Persulfate activator and preparation method thereof
By preparing nanomaterial activator combined with choline gluconate, the problem of difficulty in degradation of antibiotics in traditional processes is solved, and efficient degradation of antibiotics in wastewater is achieved, especially the removal rate of tetracycline and sulfamethoxazole is significantly improved.
Patent Information
- Application Number
- CN202510542183.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-28
- Publication Date
- 2025-08-01
AI Technical Summary
The prior art is difficult to effectively degrade antibiotics in wastewater, especially tetracycline and sulfamethoxazole. The traditional process is inefficient and an urgent need for economically feasible persulfate activators to improve oxidation efficiency.
Using nanomaterial activator, a nanomaterial activator is formed by preparing a mixture of carbon shell material with nitrogen-containing compounds, metal sources and additives, and combined with choline gluconate, activate persulfate to improve its oxidation capacity and degrade antibiotics.
The degradation efficiency of antibiotics in wastewater is significantly improved, especially the removal rate of tetracycline and sulfamethoxazole, achieving more efficient wastewater treatment.
Smart Images
Figure CN120394012A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of wastewater treatment, and particularly relates to a persulfate activator and a preparation method thereof. Background Art
[0002] Antibiotics are widely used as therapeutic agents for infectious diseases of humans and livestock, as well as growth promoters in the livestock and aquaculture industries. A large amount of antibiotics used by humans and livestock are not completely metabolized and enter the sewage system through urine and feces. Most of the antibiotic parent compounds or their metabolites are difficult to degrade. After passing through the conventional water treatment process and entering the aquatic environment, various antibiotic residues can still be detected in the wastewater. For example, the highly persistent high-priority drug sulfamethoxazole may threaten non-target organisms, contaminate food, and induce the generation and spread of antibiotic-resistant bacteria and antibiotic resistance genes. Tetracycline is also widely used in the medical, livestock, and aquaculture fields, and traditional wastewater treatment processes cannot effectively degrade tetracycline. In recent years, advanced oxidation technologies based on persulfate have received much attention due to their higher redox potential and longer lifespan. To more efficiently remove antibiotics in polluted water bodies, there is an urgent need for some economically feasible and effective persulfate activators to improve the treatment of wastewater by persulfate oxidation. Summary of the Invention
[0003] The purpose of the present invention is to provide a persulfate activator and a preparation method thereof to solve the problems such as the difficulty in effectively degrading antibiotics in existing antibiotic-containing aquaculture wastewater.
[0004] To solve the above technical problems, the present invention specifically provides the following technical solutions: The present invention discloses a persulfate activator, which at least includes a nanomaterial activator.
[0005] Preferably, the preparation method of the nanomaterial activator includes: Grind the carbon source and then calcine it to obtain a carbon shell material; then mix the nitrogen-containing compound with a solvent to obtain a mixed solution, then add a metal source and an auxiliary agent to the mixed solution and stir, and then add the carbon shell material and stir to obtain a precursor solution; the precursor solution is subjected to rotary evaporation, calcination, washing, and drying to obtain the nanomaterial activator; the nitrogen-containing compound is an acyl enamine compound and hydroxyproline, and the mass ratio of the usage amount of the acyl enamine compound to hydroxyproline is 1:0.3 - 0.8, and the acyl enamine compound is prepared by reacting 6-imino-1,6-dihydropyridine-3-carbohydrazide with diethylaminoethanol. The nanomaterial activator prepared by using the acyl enamine compound and hydroxyproline has active sites evenly distributed in the carbon skeleton, making the nanomaterial activator have high activity and showing excellent persulfate activation effect in degrading wastewater, thereby effectively degrading antibiotic substances in the wastewater.
[0006] Preferably, the carbon source is sodium L-tartrate.
[0007] Preferably, the solvent is water, and the dosage ratio of the acrylamide compound to water is 1 g: 30 - 40 ml.
[0008] Preferably, the metal source is ferric chloride hexahydrate, and the mass ratio of ferric chloride hexahydrate to the acrylamide compound is 1: 7 - 8.
[0009] Preferably, the auxiliary agent is ethanol, and the dosage ratio of the metal source to the auxiliary agent is 1 g: 10 - 20 ml.
[0010] Preferably, the mass ratio of the metal source to the carbon shell material is 1: 0.6 - 1.5.
[0011] Preferably, the heating rate for calcining the carbon source is 2 - 6 °C / min, the calcination temperature is 700 - 900 °C, and the calcination time is 0.5 - 2.5 h.
