Using a single-clamp phase W 18 O 49 Methods for Fenton-like catalysts to degrade acetaminophen in water

Abstract

This invention discloses a method using a single-clinic phase W 18 O 49 A method for co-catalyzing Fenton degradation of acetaminophen in water, including the use of monoclinic W 18 O 49 A catalyst and a Fenton-like system are added to water containing acetaminophen to catalytically degrade the acetaminophen in the water. The Fenton-like system is composed of hydrogen peroxide and iron ions, where the iron ions are either ferric (Fe3+) or a mixture of ferric (Fe3+) and ferrous (Fe2+) ions. The monoclinic phase W... 18 O 49 The catalyst is prepared by heat treatment of a mixture of tungsten chloride and anhydrous ethanol. The method of this invention has advantages such as simple process, convenient operation, high processing efficiency, high oxidation activity, good reusability, and environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of advanced oxidation treatment of environmental pollutants, specifically relating to a method utilizing monoclinic W 18 O 49 A method for the degradation of acetaminophen in water by Fenton catalysts. Background Technology

[0002] Pharmaceuticals and personal care products (PPCPs) are closely related to human activities and have a wide range of applications. Acetaminophen, as a typical antipyretic and analgesic drug, has gained increasing popularity in clinical treatment and personal health maintenance in recent years. However, due to limitations of traditional wastewater treatment methods, wastewater containing acetaminophen can flow into surface water and groundwater systems through hospital drainage, industrial wastewater, and even wastewater treatment plants, subsequently causing ecotoxicity to humans, animals, and plants through biomigration. Therefore, treating acetaminophen-containing wastewater is of scientific significance for restoring the natural aquatic environment.

[0003] Fenton and / or Fenton-like systems, which release •OH through the decomposition of hydrogen peroxide, are the most widely used and common advanced oxidation processes. However, the traditional Fenton reaction relies excessively on the reaction between ferrous ions and hydrogen peroxide due to the low reaction rate of ferric ions with hydrogen peroxide. This results in excessive ferric ion production, leading to iron sludge formation and catalyst poisoning. Furthermore, the conversion between ferric and ferrous ions in the traditional system is severely limited, resulting in incomplete decomposition of hydrogen peroxide. Therefore, addressing the rate-limiting step in the Fenton reaction and accelerating hydrogen peroxide decomposition has been a key concern. Current methods for accelerating ferrous ion regeneration mainly focus on organic cocatalysts and metal sulfides. However, organic catalysts self-decompose under the induction of •OH, and sulfur vacancies on the surface of metal sulfides trap hydrogen ions to form toxic hydrogen sulfide, causing secondary pollution. Therefore, there is an urgent need to develop a green and stable inorganic cocatalyst to achieve effective ferrous ion regeneration and efficient hydrogen peroxide decomposition, which is of practical significance for realizing environmental and economic benefits. Summary of the Invention

[0004] The technical problem to be solved by this invention is to overcome the shortcomings of the prior art and provide a method that utilizes monoclinic W, which is simple to process, easy to operate, has high processing efficiency, high oxidation activity, good reusability, and is environmentally friendly. 18 O 49 A method for the degradation of acetaminophen in water by Fenton catalysts.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution.

[0006] A method utilizing a single-clinic phase W 18 O 49A method for co-catalyzing Fenton degradation of acetaminophen in water includes the following steps: [The text abruptly shifts to a seemingly unrelated topic about a monoclinic phase W]. 18 O 49 A catalyst and a Fenton-like system are added to water containing acetaminophen to catalytically degrade the acetaminophen in the water. The Fenton-like system is composed of hydrogen peroxide and iron ions, wherein the iron ions are ferric ions or a mixture of ferric and ferrous ions. The monoclinic phase W... 18 O 49 The catalyst is prepared by heat treatment of a mixture of tungsten chloride and anhydrous ethanol at a temperature of 150℃ to 300℃, and the initial pH of the water containing acetaminophen is 3 to 10.

