A catalyst for peroxide-induced activation of dissolved oxygen to degrade pollutants, and a preparation method and application thereof
By preparing catalysts of zinc acetate, manganese chloride, and polyvinyl alcohol with sodium sulfide, the problems of narrow pH range and high energy consumption in traditional wastewater treatment technologies were solved, achieving efficient and low-energy degradation of organic pollutants.
Patent Information
- Application Number
- CN202311572757.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-22
- Publication Date
- 2026-02-10
- Estimated Expiration
- 2043-11-22
AI Technical Summary
Existing wastewater treatment technologies are ineffective at removing structurally stable new pollutants. Traditional advanced oxidation technologies have a narrow pH range, high energy consumption, and produce iron sludge.
A peroxide-induced activated dissolved oxygen catalyst was prepared by reacting zinc acetate, manganese chloride, and polyvinyl alcohol with sodium sulfide in deionized water. This catalyst is suitable for degrading pollutants, has a wide pH range, and does not require continuous addition of reagents.
It achieves efficient degradation of organic pollutants over a wide pH range, reduces energy consumption, avoids secondary pollution, has a long catalyst lifespan, and reduces treatment costs.
Smart Images
Figure CN117463367B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic pollutant treatment technology in wastewater, and in particular to a catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants, its preparation method, and its application. Background Technology
[0002] With rapid economic development, accelerated urbanization, and the continued advancement of rural revitalization policies, modern agriculture, industry, and processing and manufacturing have further developed in both urban and rural areas, leading to a rapid rise in urban and rural economic levels. However, the resulting ecological damage and pollution cannot be underestimated, and water pollution problems in both urban and rural areas are becoming increasingly serious.
[0003] Biological methods are a common wastewater treatment technology in wastewater treatment plants, but they are ineffective at removing structurally stable new pollutants. Based on these issues, advanced oxidation technologies (AORs) capable of generating highly reactive oxidizing species for intensive treatment have gradually developed. However, traditional AORs suffer from problems such as a narrow pH range (pH < 4), the generation of large amounts of iron sludge, and the need for continuous reagent addition, resulting in high energy consumption and low efficiency. Therefore, it is necessary to develop a water treatment technology that does not require continuous reagent addition, adapts to a wider pH range, and is highly efficient and energy-saving in removing organic pollutants. Summary of the Invention
[0004] The first objective of this invention is to provide a catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants. This catalyst can be applied to peroxide-induced activated dissolved oxygen degradation of pollutants, resulting in a water treatment technology that can remove organic pollutants without the need for continuous addition of reagents, adapts to a wide pH range, and is highly efficient and energy-saving.
[0005] The second objective of this invention is to provide a method for preparing a catalyst that induces dissolved oxygen to degrade pollutants using peroxides.
[0006] A third objective of this invention is to provide the application of a catalyst for the degradation of pollutants by peroxide-induced activated dissolved oxygen.
[0007] This invention provides a method for preparing a catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants, comprising the following steps:
[0008] S1: Dissolve zinc acetate, manganese chloride and polyvinyl alcohol in deionized water and stir to form solution A;
[0009] S2: Dissolve sodium sulfide in deionized water and stir to form solution B;
[0010] S3: Under continuous stirring, solution B is added to solution A, stirred evenly, and allowed to precipitate at room temperature for a period of time. The precipitate C is then filtered to obtain precipitate C. Precipitate C is washed, dried, and ground to obtain a catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants.
[0011] Preferably, in steps S1 and S2, the mass ratio of zinc acetate, manganese chloride, polyvinyl alcohol, and sodium sulfide is (3-10):(0.1-1):(1-5):(1-5). More preferably, the mass ratio of polyvinyl alcohol to sodium sulfide is 1:1.
[0012] Preferably, in step S1, the concentration of polyvinyl alcohol in solution A is 0.005-0.1 g / mL, and the stirring time is 30-120 min.
[0013] Preferably, in step S2, the concentration of sodium sulfide in solution B is 0.01-0.25 g / mL, and the stirring time is 10-30 min.
[0014] When the mass of zinc acetate, manganese chloride, polyvinyl alcohol and sodium sulfide is (3-10g):(0.1-1g):(1-5g):(1-5g), the volume of deionized water in step S1 is 50-200mL, and the volume of deionized water in step S2 is 20-100mL.
