Surfactant modified iron-loaded biochar catalyst as well as preparation method and application thereof
Through the thermal solution method of the surface active agent modified iron carbon catalyst, the problem of low catalyst activation efficiency in the existing technology and poor use of poor performance in the existing technology, achieve the effect of antibiotics in high -efficiency degradation water, and show good Repeat performance.
Patent Information
- Application Number
- CN202411480224.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-23
- Publication Date
- 2025-01-24
AI Technical Summary
In the prior art, when using peracetic acid to perform advanced oxidation and degradation of antibiotics in water, the activation efficiency of the catalyst is low, it is difficult to remove difficult-to-degrade organic pollutants, and the reuse performance of the catalyst is poor.
Surfactant-modified iron-loaded biochar catalyst was prepared by pyrolysis method, and tridecyltrimethylammonium bromide was introduced as a template agent to promote the generation of heterogeneous interface and increase the electric field intensity, and strengthen the Fe(II)/ The redox cycle of Fe(III) efficiently activates peracetic acid.
The activation efficiency of the catalyst is significantly improved, and it can efficiently degrade antibiotics in water, especially tetracycline. The catalyst has good reusability and can maintain efficient degradation effects in multiple cycles.
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Figure CN119346109A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of water treatment, and specifically relates to a surfactant-modified iron-loaded biochar catalyst and a preparation method and application thereof. Background Art
[0002] In recent years, antibiotics have been widely used to treat human and animal diseases. However, long-term overuse of antibiotics has led to higher detection frequencies and concentrations in water environments. As the second most widely used antibiotic in the world, tetracycline is difficult to be metabolized by human and animal organisms. Residual tetracycline can be detected in surface water, groundwater and even drinking water through surface runoff or leaching. Therefore, controlling antibiotic contamination in water is of great significance to solving water pollution problems and ensuring the health of drinking water.
[0003] Advanced oxidation technology can utilize highly active free radicals to oxidize and degrade antibiotics in water. The free radical precursor salts that researchers currently focus on include persulfate, ozone, hydrogen peroxide, and peracetic acid. Among them, peracetic acid has gradually attracted the attention of researchers due to its high redox potential and few toxic byproducts. In addition, compared with other oxidants, peracetic acid has a longer peroxy bond and is more prone to breakage during the reaction, so its use as a highly active free radical precursor has significant advantages. However, peracetic acid has weak oxidation ability and low reactivity with organic pollutants, and cannot remove most difficult-to-degrade organic pollutants. Catalysts are usually used to activate peracetic acid to generate highly active free radicals. How to screen and construct efficient catalysts to promote the generation of highly active free radicals is the key to the application of advanced oxidation technology based on peracetic acid.
[0004] At present, advanced oxidation technologies using transition metal ions to activate peracetic acid have attracted widespread attention from researchers. These homogeneous activation systems have the disadvantages of being greatly affected by pH and difficult to recycle catalysts. Iron-based heterogeneous catalysts have the excellent characteristics of low metal ion leaching and good recycling performance, but they have the problem of slow Fe(II) / Fe(III) redox rate. As a traditional carrier, biochar has a stable structure and high electron transfer capacity. The large number of oxygen-containing functional groups on the surface of biochar can also effectively promote electron transfer to a certain extent, accelerate the metal ion redox cycle, and activate peracetic acid. However, its practical application is still limited by the slow transition metal redox cycle rate and the low metal ion utilization rate caused by transition metal agglomeration. Therefore, the development of an iron-loaded biochar catalyst that can enhance Fe(II) / Fe(III) redox and achieve efficient activation of peracetic acid is of great significance for controlling antibiotic pollution in water bodies. Summary of the invention
[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a surfactant-modified iron-loaded biochar catalyst.
[0006] Another object of the present invention is to provide a method for preparing the above-mentioned surfactant-modified iron-loaded biochar catalyst.
[0007] Another object of the present invention is to provide the use of the above-mentioned surfactant-modified iron-loaded biochar catalyst in activating peracetic acid to degrade antibiotics in water.
[0008] The technical solution of the present invention is as follows:
[0009] A surfactant-modified iron-loaded biochar catalyst is prepared from tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder by a pyrolysis method, wherein the mass ratio of tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder is (1-5):(8-12):(8-12).
[0010] In a preferred embodiment of the present invention, the mass ratio of tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder is 2:10:10.