[0007] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the Fenton-type co-catalytic degradation of acetaminophen in water, the monoclinic phase W 18 O 49 The catalyst preparation process includes the following steps:

[0008] S1. Mix tungsten chloride and anhydrous ethanol, and sonicate to obtain a mixture;

[0009] S2. The above mixture is subjected to heat treatment to obtain monoclinic phase W. 18 O 49 .

[0010] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the Fenton-assisted degradation of acetaminophen in water, the ratio of tungsten chloride to anhydrous ethanol in step S1 is 0.3g-0.5g:40mL-70mL, and the ultrasonic treatment time is 5min-15min.

[0011] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the Fenton-assisted degradation of acetaminophen in water, the heat treatment time in step S2 is 8h to 12h.

[0012] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the Fenton-assisted degradation of acetaminophen in water, the heat treatment temperature in step S2 is 180℃~220℃.

[0013] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the Fenton-type co-catalytic degradation of acetaminophen in water, the monoclinic phase W 18 O49 The ratio of catalyst to the water containing acetaminophen is 0.2g to 0.4g:1L, the ratio of hydrogen peroxide to the water containing acetaminophen is 0.5mmol to 5mmol:1L, and the ratio of iron ions to the water containing acetaminophen is 0.1mmol to 2mmol:1L.

[0014] The above-mentioned use of monoclinic phase W 18 O 49 In a method for co-catalyzing Fenton degradation of acetaminophen in water, preferably, the source of the ferric ions includes ferric sulfate and / or ferric chloride.

[0015] The above-mentioned use of monoclinic phase W 18 O 49 In a preferred method for the catalytic degradation of acetaminophen in water by Fenton catalyst, the temperature of the catalytic degradation reaction is 20℃~30℃, and the time of the catalytic degradation reaction is 5min~10min.

[0016] The above-mentioned use of monoclinic phase W 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, preferably wherein the initial concentration of acetaminophen in the water containing acetaminophen is 2.5 mg / L to 10 mg / L.

[0017] The above-mentioned use of monoclinic phase W 18 O 49 A preferred method for the Fenton-based co-catalytic degradation of acetaminophen in water includes the following steps: [The text abruptly shifts to a seemingly unrelated topic about a monoclinic phase W]. 18 O 49 The catalyst was added to the water containing acetaminophen, and the reaction temperature was controlled at 20℃~30℃. After the adsorption-desorption equilibrium was reached, a Fenton-like system was added to carry out the catalytic degradation reaction, thereby achieving the degradation of acetaminophen in the water.

[0018] In this invention, a single-clinic phase W is used. 18 O 49 As a transition metal oxide, W is widely used in photocatalysis, electrocatalysis, and batteries due to its excellent chemical stability, ideal adsorption and oxidation properties, and abundant oxygen vacancies. In fact, W... 18 O 49 Containing both tetravalent and hexavalent tungsten, it can promote the ferric / ferrous ion cycle through efficient electron transfer, generating more •OH for pollutant degradation; in addition, W 18 O 49 The abundant oxygen vacancies on the surface have the potential to accelerate the decomposition of hydrogen peroxide and enhance the adsorption of iron ions, thereby accelerating the ferrotungsten reaction. Therefore, W possesses unique properties... 18 O49 It could be a promising Fenton and / or Fenton-like cocatalyst.

[0019] Compared with the prior art, the advantages of the present invention are as follows:

