is short, simple and easy to operate, and the production efficiency is high, which is convenient for promotion and application in industrial production.
[0027] In some embodiments, preferably, the mass ratio of CeO2, AgNO3 and NaIO4 is (10-20): (0.3-3.68): (0.6-7.36). Further preferably, the mass ratio of CeO2, AgNO3 and NaIO4 is (10-20): (0.382-3.68): (0.765-7.36), more preferably (10-20): (1.76-3.68): (3.52-7.36).
[0028] In the embodiments of the present invention, the mass ratio of CeO2, AgNO3 and NaIO4 is optimized. By limiting the amount of CeO2, AgNO3 and NaIO4, the loading amount of AgIO4 and CeO2 in the composite catalyst can be reasonably controlled, thereby obtaining a catalyst with better comprehensive performance.
[0029] In some embodiments, preferably, the drying temperature is 90-120°C, and the drying time is 2-3 hours; and / or, the calcination treatment comprises increasing the temperature to 400-800°C at a heating rate of 1-5°C / min and maintaining for 2-4 hours. Further preferably, the calcination treatment comprises increasing the temperature to 450-550°C at a heating rate of 3-5°C / min and maintaining for 2-3 hours.
[0030] In some embodiments, preferably, the AgIO4 / CeO2 composite catalyst preparation method further comprises adding CeO2, AgNO3 and NaIO4 into water and then performing ultrasonic treatment to form a sol. Further preferably, the power of the ultrasonic treatment is 100-300W, and the ultrasonic treatment time is 1-2h. More preferably, the power of the ultrasonic treatment is 150-200W, and the ultrasonic treatment time is 1.5-2h.
[0031] In the embodiment of the present invention, adding CeO2, AgNO3 and NaIO4 into water and then subjecting them to ultrasonic treatment can promote the uniform dispersion of CeO2, AgNO3 and NaIO4, so that the catalytic performance of the prepared composite catalyst is stable.
[0032] In some embodiments, preferably, the preparation method of CeO2 comprises: mixing cerium salt, anhydrous isopropyl alcohol and ammonia water to form a colloid, allowing the mixture to stand and precipitate to form a gel, and then washing, drying and grinding the gel.
[0033] In some embodiments, preferably, the mass volume ratio of the cerium salt and anhydrous isopropanol is (20g-40g): (200mL-400mL), the amount of ammonia water used is based on adjusting the pH of the system to 8-12; and / or, the time for stirring to form a colloid is 6-10 hours, the time for static precipitation is 4-5 days, the temperature of the drying treatment is 90-120°C, and the time for drying treatment is 6-8 hours. Further preferably, the cerium salt is an inorganic salt of cerium, such as cerium nitrate, cerium sulfate, etc.; the amount of ammonia water used is based on adjusting the pH of the system to 8-10; and / or, the time for stirring to form a colloid is 6-8 hours.
[0034] The embodiment of the present invention also provides an application of the above-mentioned AgIO4 / CeO2 composite catalyst or the AgIO4 / CeO2 composite catalyst prepared by the above-mentioned preparation method in treating sewage. After the AgIO4 / CeO2 composite catalyst is added to sewage, electron beam irradiation is performed.
[0035] In some embodiments, preferably, the addition amount of the AgIO4 / CeO2 composite catalyst is 0.05-10 g / L; more preferably 0.1-5 g / L; more preferably 3-5 g / L.
[0036] In the embodiments of the present invention, the dosage of the composite catalyst in the sewage treatment process is further optimized, which can reduce the sewage treatment cost as much as possible on the basis of effectively improving the treatment efficiency of pollutants.
[0037] In some embodiments, preferably, the energy of the electron beam irradiation is 1-10 MeV, the beam current is 25-300 mA, and the electron beam irradiation dose is 0.5-20 kGy. Further preferably, the energy of the electron beam irradiation is 1-5 MeV, the beam current is 50-200 mA, and the electron beam irradiation dose is 1-10 kGy.
[0038] The technical solution of the present invention is described in detail below in conjunction with specific embodiments and drawings.
[0039] Example 1
[0040] (1) Preparation of CeO2 nanoparticles: 25.0 g of cerium sulfate was added to 250 mL of anhydrous isopropanol, and then ammonia water was added until the pH of the solution was 8. After stirring for 6 h to form a colloid, the solution was allowed to stand for 4 days to precipitate into a gel. The gel was filtered, washed with distilled water, dried at 100°C for 6 h, and ground into CeO2 nanoparticles.
[0041] (2) Preparation of AgIO4 / CeO2 composite catalyst: CeO2 (10 g), AgNO3 (1.84 g) and NaIO4 (3.68 g) were added to distilled water in sequence and magnetically stirred until uniform. The mixture was then treated under 150 W ultrasonic conditions for 1.5 h to form a sol. The sol was filtered and dried at 100°C for 2 hours and then ground into particles. The temperature was increased to 450°C at a heating rate of 3 min / °C and the particles were calcined for 3 h. The particles obtained were AgIO4 / CeO2 composite catalysts. The loading amount of AgIO4 in the composite catalyst was 20 wt%.
[0042] The prepared AgIO4 / CeO2 composite catalyst was characterized by transmission electron microscopy. Figure 1 As shown in the figure, it can be seen that uniform AgIO4 / CeO2 nanoparticles are formed in the local area, the particle size is in the range of 50 to 500 nm, with a high specific surface area, and AgIO4 and CeO2 are also evenly distributed on the nanoscale.