[0012] Preferably, the stirring time after adding the metal source and the auxiliary agent is 1 - 3 h, the stirring time after adding the carbon shell material is 1 - 3 h, the heating rate for calcining the precursor solution is 1 - 5 °C / min, the calcination temperature is 600 - 1000 °C, and the calcination time is 0.5 - 5 h.
[0013] The present invention also discloses the application of the above persulfate activator in preparing antibiotic-degraded wastewater.
[0014] The present invention discloses a preparation method of a nano-material activator, comprising: After grinding the carbon source, calcine it at 700 - 900 °C for 0.5 - 2.5 h at a heating rate of 2 - 6 °C / min to obtain a carbon shell material; then mix the nitrogen-containing compound with the solvent to obtain a mixed solution, then add the metal source and the auxiliary agent to the mixed solution and stir for 1 - 3 h, and then add the carbon shell material and stir for 1 - 3 h to obtain a precursor solution; the precursor solution is subjected to rotary evaporation, and then calcine it at 600 - 750 °C, 750 - 850 °C, and 850 - 1000 °C respectively at a heating rate of 1 - 5 °C / min, with a total calcination time of 0.5 - 5 h, and finally wash and dry to obtain the nano-material activator.
[0015] Preferably, the carbon source is sodium L-tartrate.
[0016] Preferably, the nitrogen-containing compound is an acrylamide compound and hydroxyproline.
[0017] More preferably, the present invention discloses a mass ratio of 1: 0.3 - 0.8 with the usage amount of hydroxyproline.
[0018] Preferably, the solvent is water.
[0019] More preferably, the dosage ratio of the acylamide compound to water is 1 g: 30 - 40 ml.
[0020] Preferably, the metal source is ferric chloride hexahydrate.
[0021] More preferably, the mass ratio of ferric chloride hexahydrate to the usage amount of the acylamide compound is 1: 7 - 8.
[0022] Preferably, the auxiliary agent is ethanol, and the dosage ratio of the metal source to the auxiliary agent is 1 g: 10 - 20 ml.
[0023] Preferably, the mass ratio of the usage amount of the metal source to the carbon shell material is 1: 0.6 - 1.5.
[0024] Preferably, the solvents used for washing are hydrochloric acid solution and water, and the washing is carried out with hydrochloric acid solution and water in sequence.
[0025] More preferably, the hydrochloric acid solution is composed of hydrochloric acid and water, and the dosage ratio of hydrochloric acid to water is 1 g: 200 - 300 ml.
[0026] The present invention discloses a preparation method of an acylamide compound, specifically as follows: Mix 6 - imino - 1,6 - dihydropyridine - 3 - carbohydrazide, diethylaminoethanol, copper bromide, and tert - butyl hydroperoxide, and then react at 70 - 80 °C for 6 - 10 h. After the reaction is completed, distill under reduced pressure to obtain a crude product, and the crude product is purified by silica gel column chromatography to obtain the acylamide compound.
[0027] Preferably, the mass ratio of the usage amount of 6 - imino - 1,6 - dihydropyridine - 3 - carbohydrazide to diethylaminoethanol is 1: 1.5 - 2.
[0028] Preferably, the mass ratio of the usage amount of 6 - imino - 1,6 - dihydropyridine - 3 - carbohydrazide to copper bromide is 1: 0.3 - 0.6.
[0029] Preferably, the mass ratio of the usage amount of 6 - imino - 1,6 - dihydropyridine - 3 - carbohydrazide to tert - butyl hydroperoxide is 1: 2 - 3.5.
[0030] The present invention discloses a catalytic degradation method for wastewater, specifically as follows: Add the nanomaterial activator and persulfate into the wastewater simultaneously, stir at 20 - 30 °C for 10 - 20 min. After the stirring is completed, filter out the liquid, and then add methanol to the liquid to quench the reaction to obtain the degraded wastewater.
[0031] Preferably, the mass ratio of the usage amount of persulfate to the nanomaterial activator is 1: 0.4 - 1.6.
[0032] Preferably, the dosage ratio of persulfate to the aquaculture wastewater is 1 g: 4 - 6 L.
[0033] More preferably, the persulfate activator of the present invention further includes choline gluconate. In the catalytic degradation of wastewater, on the basis of using a nanomaterial activator to activate persulfate, choline gluconate can also be used. The synergistic use of choline gluconate and the nanomaterial activator can further enhance the activation of persulfate, and improve the degradation effect of persulfate on antibiotics by solubilizing antibiotics in wastewater, effectively degrading the wastewater.