[0015] Preferably, in step S3, solution B is added dropwise to solution A, and the stirring temperature is 50-100℃ and the stirring time is 20-120 min when the mixture is stirred evenly.
[0016] Preferably, in step S3, the precipitation time is 12-36 hours at room temperature.
[0017] Preferably, in step S3, washing is performed by alternating between deionized water and methanol, and the number of washing cycles is 3-10; the drying temperature is 80-120℃, and the drying time is 3-6 hours; and the material is ground to 50-100 mesh.
[0018] The present invention also provides a catalyst for the degradation of pollutants by peroxide-induced activated dissolved oxygen prepared by the above preparation method.
[0019] The present invention also provides an application of the above-mentioned catalyst in the treatment of organic pollutants in water by using peroxide-induced activated dissolved oxygen to degrade pollutants.
[0020] Preferably, the peroxide includes persulfate, and the organic pollutant includes at least one of rhodamine B, Acid Orange 7, ciprofloxacin, bisphenol A, ibuprofen, diphenhydramine, and phenytoin.
[0021] Beneficial effects:
[0022] The catalyst provided by this invention can activate dissolved oxygen in water under the induction of peroxides, utilizing the energy of organic pollutants in wastewater to treat organic pollutants. During the treatment process, no continuous addition of energy is required, and no secondary pollution is generated, thus reducing energy consumption and accelerating the treatment speed.
[0023] The catalyst provided by this invention can treat a variety of organic pollutants and can adapt to a wide pH range and a complex anionic environment.
[0024] The catalyst provided by this invention is a solid powder catalyst with a large specific surface area, which can increase the probability of contact with pollutants and ensure the full degradation of pollutants.
[0025] The catalyst of this invention also has a long service life and can maintain a long-term treatment effect, thereby reducing the cost of wastewater treatment.
[0026] The preparation method used in this invention is simple and effective, easy to promote and apply, and has high practicality. Attached Figure Description
[0027] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0028] Figure 1 A scanning electron microscope image of the catalyst prepared in Example 1;
[0029] Figure 2 The degradation curves of the catalyst prepared in Example 1 on Rhodamine B (RhB), Acid Orange 7 (AO7), Ciprofloxacin (CIP), Bisphenol A (BPA), Ibuprofen (IBU), and Diphenhydramine (DP) are shown.
[0030] Figure 3 The degradation curves of diphenhydramine (DP) by the catalyst prepared in Example 1 at different pH values are shown.
[0031] Figure 4 The degradation curves of diphenhydramine (DP) by the catalyst prepared in Example 1 under different anions are shown.
[0032] Figure 5 The image shows the effect of the catalyst prepared in Example 1 on the continuous degradation of diphenhydramine (DP). Detailed Implementation
[0033] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.
[0034] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.
[0035] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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.
[0036] Example 1
[0037] A catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants includes the following steps:
[0038] S1: Mix 5g of zinc acetate, 0.6g of manganese chloride and 3g of polyvinyl alcohol and dissolve them in 80mL of deionized water. At this time, the concentration of polyvinyl alcohol is 0.0375g / mL. Stir for 60min to form solution A.
[0039] S2: Dissolve sodium sulfide in 50 mL of deionized water at a mass ratio of 1:1 with polyvinyl alcohol. The concentration of sodium sulfate at this time is 0.06 g / mL. Stir for 10 min to form solution B.
[0040] S3: Under continuous stirring, solution B was added dropwise to solution A. The mixture was stirred at 60°C for 60 minutes until homogeneous. The precipitate was then stored at room temperature for 12 hours and filtered to obtain precipitate C. Precipitate C was washed three times, alternating between deionized water and methanol. It was then dried at 80°C for 6 hours and ground to 60 mesh to obtain a peroxide-induced activated dissolved oxygen degradation catalyst (MnZnS QDs). Its scanning electron microscope image is shown below. Figure 1 As shown.
[0041] Example 2
[0042] A catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants includes the following steps:
[0043] S1: Mix 6g of zinc acetate, 0.7g of manganese chloride and 4g of polyvinyl alcohol and dissolve them in 80mL of deionized water. At this time, the concentration of polyvinyl alcohol is 0.05g / mL. Stir for 90min to form solution A.
[0044] S2: Dissolve 4g of sodium sulfide in 60mL of deionized water. The mass ratio of sodium sulfate to polyvinyl alcohol is 1:1. At this time, the concentration of sodium sulfide is 0.067g / mL. After stirring for 20min, solution B is formed.