[0020] In existing technologies, organic cocatalysts are prone to self-decomposition induced by •OH in Fenton-like processes, and metal sulfide cocatalysts easily form toxic hydrogen sulfide. To address these technical shortcomings, this invention proposes utilizing monoclinic W... 18 O 49 The present invention employs a monoclinic phase W-type catalyst for the Fenton-like degradation of acetaminophen in water. 18 O 49 The catalyst is prepared by simple hydrothermal pyrolysis of tungsten chloride. The monoclinic W of this invention... 18 O 49 The catalyst contains abundant oxygen vacancies and tungsten in mixed valence states, which accelerates the adsorption of iron ions, the regeneration of ferrous ions, and the activation of hydrogen peroxide through effective electron transfer, thereby achieving efficient degradation of acetaminophen. In this invention, W 18 O 49 / Fe 3+ / H2O2 achieved a 94% degradation rate of acetaminophen within 5 minutes, with a reaction rate of Fe 3+ / H2O2 is 4.3 times stronger, and the dual driving force of enhanced oxidation activity is W 4+ / W 6+ Fe of change control 2+ / Fe 3+ This method accelerates the cycle and stabilizes the intermediate •OH group via oxygen vacancies, thereby promoting the generation of more free radicals from the breaking of the OO bond in H₂O₂. In particular, this method achieves ideal acetaminophen degradation rates over a wide pH range, effectively overcoming the limitations of the traditional Fenton reaction (pH=2-4) under alkaline conditions. The method of this invention utilizes a monoclinic phase W 18 O 49 The catalyst effectively co-catalyzes the Fenton-like system, thereby efficiently degrading acetaminophen. It has the advantages of simple process, convenient operation, wide pH range, fast degradation efficiency and good removal effect. It is a stable and environmentally friendly method with practical significance for wastewater treatment in the environment. Attached Figure Description

[0021] Figure 1 The monoclinic phase W obtained in Embodiment 1 of the present invention 18 O 49 TEM image of the catalyst.

[0022] Figure 2 The monoclinic phase W obtained in Embodiment 1 of the present invention 18 O49 XRD pattern of the catalyst.

[0023] Figure 3 The monoclinic phase W obtained in Embodiment 1 of the present invention 18 O 49 The degradation effect of Fenton catalyst-assisted degradation of acetaminophen.

[0024] Figure 4 Different Fe in Embodiment 2 of the present invention 3+ Add quantity to single oblique phase W 18 O 49 The degradation effect of Fenton catalyst-assisted degradation of acetaminophen.

[0025] Figure 5 Monoclinic phase W under different hydrogen peroxide addition amounts in Example 3 of this invention 18 O 49 The degradation effect of Fenton catalyst-assisted degradation of acetaminophen.

[0026] Figure 6 The monoclinic phase W under different pH conditions in Example 4 of this invention 18 O 49 The degradation effect of Fenton catalyst-assisted degradation of acetaminophen.

[0027] Figure 7 In Embodiment 5 of the present invention, the single-clinic phase W 18 O 49 In the process of catalyst-co-catalysis, iron ions (Fe) are involved in Fenton-like processes. 3+ The consumption rate of ).

[0028] Figure 8 In Embodiment 5 of the present invention, the single-clinic phase W 18 O 49 In the process of catalyst-co-catalysis similar to Fenton, ferrous ions (Fe) 2+ The generation rate of ).

[0029] Figure 9 The monoclinic phase W in Embodiments 1 and 6 of this invention 18 O 49 XPS spectra of W4f before and after the catalyst reaction. Detailed Implementation

[0030] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention. All materials and instruments used in the following embodiments are commercially available. mM refers to mmol / L.

[0031] Example 1

[0032] The present invention utilizes a monoclinic phase W18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water using a co-catalyst includes the following steps:

[0033] Weigh 30mg of monoclinic phase W 18 O 49 The catalyst was added to 100 mL of a 5 mg / L acetaminophen solution with an initial pH of 5.8. The temperature was maintained at 25°C using a low-temperature circulating water system, and the mixture was stirred for 30 min to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to achieve a H₂O₂ concentration of 1 mM and a Fe₂(SO₄)₃ concentration of 1 mM. 3+ The concentration of 0.5 mM was used to carry out the catalytic degradation reaction for 5 minutes to complete the degradation of acetaminophen in the water.

[0034] During the catalytic degradation reaction, 1 mL of the reaction solution was taken at time points of 0 min (adsorption 30 min), 1 min, 2 min, 3 min, 4 min, and 5 min, filtered through a 0.22 μm filter, and added to a liquid chromatography vial containing 0.5 mL of anhydrous methanol solution. The concentration of acetaminophen in the solution was detected by liquid chromatography.

[0035] Control experiment:

[0036] W 18 O 49 / H2O2 group: Fe2(SO4)3 is not added, and other conditions are the same.