[0034] The present invention has the following beneficial effects compared with the prior art: The present invention provides a persulfate activator and a preparation method thereof. First, a carbon source is ground and then calcined to obtain a carbon shell material; then a nitrogen-containing compound is mixed with a solvent, a metal source and an auxiliary agent are added and stirred, and then the carbon shell material is added and stirred to obtain a precursor solution; the precursor solution is subjected to rotary evaporation, calcination, washing and drying to obtain a nanomaterial activator. The nanomaterial activator is used as a persulfate activator, or together with choline gluconate as a persulfate activator. The persulfate activator prepared by the present invention has a good activation effect on persulfate and can effectively degrade antibiotics such as tetracycline and sulfamethoxazole in wastewater. BRIEF DESCRIPTION OF THE DRAWINGS
[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only exemplary, and for those of ordinary skill in the art, without creative efforts, other implementation drawings can be obtained according to the provided drawings.
[0036] Figure 1 It is a graph for measuring the removal rate of tetracycline in wastewater; Figure 2 It is a graph for measuring the removal rate of sulfamethoxazole in wastewater. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0037] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
[0038] First, the concepts involved in this application will be described in conjunction with the accompanying drawings. It should be noted here that the following descriptions of each concept are only for making the content of this application easier to understand, and do not represent a limitation on the protection scope of this application; at the same time, without conflict, the embodiments and features in the embodiments of this application can be combined with each other. This application will be described in detail below with reference to the drawings and in conjunction with the embodiments.
[0039] The specific meanings of the abbreviations used in the specification and claims are as follows: Example 1: Preparation of acylamide compound: Mix 6-imino-1,6-dihydropyridine-3-carbohydrazide, diethylaminoethanol, copper bromide, and tert-butyl hydroperoxide, and then react at 75 °C for 8 h. After the reaction, distill under reduced pressure to obtain a crude product, and the crude product is purified by silica gel column chromatography to obtain the acylamide compound. The mass ratio of the usage amounts of 6-imino-1,6-dihydropyridine-3-carbohydrazide to diethylaminoethanol is 1:1.62, the mass ratio of the usage amounts of 6-imino-1,6-dihydropyridine-3-carbohydrazide to copper bromide is 1:0.46, and the mass ratio of the usage amounts of 6-imino-1,6-dihydropyridine-3-carbohydrazide to tert-butyl hydroperoxide is 1:2.95.
[0040] Preparation of nanomaterial activator: Grind sodium L-tartrate into powder, and then calcine at 800 °C for 1 h at a heating rate of 3 °C / min under nitrogen atmosphere to obtain a carbon shell material. Mix the acylamide compound, hydroxyproline, and water to obtain a mixed solution, then add ferric chloride hexahydrate and ethanol to the mixed solution and stir for 2 h, and then add the carbon shell material and stir for 2 h to obtain a precursor solution. Rotate evaporate the precursor solution, and then calcine at 700 °C, 800 °C, and 900 °C at a heating rate of 2 °C / min for 1 h respectively. After the calcination, wash with hydrochloric acid solution and water in sequence, and finally dry to obtain the nanomaterial activator. The mass ratio of the usage amounts of the acylamide compound to hydroxyproline is 1:0.5, the usage ratio of the acylamide compound to water is 1 g:35 ml, the mass ratio of the usage amounts of ferric chloride hexahydrate to the acylamide compound is 1:7.69, the usage ratio of ferric chloride hexahydrate and ethanol is 1 g:12.5 ml, the mass ratio of the usage amounts of ferric chloride hexahydrate and the carbon shell material is 1:1, the hydrochloric acid solution is composed of hydrochloric acid and water, and the usage ratio of hydrochloric acid and water is 1 g:270 ml.
[0041] Catalytic degradation of wastewater: Add the nanomaterial activator and persulfate into the wastewater simultaneously, stir at 25 °C for 15 min, filter out the liquid after stirring, and then add methanol to the liquid to quench the reaction to obtain the degraded wastewater. The mass ratio of the usage amounts of persulfate to the nanomaterial activator is 1:1, and the usage ratio of persulfate to the aquaculture wastewater is 1 g:5 L.
[0042] Example 2: The preparation of the acrylamide compound is the same as that in Example 1.
[0043] The preparation of the persulfate activator is the same as that in Example 1.
[0044] Catalytic degradation of wastewater: In this example, the catalytic degradation of wastewater is different from that in Example 1 in that the mass ratio of the usage amounts of persulfate to the nanomaterial activator is 1:1.4, and other conditions and parameters are the same as those in Example 1.
[0045] Example 3: The preparation of the acrylamide compound is the same as that in Example 1.
