Fenton-like catalyst derived from polymer adsorbent and preparation method of Fenton-like catalyst
By designing Cu@C carbon-based Fenton catalyst derived from polymer adsorbents, the problems of low degradation efficiency and secondary pollution of heavy metals and organic pollutants in industrial wastewater are solved, and efficient degradation and secondary utilization of catalysts are achieved.
Patent Information
- Application Number
- CN202510319034.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-18
- Publication Date
- 2025-06-17
AI Technical Summary
In the prior art, when dealing with heavy metals and organic pollutants in industrial wastewater, there are problems of secondary pollution and the difficulty in achieving effective degradation.
A Fenton-like catalyst derived from polymer adsorbents is designed, specifically Cu@C carbon-based Fenton-like catalyst. Through specific preparation steps, copper ions are dispersed and supported on carbon materials to form a carbon-based Fenton-like catalyst.
This catalyst can effectively degrade a variety of pollutants in industrial wastewater in a short period of time, reduce the secondary pollution problem of transition metals, and realize the secondary utilization of the catalyst.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of catalyst preparation, and particularly relates to a Fenton-like catalyst derived from a polymer adsorbent and a preparation method thereof. Background Art
[0002] Typical industrial wastewater includes two categories. One is wastewater containing toxic metal ion pollutants such as chromium (Cr), copper (Cu), nickel (Ni), and cobalt (Co); the other is fine chemical wastewater, mainly wastewater containing various aromatic organic pollutants. Heavy metal ions are pollutants that cannot be naturally degraded and cannot be metabolized by the human body, causing serious harm to the ecological environment system and human health. At present, the commonly used methods for treating metal ion pollutants are divided into three categories: physical methods, chemical methods, and biological methods. Among them, the adsorption method, which belongs to the physical method, is widely used in treating heavy metal polluted wastewater due to its advantages such as high efficiency, economy, and environmental friendliness. This method enriches heavy metal ions onto the adsorbent through the interaction between the adsorbent and heavy metal ions to achieve the purpose of removing heavy metal ions from water bodies.
[0003] In addition to metal ion pollutants, organic pollutants such as phenols in the discharged wastewater are also difficult to be naturally degraded, seriously endangering human health. Researchers have been exploring methods such as adsorption, biodegradation, membrane separation, and advanced oxidation processes (AOPs) to completely remove these organic pollutants. In recent years, AOPs based on peroxymonosulfate (PMS) have received extensive attention due to the strong oxidation ability of the reactive oxygen species (ROS) generated. The ROS generated after PMS activation can efficiently mineralize a variety of organic pollutants within a wide pH range and produce less secondary pollution. PMS can be activated by various methods, including heat treatment, microwave, ultraviolet irradiation, ultrasound, or transition metal catalysis. Various transition metals, including Fe, Co, Cu, Ni, Mn, and their oxides, can activate PMS to generate ROS. Among them, Co 3+ / Co 2+ has a relatively high redox potential (E0 = 1.92V), so Co-based catalysts are considered to be one of the most effective catalysts for activating PMS. However, traditional heterogeneous Co-based catalysts and Co oxide catalysts have serious secondary pollution problems. It has been found that dispersing and loading Co on carbon materials can expose more active sites, which can improve the catalytic activity while reducing the secondary pollution problem of Co metal leaching. Cobalt-modified carbon nanocomposites are one of the research hotspots of AOP catalytic materials in recent years.
[0004] "Turning waste into treasure and treating waste with waste" refers to a method of treating pollution problems by utilizing waste. This method can not only solve environmental pollution problems, but also make full use of waste, with high economic and environmental benefits. However, at present, many water treatment solid wastes containing metal elements are difficult to be reused after element extraction. Summary of the Invention
[0005] To solve the above problems, this application designs a Fenton-like catalyst derived from a polymer adsorbent and its preparation method, aiming to effectively degrade various pollutants in industrial wastewater within a short time and achieve secondary utilization through the Cu@C carbon-based Fenton-like catalyst developed in this application.
[0006] A Fenton-like catalyst derived from a polymer adsorbent, and the catalyst is a Cu@C carbon-based Fenton-like catalyst.
[0007] Preferably, it includes the following steps:
[0008] Step S1: Weigh N-methyldiallylammonium chloride, allyl chloride and acetone, and stir to prepare the crosslinking agent TAMAC;
[0009] Step S2: Weigh acrylic acid, crosslinking agent TAMAC, ammonium persulfate and deionized water, and heat and stir to react to prepare the intermediate PAGH;
[0010] Step S3: Wash the intermediate PAGH with sodium hydroxide solution to prepare the adsorbent PAG;
[0011] Step S4: Put the adsorbent PAG into copper sulfate solution, stir until adsorption equilibrium is reached; filter the adsorbent and dry it to obtain PAG-Cu;
[0012] Step S5: Place PAG-Cu in a tube furnace and calcine it at high temperature in a nitrogen atmosphere to obtain the Cu@C carbon-based Fenton-like catalyst.