[0045] S3: Under continuous stirring, solution B was added dropwise to solution A. The mixture was stirred at 90°C for 90 min. After stirring until homogeneous, the precipitate was stored at room temperature for 24 h. The precipitate C was obtained by filtration. Precipitate C was washed with deionized water and methanol alternately for 5 washes. The precipitate C was dried at 100°C for 5 h. The precipitate C was ground to 80 mesh to obtain a peroxide-induced activated dissolved oxygen degradation catalyst (MnZnS QDs).
[0046] Example 3
[0047] A catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants includes the following steps:
[0048] S1: Mix 10g of zinc acetate, 1g of manganese chloride and 5g of polyvinyl alcohol and dissolve them in 200mL of deionized water. The concentration of polyvinyl alcohol is 0.025g / mL. Stir for 120min to form solution A.
[0049] S2: Dissolve 5g of sodium sulfide in 100mL of deionized water. The mass ratio of sodium sulfate to polyvinyl alcohol is 1:1. The concentration of sodium sulfide is 0.05g / mL. Stir for 30min to form solution B.
[0050] S3: Under continuous stirring, solution B was added dropwise to solution A. The mixture was stirred at 100°C for 120 min. After stirring until homogeneous, the mixture was allowed to precipitate at room temperature for 36 h. The precipitate C was then filtered to obtain precipitate C. Precipitate C was washed with deionized water and methanol alternately for 8 washes. The precipitate C was then dried at 120°C for 3 h. Finally, it was ground to 100 mesh to obtain a peroxide-induced activated dissolved oxygen catalyst for pollutant degradation (MnZnS QDs).
[0051] Example 4
[0052] A catalyst for peroxide-induced activated dissolved oxygen degradation of pollutants includes the following steps:
[0053] S1: Mix 3g of zinc acetate, 0.1g of manganese chloride and 1g of polyvinyl alcohol and dissolve them in 50mL of deionized water. The concentration of polyvinyl alcohol is 0.02g / mL. Stir for 30min to form solution A.
[0054] S2: Dissolve 2g of sodium sulfide in 20mL of deionized water. The concentration of sodium sulfide is 0.1g / mL. Stir for 10min to form solution B.
[0055] S3: Under continuous stirring, solution B was added dropwise to solution A. The mixture was stirred at 50°C for 20 minutes. After stirring until homogeneous, the precipitate was stored at room temperature for 24 hours and filtered to obtain precipitate C. Precipitate C was washed with alternating deionized water and methanol for 10 washes. It was then dried at 100°C for 4 hours and ground to 50 mesh to obtain a peroxide-induced activated dissolved oxygen catalyst for pollutant degradation (MnZnS QDs).
[0056] Test Example 1
[0057] The catalyst prepared in Example 1, which uses peroxide-induced activated dissolved oxygen to degrade pollutants, was used to remove organic pollutants from water; the specific steps are as follows:
[0058] 0.025 g of the catalyst from Example 1 (MnZnS QDs) and 5 mM permonosulfate (PMS) were added to 50 mL of a 10 ppm contaminant solution. The solution was kept at a constant temperature of 35 °C with continuous stirring. Samples were taken at different time points to detect changes in contaminant concentration. The results are as follows: Figure 2 As shown.
[0059] Depend on Figure 2 It can be seen that: within approximately 30 minutes, the degradation efficiency of Rhodamine B (RhB) reaches 99%; the degradation efficiency of Acid Orange 7 (AO7), Ciprofloxacin (CIP), Bisphenol A (BPA), and Diphenhydramine (DP) reaches approximately 90%; and the degradation efficiency of Ibuprofen (IBU) reaches approximately 70%. The catalyst in Example 1 of this invention can rapidly treat organic pollutants in water.
[0060] Test Example 2
[0061] The peroxide-induced activated dissolved oxygen catalyst prepared in Example 1 was used to remove organic pollutants from water at different pH values; details are as follows:
[0062] 0.025 g of the catalyst from Example 1 (MnZnS QDs) and 5 mM persulfate were added to 50 mL of a 10 ppm diphenhydramine (DP) contaminant solution. The pH of the contaminant solution was adjusted to 3, 5, 7, 9, and 11, respectively. The solution was kept at a constant temperature of 35°C with continuous stirring. Samples were taken at different time points to detect changes in the concentration of the contaminants. The detection results are as follows: Figure 3 As shown.