[0046] The preparation of the persulfate activator is the same as that in Example 1.
[0047] Catalytic degradation of wastewater: In this example, the catalytic degradation of wastewater is different from that in Example 1 in that the mass ratio of the usage amounts of persulfate to the nanomaterial activator is 1:0.5, and other conditions and parameters are the same as those in Example 1.
[0048] Example 4: The preparation of the acrylamide compound is the same as that in Example 1.
[0049] The preparation of the persulfate activator is the same as that in Example 1.
[0050] Catalytic degradation of wastewater: First, choline gluconate is added to the wastewater, then the nanomaterial activator and persulfate are added, and the mixture is stirred at 25 °C for 15 min. After stirring, the liquid is filtered out, and then methanol is added to the liquid to quench the reaction, obtaining the degraded wastewater. The mass ratio of the usage amounts of persulfate to choline gluconate is 1:1.5, the mass ratio of the usage amounts of persulfate to the nanomaterial activator is 1:1, and the usage ratio of persulfate to the aquaculture wastewater is 1 g:5 L.
[0051] Example 5: The preparation of the acrylamide compound is the same as that in Example 1.
[0052] The preparation of the persulfate activator is the same as that in Example 1.
[0053] Catalytic degradation of wastewater: In this example, the catalytic degradation of wastewater is different from that in Example 4 in that the mass ratio of the usage amounts of persulfate to choline gluconate is 1:2, and other conditions and parameters are the same as those in Example 4.
[0054] Example 6: The preparation of the acrylamide compound is the same as that in Example 1.
[0055] The preparation of the persulfate activator is the same as that in Example 1.
[0056] Catalytic degradation of wastewater: In this example, the catalytic degradation of wastewater is different from that in Example 4 in that the mass ratio of the amount of persulfate to choline gluconate used is 1:0.5, and other conditions and parameters are the same as those in Example 4.
[0057] Comparative Example 1: The preparation of the acrylamide compound is the same as that in Example 1.
[0058] The preparation of the persulfate activator is the same as that in Example 1.
[0059] Catalytic degradation of wastewater: In this example, the catalytic degradation of wastewater is different from that in Example 4 in that the mass ratio of the amount of persulfate to the nanomaterial activator used is 1:0.05, and other conditions and parameters are the same as those in Example 4.
[0060] Experimental Example 1: Determination of the removal rate of tetracycline in wastewater. The content of tetracycline in the initial wastewater and the degraded wastewater in Examples 1-6 and Comparative Example 1 was determined by spectrophotometry. The removal rate = (tetracycline concentration in the initial wastewater - tetracycline concentration in the degraded wastewater) / tetracycline concentration in the initial wastewater × 100%.
[0061] The determination results of the removal rate of tetracycline in wastewater are as Figure 1 shown. Comparing Example 1 with Example 2 indicates that an increase in the amount of the nanomaterial activator used within a certain range can enhance the activation of persulfate, accelerate the decomposition of persulfate to generate more free radicals, thereby increasing the removal rate of tetracycline in wastewater; comparing Example 1 with Example 3 indicates that a decrease in the amount of the nanomaterial activator used within a certain range will reduce the activation of persulfate, and thus reduce the removal rate of tetracycline in wastewater; comparing Example 1 with Example 4 indicates that on the basis of using the nanomaterial activator, using choline gluconate can further enhance the activation of persulfate and increase the removal rate of tetracycline in wastewater; comparing Example 4 with Example 5 indicates that an increase in the amount of choline gluconate used within a certain range can enhance the activation of persulfate and increase the removal rate of tetracycline in wastewater; comparing Example 4 with Example 6 indicates that a decrease in the amount of choline gluconate used within a certain range will reduce the activation of persulfate, and thus reduce the removal rate of tetracycline in wastewater; comparing Example 1 with Comparative Example 1 indicates that choline gluconate needs to be used in combination with the nanomaterial activator, and too low an amount of the nanomaterial activator will reduce the removal rate of tetracycline in wastewater.
[0062] Experimental Example 2: Determination of the removal rate of sulfamethoxazole in wastewater. The content of sulfamethoxazole in the initial wastewater and the degraded wastewater in Examples 1-6 and Comparative Example 1 was determined by high performance liquid chromatography. The removal rate = (concentration of sulfamethoxazole in the initial wastewater - concentration of sulfamethoxazole in the degraded wastewater) / concentration of sulfamethoxazole in the initial wastewater × 100%.