[0011] The preparation method of the surfactant-modified iron-loaded biochar catalyst comprises the following steps:
[0012] (1) dissolving tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder in deionized water in a mass ratio of (1-5):(8-12):(8-12), stirring thoroughly at room temperature, and completely dissolving to obtain a dark yellow precursor mixed solution; the mass ratio of the total mass of tridecyltrimethylammonium bromide and anhydrous ferric chloride to deionized water is 1:(20-30);
[0013] (2) drying the precursor mixed solution in a 90°C to 110°C forced air oven for 18-24 hours, and then cooling it naturally to room temperature;
[0014] (3) The dried material obtained in step (2) is placed in a quartz boat and heated in an atmosphere tube furnace at a heating rate of 3°C / min to 7°C / min to a pyrolysis temperature of 500 to 800°C for 1 h to 3 h to obtain a black powder, which is then ground and sieved to obtain a surfactant-modified iron-loaded biochar catalyst powder with a particle size of less than 200 nm.
[0015] In a preferred embodiment of the present invention, the temperature in step (2) is 600° C. and the time is 2 hours.
[0016] The above surfactant-modified iron-loaded biochar catalyst is used in activating peracetic acid to degrade antibiotics in water.
[0017] In a preferred embodiment of the present invention, the surfactant-modified iron-loaded biochar catalyst is placed in a water body to be treated containing antibiotics, the pH is adjusted to 4-10, and then peracetic acid is added for treatment; in the water body to be treated, the concentration of the surfactant-modified iron-loaded biochar catalyst is 0.005-0.05 g / L, the concentration of the antibiotic is 3-20 μM, and the concentration of the peracetic acid is 30-200 μM.
[0018] More preferably, the antibiotic is tetracycline.
[0019] A method for degrading antibiotics in water comprises: placing the surfactant-modified iron-loaded biochar catalyst in a water body to be treated containing antibiotics, adjusting the pH to 4-10, and then adding peracetic acid for treatment.
[0020] In a preferred embodiment of the present invention, in the water body to be treated, the concentration of the surfactant-modified iron-loaded biochar catalyst is 0.005-0.05 g / L, the concentration of the antibiotic is 3-20 μM, and the concentration of the peracetic acid is 30-200 μM.
[0021] More preferably, the antibiotic is tetracycline.
[0022] Compared with the background technology, this technical solution has the following advantages:
[0023] 1. The surfactant-modified iron-loaded biochar catalyst prepared by the pyrolysis method of the present invention introduces the surfactant tridecyltrimethylammonium bromide as a template agent, and the surfactant is combined with the metal, and the steric hindrance is used to effectively prevent the agglomeration of metal particles, thereby improving the utilization efficiency of the metal.
[0024] 2. The introduction of surfactant tridecyltrimethylammonium bromide promotes the formation of heterogeneous interfaces and significantly increases the electric field strength. Electrons are transferred from the carbon ring to iron oxide, strengthening the redox cycle of Fe(II) / Fe(III), promoting the formation of Fe(II), and efficiently activating peracetic acid.
[0025] 3. The oxygen-containing functional groups on the surface of biochar can accelerate the electron transfer efficiency during the activation process of peracetic acid to a certain extent, promote the regeneration of Fe(II), and combine free radical and non-free radical pathways to more efficiently activate peracetic acid to produce highly active free radicals to degrade antibiotics in water. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is the degradation efficiency curve of tetracycline in the peracetic acid system activated by the surfactant-modified iron-loaded biochar catalyst in Example 1 of the present invention. Among them, CFC / PAA is a modified iron-loaded catalyst; FC / PAA is an unmodified iron-loaded catalyst.
[0027] Figure 2 The degradation efficiency of tetracycline in the surfactant-modified iron-loaded biochar catalyst activated peracetic acid system at different pH values in Example 2 of the present invention.
[0028] Figure 3 This is the tetracycline degradation efficiency curve of the surfactant-modified iron-loaded biochar catalyst activated peracetic acid system in Example 3 of the present invention, which was repeated 1-3 times. DETAILED DESCRIPTION
[0029] The technical solution of the present invention is further illustrated and described below through specific implementation modes in combination with the accompanying drawings.