[0063] Depend on Figure 3It can be seen that within 60 minutes, the catalyst (MnZnS QDs) achieved a degradation efficiency of approximately 90% for DP at pH 3 and 7; approximately 80% at pH 5 and 9; and approximately 50% at pH 11. In Example 1, the catalyst (MnZnS QDs) showed better degradation efficiency for DP at pH 3 and 7.
[0064] Test Example 3
[0065] The peroxide-induced activated dissolved oxygen catalyst prepared in Example 1 was used to remove organic pollutants from water at different pH values; details are as follows:
[0066] 0.025g of the catalyst from Example 1 (MnZnS QDs) and 5mM persulfate were added to 50mL of a 10ppm contaminant solution to obtain a treatment solution. Five identical treatment solutions were prepared, one as a blank control without anion addition, and the other four were respectively treated with 1mM of four inorganic salts: Na₂HPO₄, Na₂SO₄, NaCl, and NaHCO₃. The solutions were kept at a constant temperature of 35℃ with continuous stirring. Samples were taken at different time points to detect the contaminant concentration changes. The detection results are as follows: Figure 4 As shown.
[0067] Depend on Figure 4 It can be seen that within 60 min, the catalyst (MnZnS QDs) achieved a degradation rate of about 90% for DP in Na2SO4 and NaHCO3 environments; the degradation rate for DP in the anion-free environment also reached about 90%, but the degradation rate stagnated between 5 and 15 min; the degradation rate for DP in NaCl environment reached about 80%; and the degradation rate for DP in Na2HPO4 environment reached about 50%.
[0068] Test Example 4
[0069] The catalyst prepared in Example 1, which uses peroxide-induced activated dissolved oxygen to degrade pollutants, was used for continuous removal of DP; the details are as follows:
[0070] The catalyst (MnZnS QDs) from Example 1, persulfate (PMS), and the pollutant diphenhydramine (DP) were used to construct a self-purification system in a fixed-bed column reactor (catalyst concentration: 0.5 g / L, PMS concentration: 14 mM, DP concentration: 10 ppm). The hydraulic retention time was 30 minutes, and the sampling interval was 24 hours to detect changes in pollutant concentration. The results are as follows: Figure 5 As shown.
[0071] Figure 5The results showed that after 336 hours of continuous degradation, the degradation efficiency of DP remained above 80%, indicating that the catalyst has a long lifespan and can maintain a long-term treatment effect, which is convenient for practical application.
[0072] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. The application of a catalyst in the degradation of organic pollutants in wastewater using peroxide-induced activated dissolved oxygen, characterized in that, The method for preparing the catalyst includes the following steps: S1: Dissolve zinc acetate, manganese chloride and polyvinyl alcohol in deionized water, stir for 30-120 min to form solution A, the concentration of polyvinyl alcohol in solution A is 0.005-0.1 g / mL; S2: Dissolve sodium sulfide in deionized water and stir for 10-30 min to form solution B. The concentration of sodium sulfide in solution B is 0.01-0.25 g / mL. In steps S1 and S2, the mass ratio of zinc acetate, manganese chloride, polyvinyl alcohol and sodium sulfide is (3-10):(0.1-1):(1-5):(1-5). S3: Under continuous stirring, solution B is added to solution A, stirred evenly, and allowed to precipitate at room temperature for a period of time. The precipitate C is then filtered to obtain precipitate C. Precipitate C is washed, dried, and ground to obtain a catalyst for peroxide-induced activated dissolved oxygen degradation of organic pollutants in wastewater.
2. The application according to claim 1, characterized in that, In step S3, solution B is added dropwise to solution A, and the stirring temperature is 50-100℃ and the stirring time is 20-120 min when the mixture is stirred evenly.
3. The application according to claim 1, characterized in that, In step S3, the precipitation time is 12-36 hours at room temperature.
4. The application according to claim 1, characterized in that, In step S3, washing is performed by alternating between deionized water and methanol, with 3-10 washing cycles; drying temperature is 80-120℃, drying time is 3-6 hours; grinding is performed to 50-100 mesh.
5. The application according to claim 1, characterized in that, Peroxides include persulfate, and organic pollutants include at least one of rhodamine B, Acid Orange 7, ciprofloxacin, bisphenol A, ibuprofen, diphenhydramine, and phenytoin.