[0037] W 18 O 49 / Fe 3+ Group: No H2O2 added, all other conditions are the same.

[0038] Fe 3+ / H2O2 group: No catalyst added, all other conditions are the same.

[0039] W 18 O 49 Group: Add only W 18 O 49 Without adding H2O2 and Fe2(SO4)3, all other conditions remain the same.

[0040] H2O2 group: No catalyst or Fe2(SO4)3 was added, and all other conditions were the same.

[0041] Fe 3+ Group: No catalyst or H2O2 added, all other conditions are the same.

[0042] In this embodiment, a single-slant phase W is used. 18 O49 The catalyst preparation method includes the following steps:

[0043] (1) Weigh 0.405g of tungsten chloride and add it to 60mL of anhydrous ethanol. Disperse it by sonication for 10min to completely dissolve it and obtain a yellow transparent solution.

[0044] (2) The above yellow transparent solution was transferred to a high-pressure reactor lined with polytetrafluoroethylene. The reactor was placed in a forced-air drying oven and heat-treated at 200°C for 10 hours. After natural cooling, it was taken out, filtered, washed, and dried. The dried product was then ground to obtain the monoclinic phase W. 18 O 49 Catalyst, named W 18 O 49 .

[0045] Figure 1 The monoclinic phase W prepared in Example 1 18 O 49 TEM image of the catalyst. From Figure 1 From this, we can see that the monoclinic phase W 18 O 49 It exhibits a microrod structure, and in magnified HRTEM images, lattice fringes were measured at 0.370 nm and 0.364 nm, consistent with monoclinic W... 18 O 49 The (010) crystal planes correspond well.

[0046] Figure 2 The monoclinic phase W prepared in Example 1 18 O 49 Catalyst (W) 18 O 49 XRD pattern of ). From Figure 2 From this, we can see that the monoclinic phase W 18 O 49 The positions and relative relationships of the diffraction peaks of the catalyst agree well with the standard card, indicating that the monoclinic W of the present invention... 18 O 49 The main phase composition of the catalyst is monoclinic W. 18 O 49 Furthermore, the (010) diffraction peak is strong and sharp, indicating that the monoclinic phase W of the present invention... 18 O 49 The structure of the catalyst mainly develops along the (010) direction.

[0047] Figure 3 The monoclinic phase W prepared in Example 1 18 O 49 A graph showing the degradation effect of acetaminophen on Fenton catalysts (as co-catalysts). From... Figure 3 It can be known that Fe 3+Group, H2O2 group, W 18 O 49 Group, W 18 O 49 / Fe 3+ Group, W 18 O 49 In the H2O2 group, the degradation rate of acetaminophen in all five groups was very low (maximum 20%) within 5 minutes. 3+ The / H2O2 group can degrade ~50% of acetaminophen. And in W... 18 O 49 / Fe 3+ In the / H2O2 system, W 18 O 49 It can effectively co-catalyze Fenton-like reactions, resulting in a 94% degradation rate of acetaminophen within 5 minutes. Therefore, W... 18 O 49 The addition of [a substance] can accelerate the iron cycle and promote the decomposition of hydrogen peroxide, thereby greatly improving the degradation rate of acetaminophen.

[0048] In summary, at an initial pH of 5.8 and an H₂O₂ concentration of 1 mM, Fe 3+ Under the conditions of a concentration of 0.5 mM and a catalyst dosage of 0.3 g / L, W 18 O 49 It exhibits excellent catalytic performance, degrading 94% of acetaminophen within 5 minutes. Therefore, the monoclinic W of this invention... 18 O 49 Catalyst (W) 18 O 49 It can achieve efficient removal of acetaminophen.