[0043] Example 2
[0044] The preparation method of the AgIO4 / CeO2 composite catalyst is the same as that in Example 1, except that in step (2), the amounts of CeO2, AgNO3 and NaIO4 used are 10 g, 0.3 g and 0.6 g respectively; the loading amount of AgIO4 in the composite catalyst is 3 wt %, and the morphology, structure and other characteristics of the composite catalyst are similar to those in Example 1.
[0045] Example 3
[0046] The preparation method of the AgIO4 / CeO2 composite catalyst is the same as that in Example 1, except that in step (2): the calcination temperature is 800°C.
[0047] Example 4
[0048] The preparation method of the AgIO4 / CeO2 composite catalyst is the same as that in Example 1, except that in step (2): the power of the ultrasound is 300W.
[0049] Application Example 1
[0050] The AgIO4 / CeO2 composite catalyst powder prepared in Example 1 was added to pharmaceutical wastewater, the COD of which was about 540 mg / L, the amount of the composite catalyst added was 3 g / L, and electron beam irradiation was performed, the energy of the electron beam irradiation was 5 MeV, the beam intensity was 200 mA, and the irradiation dose was 8 kGy.
[0051] Application Examples 2 to 4
[0052] The method is the same as that of Example 1, except that the AgIO4 / CeO2 composite catalysts prepared in Examples 2 to 4 are used respectively.
[0053] Application Example 5
[0054] The same as Application Example 1, the only difference is that the addition amount of the composite catalyst is 10 g / L.
[0055] Example 6
[0056] The same as Application Example 1, the only difference is that the addition amount of the composite catalyst is 0.05 g / L.
[0057] Application Example 7
[0058] The same as application example 1, except that the electron beam irradiation dose is 6 kGy.
[0059] Application Comparative Example 1
[0060] The same as Application Example 1, the only difference is that only electron beam irradiation treatment is performed without adding a catalyst.
[0061] The COD content in the wastewater treated by Examples 1 to 7 and Comparative Example 1 was tested by potassium dichromate method, and the results are shown in Table 1.
[0062] Table 1
[0063]
[0064] As can be seen from the data in Table 1, the AgIO4 / CeO2 composite catalyst prepared in Examples 1 to 4 can achieve a degradation rate of COD in wastewater of more than 45% by using electron beam irradiation, which greatly improves the degradation effect of electron beam irradiation on COD in wastewater. In addition, after 10 cycles of use, the degradation rate of COD does not decrease significantly, indicating that the AgIO4 / CeO2 composite catalyst prepared in the example has very good stability.
[0065] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.
[0066] Although the above embodiments have been shown and described, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those of ordinary skill in the art are all within the scope of protection of the present invention.
Claims
1. An AgIO4 / CeO2 composite catalyst, characterized in that: The particle size of the AgIO4 / CeO2 composite catalyst is 10nm-100μm.
2. The AgIO4 / CeO2 composite catalyst according to claim 1, characterized in that: The loading amount of AgIO4 in the composite catalyst is 1 to 30 wt%.
3. A method for preparing a AgIO4 / CeO2 composite catalyst, characterized in that: include: CeO2, AgNO3 and NaIO4 are added into water to form a sol, and the sol is dried and calcined to prepare an AgIO4 / CeO2 composite catalyst.
4. The method for preparing the AgIO4 / CeO2 composite catalyst according to claim 3, characterized in that: The mass ratio of CeO2, AgNO3 and NaIO4 is (10-20): (0.3-3.68): (0.6-7.36).
5. The method for preparing the AgIO4 / CeO2 composite catalyst according to claim 3, characterized in that: The drying treatment temperature is 90-120° C., and the drying treatment time is 2-3 hours; and / or, the calcination treatment includes increasing the temperature to 400-800° C. at a heating rate of 1-5° C. / min and maintaining it for 2-4 hours.
6. The method for preparing the AgIO4 / CeO2 composite catalyst according to any one of claims 3 to 5, characterized in that: The method also includes adding CeO2, AgNO3 and NaIO4 into water and then performing ultrasonic treatment to form a sol.
7. The method for preparing the AgIO4 / CeO2 composite catalyst according to claim 3, characterized in that: The preparation method of CeO2 comprises: mixing cerium salt, anhydrous isopropyl alcohol and ammonia water to form a colloid, allowing the mixture to stand and precipitate to form a gel, and then washing, drying and grinding the gel.
8. The method for preparing the AgIO4 / CeO2 composite catalyst according to claim 7, characterized in that: The mass volume ratio of the cerium salt and anhydrous isopropanol is (20g-40g): (200mL-400mL), the amount of ammonia water used is based on adjusting the pH of the system to 8-12; and / or, the time for stirring to form a colloid is 6-10 hours, the time for static precipitation is 4-5 days, the temperature of the drying treatment is 90-120°C, and the time for the drying treatment is 6-8 hours.
9. Use of the AgIO4 / CeO2 composite catalyst according to claim 1 or 2 or the AgIO4 / CeO2 composite catalyst prepared by the preparation method according to any one of claims 3 to 8 in treating sewage, characterized in that: After the AgIO4 / CeO2 composite catalyst is added into sewage, electron beam irradiation is performed.
10. The use of the AgIO4 / CeO2 composite catalyst in treating sewage according to claim 9, characterized in that: The added amount of the AgIO4 / CeO2 composite catalyst is 0.05-10 g / L.