[0013] Preferably, in the step S1, the mass ratio of N-methyldiallylammonium chloride, allyl chloride and acetone is 3-5:2-4:4-6.
[0014] Preferably, in the step S2, the mass ratio of acrylic acid, crosslinking agent TAMAC, ammonium persulfate and deionized water is 5-7:0.5-2:1-3:8-12.
[0015] Preferably, in the step S2, the heating and stirring reaction temperature is 50-90 °C.
[0016] Preferably, in the step S2, the heating and stirring reaction time is 10-50 h.
[0017] Preferably, in the step S4, the concentration of copper ions in the copper sulfate solution is 200 - 2000 mg / L.
[0018] Preferably, in the step S5, the temperature of high-temperature calcination is 12 - 36 h.
[0019] Preferably, in the step S5, the time of high-temperature calcination is 2 - 5 h.
[0020] The advantages and effects of this application are as follows:
[0021] The Cu@C carbon-based Fenton-like catalyst prepared by the present invention can effectively degrade various pollutants in industrial wastewater in a short time. Compared with the application of copper oxide in the Fenton-like reaction, the introduction of carbon can effectively solve the problem of secondary pollution of transition metals and expand the application of supported catalysts in the Fenton-like system.
[0022] The above description is only an overview of the technical solution of this application. In order to understand the technical means of this application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features, and advantages of this application more obvious and understandable, the following is a detailed description of the preferred embodiments of this application in conjunction with the drawings.
[0023] According to the following detailed description of the specific embodiments of this application in conjunction with the drawings, those skilled in the art will understand the above and other purposes, advantages, and features of this application more clearly. Description of the Drawings
[0024] In order to more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings. In all the drawings, similar elements or parts are generally marked with similar reference numerals. In the drawings, the elements or parts are not necessarily drawn to scale.
[0025] Figure 1 It is a flowchart for the preparation of a Fenton-like catalyst derived from a polymer adsorbent designed for this application;
[0026] Figure 2 It is the effect diagram of the degradation of 2,4-DCP by pure metallic copper, pure carbon, and adsorbent-derived Cu@C.
[0027] Figure 3 It is the effect diagram of the degradation of 2,4-DCP by the adsorbent-derived catalyst prepared at different heating temperatures.
[0028] Figure 4It is the effect diagram of the adsorbent-derived catalyst prepared under different heating times for degrading 2,4-DCP.
[0029] Figure 5 It is the effect diagram of the adsorbent-derived catalyst adsorbing different copper ion concentrations for degrading 2,4-DCP.
[0030] Figure 6 It is the effect diagram of the catalyst prepared at different calcination temperatures for degrading 2,4-DCP.
[0031] Figure 7 It is the effect diagram of the catalyst prepared at different calcination times for degrading 2,4-DCP.
[0032] Figure 8 It is the effect diagram of the catalyst Cu@C for degrading other pollutants. Specific implementation manners
[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. In the following description, specific details such as specific configurations and components are provided only to assist in a comprehensive understanding of the embodiments of the present application. Therefore, those skilled in the art should understand that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the present application. Additionally, descriptions of known functions and structures are omitted for clarity and conciseness in the embodiments.
[0034] It should be understood that the "one embodiment" or "the present embodiment" mentioned throughout the specification means that the specific features, structures, or characteristics related to the embodiment are included in at least one embodiment of the present application. Therefore, the "one embodiment" or "the present embodiment" that appears throughout the specification does not necessarily refer to the same embodiment. In addition, these specific features, structures, or characteristics can be combined in one or more embodiments in any suitable manner.
[0035] In addition, the present application may repeat reference numerals and / or letters in different examples. This repetition is for the purpose of simplification and clarity, and does not itself indicate the relationship between the various embodiments and / or settings discussed.
[0036] In this text, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, B exists alone, and both A and B exist simultaneously. In this text, the term " / and" describes another relationship between related objects, indicating that there can be two relationships. For example, A / and B can represent two situations: A exists alone, and both A and B exist. Additionally, in this text, the character " / " generally indicates that the related objects before and after are in an "or" relationship.