[0030] Example 1
[0031] (1) Dissolve 0.2 g of tridecyltrimethylammonium bromide, 1 g of anhydrous ferric chloride, and 1 g of corn straw powder in 50 mL of deionized water and stir thoroughly at room temperature until they are completely dissolved to obtain a dark yellow precursor mixed solution.
[0032] (2) drying the precursor mixture in a 100° C. forced air oven for 24 h, and then cooling it naturally to room temperature;
[0033] (3) placing the dried material obtained in step (2) in a quartz boat, heating it in an atmosphere tube furnace at 5°C / min, and pyrolyzing it at 600°C for 2h to obtain a black powder, which was then ground and sieved in a glass grinder to obtain a surfactant-modified iron-loaded biochar catalyst powder with a particle size of less than 200nm;
[0034] (4) The obtained surfactant-modified iron-loaded biochar catalyst (0.01 g / L) was placed in the water to be treated with the antibiotic tetracycline (10 μM), the pH value was adjusted to 7.0, and then peracetic acid (50 μM) was added. The reaction was stirred and sampled at certain reaction time intervals (0, 10, 20, 30, 40, 50, 60, 70 s). Then, the residual antibiotic concentration was determined, and the degradation of tetracycline at different reaction times was plotted ( Figure 1 );
[0035] like Figure 1As shown in the data, the tetracycline content in the treated water body gradually decreased with time. After 70 seconds of reaction, the degradation rate of tetracycline in the system activated by peracetic acid using the surfactant-modified iron-loaded biochar catalyst reached 100%, indicating that the surfactant-modified iron-loaded biochar catalyst prepared by pyrolysis method can efficiently activate peracetic acid to degrade tetracycline. The degradation efficiency of the system activated by peracetic acid to degrade tetracycline using the surfactant-modified iron-loaded biochar catalyst (CFC / PAA) was significantly better than that of the unmodified iron-loaded catalyst (FC / PAA). The addition of tridecyltrimethylammonium bromide promoted the regeneration of Fe(II), accelerated the activation of peracetic acid, and thus promoted the degradation of tetracycline.
[0036] Example 2
[0037] (1) Dissolve 0.2 g of tridecyltrimethylammonium bromide, 1 g of anhydrous ferric chloride, and 1 g of corn straw powder in 50 mL of deionized water, stir thoroughly at room temperature, and completely dissolve to obtain a dark yellow precursor mixed solution.
[0038] (2) drying the precursor mixture in a 100° C. forced air oven for 24 h, and then cooling it naturally to room temperature;
[0039] (3) placing the dried material obtained in step (2) in a quartz boat, heating it in an atmosphere tube furnace at 5°C / min, and pyrolyzing it at 600°C for 2h to obtain a black powder, which was then ground and sieved in a glass grinder to obtain a surfactant-modified iron-loaded biochar catalyst powder with a particle size of less than 200nm;
[0040] (4) The obtained surfactant-modified iron-loaded biochar catalyst (0.01 g / L) was placed in the water body to be treated with the antibiotic tetracycline (10 μM), and the pH value was adjusted to 3.0, 5.0, 7.0, 9.0, and 11.0. Then, peracetic acid (50 μM) was added, and the water sample was taken after stirring for 2 minutes. The remaining antibiotic concentration was then determined, and the degradation of tetracycline at different pH values was plotted ( Figure 2 ).
[0041] like Figure 2 As shown, the ordinate represents the ratio of the remaining amount of tetracycline to the initial amount. The degradation efficiency of tetracycline is almost above 80% under the conditions of pH 4.0-10.0, especially when the pH value is 6.0-9.0, the degradation efficiency can reach 100% within 2 minutes. This shows that the surfactant-modified iron-loaded biochar catalyst prepared by the hydrothermal method can efficiently activate peracetic acid to degrade tetracycline in a wide pH range.
[0042] Example 3
[0043] (1) Dissolve 0.2 g of tridecyltrimethylammonium bromide, 1 g of anhydrous ferric chloride, and 1 g of corn straw powder in 50 mL of deionized water, stir thoroughly at room temperature, and completely dissolve to obtain a dark yellow precursor mixed solution.