[0063] The determination results of the removal rate of sulfamethoxazole in wastewater are as Figure 2 shown. Comparing Example 1 with Example 2 indicates that an increase in the dosage of the nanomaterial activator within a certain range can enhance the activation of persulfate and improve the removal rate of sulfamethoxazole in wastewater. Comparing Example 1 with Example 3 shows that a decrease in the dosage of the nanomaterial activator within a certain range will reduce the activation of persulfate, thereby reducing the removal rate of sulfamethoxazole in wastewater. Comparing Example 1 with Example 4 shows that on the basis of using the nanomaterial activator, the use of choline gluconate can further enhance the activation of persulfate and improve the removal rate of sulfamethoxazole in wastewater. Comparing Example 4 with Example 5 shows that an increase in the dosage of choline gluconate within a certain range can enhance the activation of persulfate and improve the removal rate of sulfamethoxazole in wastewater. Comparing Example 4 with Example 6 shows that a decrease in the dosage of choline gluconate within a certain range will reduce the activation of persulfate, thereby reducing the removal rate of sulfamethoxazole in wastewater. Comparing Example 1 with Comparative Example 1 shows that choline gluconate needs to be used together with the nanomaterial activator, and too low a dosage of the nanomaterial activator will reduce the removal rate of sulfamethoxazole in wastewater.
[0064] The above-described embodiments and / or implementation manners are merely used to illustrate the preferred embodiments and / or implementation manners for realizing the technology of the present invention, and do not impose any form of limitation on the implementation manners of the technology of the present invention. Any person skilled in the art, without departing from the scope of the technical means disclosed in the content of the present invention, may make some modifications or changes to other equivalent embodiments, but should still be regarded as the same technology or embodiment as the present invention in essence.
[0065] Specific examples are used in this article to elaborate on the principles and implementation manners of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application. The above are only the preferred implementation manners of the present application. It should be noted that due to the limitation of literal expression and objectively existing infinite specific structures, for those of ordinary skill in the art, without departing from the principle of the present application, several improvements, refinements or changes can be made, or the above technical features can be combined in an appropriate manner; these improvements, refinements, changes or combinations, or directly applying the concept and technical solution of the invention to other occasions without improvement, should all be regarded as the protection scope of the present application.
Claims
1. A persulfate activator, at least including a nanomaterial activator.
2. The persulfate activator according to claim 1, wherein The preparation method of the nanomaterial activator includes: Grinding a carbon source and then calcining it to obtain a carbon shell material; then mixing a nitrogen-containing compound with a solvent to obtain a mixed solution, then adding a metal source and an auxiliary agent to the mixed solution and stirring, and then adding the carbon shell material and stirring to obtain a precursor solution; the precursor solution is subjected to rotary evaporation, calcination, washing and drying to obtain the nanomaterial activator; the nitrogen-containing compound is an acyl enamine compound and hydroxyproline, and the mass ratio of the usage amounts of the acyl enamine compound and hydroxyproline is 1:0.3 - 0.8, and the acyl enamine compound is prepared by reacting 6-imino-1,6-dihydropyridine-3-carbohydrazide with diethylaminoethanol.
3. The persulfate activator according to claim 2, wherein The carbon source is sodium L-tartrate.
4. The persulfate activator according to claim 2, wherein The solvent is water, and the usage ratio of the acyl enamine compound to water is 1 g:30 - 40 ml.
5. An ammonium persulfate activator according to claim 2, characterized in that, The metal source is ferric chloride hexahydrate, and the mass ratio of the usage amount of ferric chloride hexahydrate to the acyl enamine compound is 1:7 - 8.
6. The persulfate activator according to claim 2, characterized in that, The auxiliary agent is ethanol, and the usage ratio of the metal source to the auxiliary agent is 1 g:10 - 20 ml.
7. The persulfate activator according to claim 2, characterized in that, The mass ratio of the usage amounts of the metal source and the carbon shell material is 1:0.6 - 1.
5.
8. The persulfate activator according to claim 2, characterized in that, The heating rate of the carbon source during calcination is 2 - 6 °C / min, the calcination temperature is 700 - 900 °C, and the calcination time is 0.5 - 2.5 h.
9. The persulfate activator according to claim 2, characterized in that, The stirring time after adding the metal source and the auxiliary agent is 1 - 3 h, the stirring time after adding the carbon shell material is 1 - 3 h, the heating rate of the precursor solution during calcination is 1 - 5 °C / min, the calcination temperature is 600 - 1000 °C, and the calcination time is 0.5 - 5 h.
10. The application of the persulfate activator prepared by any one of the methods of claims 1 - 9 in the preparation of antibiotic-degrading wastewater.