[0037] In this text, the term "at least one" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, at least one of A and B can represent three situations: A exists alone, both A and B exist simultaneously, and B exists alone.
[0038] It should also be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion.
[0039] Example 1
[0040] Please refer to Figure 1 , this example mainly introduces an optimal preparation method of a Fenton-like catalyst derived from a polymer adsorbent, including the following steps:
[0041] Step S1: Weigh 21.15 mL of N-methyldiallylammonium chloride, 14.68 mL of allyl chloride, and 25 mL of acetone, and stir and react at 30 °C for 48 h to obtain the crosslinking agent TAMAC;
[0042] Step S2: Weigh 3 g of acrylic acid, 0.41 g of the crosslinking agent TAMAC, 1 g of ammonium persulfate, and 5 mL of deionized water, heat and stir at 50 °C for 30 h to react and prepare the intermediate PAGH;
[0043] Step S3: Wash the intermediate PAGH with a sodium hydroxide solution to prepare the adsorbent PAG;
[0044] Step S4: Put the adsorbent PAG into a 2000 mg / L copper sulfate solution, stir until adsorption equilibrium is reached; filter the adsorbent and dry it to obtain PAG-Cu;
[0045] Step S5: Place PAG-Cu in a tubular furnace and calcine it at 800 °C in a nitrogen atmosphere to obtain the Cu@C carbon-based Fenton-like catalyst.
[0046] Further, in the step S1, the mass ratio of N-methyldiallylammonium chloride, allyl chloride and acetone is 3-5:2-4:4-6.
[0047] Further, in the step S2, the mass ratio of acrylic acid, cross-linking agent TAMAC, ammonium persulfate and deionized water is 5-7:0.5-2:1-3:8-12.
[0048] Further, in the step S2, the heating and stirring reaction temperature is 50-90 °C.
[0049] Further, in the step S2, the heating and stirring reaction time is 10-50 h.
[0050] Further, in the step S4, the concentration of copper ions in the copper sulfate solution is 200-2000 mg / L.
[0051] Further, in the step S5, the temperature of high-temperature calcination is 12-36 h.
[0052] Further, in the step S5, the time of high-temperature calcination is 2-5 h.
[0053] Example 2
[0054] Based on Example 1, this example mainly introduces the data verification of the Cu@C carbon-based Fenton-like catalyst designed in this application. The catalyst was applied to the advanced oxidation reaction of activating PMS to degrade 2,4-dichlorophenol (2,4-DCP), and its catalytic performance was tested and evaluated.
[0055] The comparative samples of elemental copper, carbon and Cu@C were used to catalyze the degradation of 100 mL of 2,4-DCP with a concentration of 20 μM by PMS. The concentration of 2,4-DCP in the solution after different reaction times was tested by high performance liquid chromatography to evaluate the performance of the catalyst. The results are as Figure 2 shown. It can be seen that after 30 minutes, the elemental copper system only degraded 28.1% of 2,4-DCP, the elemental carbon system degraded 28.5% of 2,4-DCP, and the Cu@C system could degrade 97.1% of 2,4-DCP. It can be seen that the catalytic performance of Cu@C is much higher than that of single active metal copper or carrier carbon, proving that metal copper and carbon synergistically promoted the catalytic performance.
[0056] The catalysts prepared at the adsorbent synthesis temperatures of 50 °C, 70 °C and 90 °C were respectively used to activate PMS to degrade 2,4-DCP. After reacting for 30 min, the concentration of 2,4-DCP in the solution was tested. The results are as Figure 3As shown, by comparison, it can be seen that the catalyst prepared from the adsorbent synthesized at 90 °C has the best performance, and the degradation of 2,4-DCP can reach 97.1% in 30 min. Therefore, the optimal synthesis temperature of the adsorbent is 90 °C.
[0057] The catalysts prepared with the polymerization time of the adsorbent being 10 h, 30 h, and 50 h respectively were used to activate PMS to degrade 2,4-DCP. After reacting for 30 min, the concentration of 2,4-DCP in the solution was measured. The results are as Figure 4 shown. By comparison, it can be seen that the catalyst prepared from the adsorbent synthesized with a polymerization time of 30 h has the best performance, and the degradation of 2,4-DCP can reach 97.1% in 30 min. Therefore, the optimal polymerization time of the adsorbent is 30 h.