[0044] (2) drying the precursor mixture in a 100° C. forced air oven for 24 h, and then cooling it naturally to room temperature;
[0045] (3) placing the dried material obtained in step (2) in a quartz boat, heating it in an atmosphere tube furnace at 5°C / min, and pyrolyzing it at 600°C for 2h to obtain a black powder, which was then ground and sieved in a glass grinder to obtain a surfactant-modified iron-loaded biochar catalyst powder with a particle size of less than 200nm;
[0046] (4) placing the obtained catalysts (1), (2) and (3) (0.01 g / L) in a water body to be treated containing an antibiotic, tetracycline (10 μM), adjusting the pH value to 7.0, then adding peracetic acid (50 μM), stirring the reaction, sampling at certain reaction time intervals (0, 10, 20, 30, 40, 50, 60, 70 s), and then determining the residual antibiotic concentration;
[0047] (5) After the reaction, the surfactant-modified iron-loaded biochar catalyst was taken out, rinsed with deionized water and ethanol, dried in a blower dryer, ground and sieved, and added to a new water body containing tetracycline to be treated (tetracycline concentration: 10 μM; pH: 7.0; peracetic acid: 50 μM), stirred for reaction, and samples were taken at certain reaction time intervals (0, 10, 20, 30, 40, 50, 60, 70 s) to determine the remaining antibiotic concentration; this method was repeated 3 times. Plot the tetracycline degradation effect curve ( Figure 3 );
[0048] like Figure 3 As shown, the ordinate represents the ratio of the remaining amount of tetracycline to the initial amount. After recycling three times, the tetracycline degradation efficiency can still reach 80% within 2 minutes. The surfactant-modified iron-loaded biochar catalyst has a good effect on degrading tetracycline by repeated recycling, indicating that the surfactant-modified iron-loaded biochar catalyst can be reused many times.
[0049] The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.
Claims
1. A surfactant-modified iron-loaded biochar catalyst, characterized in that: The invention is prepared by thermal decomposition of tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder, wherein the mass ratio of tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder is (1-5):(8-12):(8-12).
2. The method for preparing a surfactant-modified iron-loaded biochar catalyst according to claim 1, characterized in that: The steps include: (1) dissolving tridecyltrimethylammonium bromide, anhydrous ferric chloride and corn straw powder in deionized water in a mass ratio of (1-5):(8-12):(8-12), stirring thoroughly at room temperature, and completely dissolving to obtain a dark yellow precursor mixed solution; the mass ratio of the total mass of tridecyltrimethylammonium bromide and anhydrous ferric chloride to deionized water is 1:(20-30); (2) drying the precursor mixed solution in a 90°C to 110°C forced air oven for 18-24 hours, and then cooling it naturally to room temperature; (3) The dried material obtained in step (2) is placed in a quartz boat and heated in an atmosphere tube furnace at a heating rate of 3°C / min to 7°C / min to a pyrolysis temperature of 500 to 800°C for 1 h to 3 h to obtain a black powder, which is then ground and sieved to obtain a surfactant-modified iron-loaded biochar catalyst powder with a particle size of less than 200 nm.
3. The method for preparing a surfactant-modified iron-loaded biochar catalyst according to claim 1, characterized in that: The pyrolysis temperature in step (3) is 600° C. and the time is 2 h.
4. Use of the surfactant-modified iron-loaded biochar catalyst according to any one of claims 1 to 3 in activating peracetic acid to degrade antibiotics in water.
5. The use according to claim 4, characterized in that: The method comprises placing the surfactant-modified iron-loaded biochar catalyst in a water body to be treated containing antibiotics, adjusting the pH to 4-10, and then adding peracetic acid for treatment; in the water body to be treated, the concentration of the surfactant-modified iron-loaded biochar catalyst is 0.005-0.05 g / L, the concentration of the antibiotic is 3-20 μM, and the concentration of the peracetic acid is 30-200 μM.
6. The use according to claim 4, characterized in that: The antibiotic is tetracycline.
7. A method for degrading antibiotics in water, comprising: The surfactant-modified iron-loaded biochar catalyst according to claim 1, 2 or 3 is placed in a water body to be treated containing antibiotics, the pH is adjusted to 4-10, and then peracetic acid is added for treatment.
8. A method for degrading antibiotics in water according to claim 7, characterized in that: In the water body to be treated, the concentration of the surfactant-modified iron-loaded biochar catalyst is 0.005-0.05 g / L, the concentration of the antibiotic is 3-20 μM, and the concentration of the peracetic acid is 30-200 μM.
9. A method for degrading antibiotics in water according to claim 7, characterized in that: The antibiotic is tetracycline.