[0058] Three catalysts obtained by the adsorbent adsorbing copper ion solutions with different concentrations (200, 1000, 2000 mg / L), namely Cu@C-200, Cu@C-1000, and Cu@C, were used to activate PMS to degrade 2,4-DCP. After reacting for 30 min, the concentration of 2,4-DCP in the solution was measured. The results are as Figure 5 shown. By comparison, it can be seen that the catalyst obtained by adsorbing the copper ion solution with a concentration of 2000 mg / L has the best performance, and the degradation of 2,4-DCP can reach 97.1% in 30 min. Therefore, the optimal concentration of the adsorbed copper ion solution is 2000 mg / L. It shows that the higher the concentration of copper ions in the adsorbed copper ion solution, the higher the activity of the obtained catalyst. This may be because the higher the copper ion concentration, the more copper ions are adsorbed, and the higher the copper content in the prepared catalyst.
[0059] The calcination temperatures of the catalyst were set at 600, 800, and 1000 °C respectively. The obtained catalysts were used to activate PMS to degrade 2,4-DCP. After reacting for 30 min, the concentration of 2,4-DCP in the solution was measured. The results are as Figure 6 shown. By comparison, it can be seen that the catalyst synthesized at a calcination temperature of 800 °C has the best performance, and the degradation of 2,4-DCP can reach 97.1% in 30 min. Therefore, the optimal calcination temperature is 800 °C.
[0060] The calcination temperature of the catalyst was set at 800 °C. The catalysts obtained by setting the calcination time at 2, 3, 4, and 5 h respectively were used to activate PMS to degrade 2,4-DCP. After reacting for 30 min, the concentration of 2,4-DCP in the solution was measured. The results are as Figure 7 shown. By comparison, it can be seen that the catalyst synthesized with a calcination time of 3 h has the best performance, and the degradation of 2,4-DCP can reach 97.1% in 30 min. Therefore, the optimal calcination time is 3 h.
[0061] It can be seen that the optimal preparation conditions for the catalyst Cu@C are that the adsorbent synthesis temperature is 90 °C and heated for 30 h. When the adsorbent treats copper ions at 2000 mg / L, the used adsorbent is calcined at 800 °C for 3 h under a nitrogen atmosphere.
[0062] To further investigate the universality of the obtained catalyst Cu@C, it was used to degrade several common pollutants, bisphenol A, benzoic acid, and atrazine, respectively. The results are as Figure 8 shown. After 30 min, the degradation of bisphenol A can reach 97.0%, the degradation of benzoic acid can reach 98.0%, and the degradation of atrazine can reach 91.2%. This shows that the catalyst Cu@C has good universality for common pollutants in water.
[0063] The above are only the preferred embodiments of the present invention, and it does not limit the protection scope of the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any changes, modifications, substitutions, integrations, and parameter changes made to these embodiments by conventional substitutions or capable of achieving the same functions without departing from the principle and spirit of the present invention fall within the protection scope of the present invention.
Claims
1. A Fenton-like catalyst derived from a polymer adsorbent, characterized in that: The catalyst is a Cu@C carbon-based Fenton catalyst.
2. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 1, characterized in that: The following steps are involved: Step S1, weighing N-methyldiallyl ammonium chloride, allyl chloride and acetone, and stirring to prepare a crosslinking agent TAMAC; Step S2, weighing acrylic acid, crosslinking agent TAMAC, ammonium persulfate and deionized water, heating and stirring to react to prepare intermediate PAGH; Step S3, using a sodium hydroxide solution to wash the intermediate PAGH to prepare the adsorbent PAG; Step S4, adding the adsorbent PAG into the copper sulfate solution, stirring and adsorbing to equilibrium; filtering the adsorbent and drying to obtain PAG-Cu; Step S5: placing PAG-Cu in a tubular furnace and calcining at high temperature in a nitrogen atmosphere to obtain a Cu@C carbon-based Fenton-type catalyst.
3. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 2, characterized in that: In the step S1, the mass ratio of the N-methyldiallyl ammonium chloride, allyl chloride and acetone is 3-5:2-4:4-6.
4. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 2, characterized in that: In the step S2, the mass ratio of acrylic acid, crosslinking agent TAMAC, ammonium persulfate and deionized water is 5-7:0.5-2:1-3:8-12.
5. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 2, characterized in that: In step S2, the heating and stirring reaction temperature is 50-90°C.
6. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 5, characterized in that: In step S2, the heating and stirring reaction time is 10 to 50 hours.
7. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 2, characterized in that: In step S4, the concentration of copper ions in the copper sulfate solution is 200-2000 mg / L.
8. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 2, characterized in that: In the step S5, the high temperature calcination temperature is 12 to 36 hours.
9. The method for preparing a Fenton-like catalyst derived from a polymer adsorbent according to claim 8, characterized in that: In step S5, the high temperature calcination time is 2 to 5 hours.