[0049] Example 2

[0050] Examining different Fe 3+ The effect of the amount added on the degradation effect of acetaminophen was specifically investigated using monoclinic W... 18 O 49 The Fenton catalyst-assisted degradation of acetaminophen in water includes the following steps:

[0051] Weigh out 5 portions of 30mg of monoclinic phase W from Example 1 18 O 49 The catalyst was added to 100 mL and 5 mg / L acetaminophen solutions, respectively. The initial pH of the solution was 5.8. The temperature was maintained at 25 °C using a low-temperature circulating water device, and the mixture was stirred for 30 min to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to ensure that the concentration of H₂O₂ in the system was 1 mM and the concentration of Fe₂(SO₄)₃ was 1 mM. 3+The concentrations of acetaminophen were 0.1 mM, 0.3 mM, 0.5 mM, 1 mM and 2 mM, respectively, and the catalytic degradation reaction was carried out for 5 min to complete the degradation of acetaminophen in the water.

[0052] Figure 4 For different Fe in Example 2 3+ Add quantity to single oblique phase W 18 O 49 A graph showing the degradation effect of acetaminophen on Fenton catalysts (as co-catalysts). From... Figure 4 From this, we can know that when Fe 3+ Increasing the concentration from 0.1 mmol / L to 2 mmol / L did not initially increase the degradation efficiency of acetaminophen; instead, it remained constant. This may be because the limited number of active catalyst sites and the inability of hydrogen peroxide to simultaneously react with excess Fe2+ 3+ A reaction occurs.

[0053] Example 3

[0054] The effect of different amounts of hydrogen peroxide added on the degradation of acetaminophen was investigated, specifically using monoclinic W... 18 O 49 The Fenton catalyst-assisted degradation of acetaminophen in water includes the following steps:

[0055] Weigh out 3 portions of 30mg of monoclinic phase W from Example 1 18 O 49 The catalyst was added to 100 mL and 5 mg / L acetaminophen solutions, respectively. The initial pH of the solution was 5.8. The temperature was maintained at 25 °C using a low-temperature circulating water device, and the mixture was stirred for 30 min to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to make the concentrations of H₂O₂ in the system 1 mM, 3 mM, and 5 mM, respectively. 3+ The concentration of each substance was 0.5 mM, and the catalytic degradation reaction was carried out for 5 minutes to complete the degradation of acetaminophen in the water.

[0056] Figure 5 Monoclinic phase W under different hydrogen peroxide addition amounts in Example 3 of this invention 18 O 49 A graph showing the degradation effect of acetaminophen on Fenton catalysts (as co-catalysts). From... Figure 5 It can be seen that when the amount of hydrogen peroxide increases from 1 mmol / L to 5 mmol / L, the degradation efficiency of acetaminophen first increases slightly and then decreases. This may be attributed to the fact that excess hydrogen peroxide captures •OH to form H2O and •O2H, which hinders the oxidative degradation of acetaminophen.

[0057] Example 4

[0058] The effect of different pH values ​​on the degradation of acetaminophen was investigated, specifically using monoclinic W 18 O 49 The Fenton catalyst-assisted degradation of acetaminophen in water includes the following steps:

[0059] Take four portions of acetaminophen solution, each with a concentration of 5 mg / L and a volume of 100 mL. Adjust the pH of the four acetaminophen solutions to 3, 5, 7, and 10 respectively using 0.1 mol / L hydrochloric acid and sodium hydroxide solution. Add 30 mg of the monoclinic phase W from Example 1 to each portion. 18 O 49 The catalyst was maintained at 25°C using a low-temperature circulating water system and stirred for 30 minutes to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to achieve a H₂O₂ concentration of 1 mM and a Fe₂(SO₄)₃ concentration of 1 mM. 3+ The concentration of 0.5 mM was used to carry out the catalytic degradation reaction for 5 minutes to complete the degradation of acetaminophen in the water.

[0060] During the catalytic degradation reaction, 1 mL of the reaction solution was taken at time points of 0 min (adsorption 30 min), 1 min, 2 min, 3 min, 4 min, and 5 min, filtered through a 0.22 μm filter, and added to a liquid chromatography vial containing 0.5 mL of anhydrous methanol solution. The concentration of acetaminophen in the solution was detected by liquid chromatography.

[0061] Figure 6 The monoclinic phase W under different pH conditions in Example 4 of this invention 18 O 49 A graph showing the degradation effect of acetaminophen on Fenton catalysts (as co-catalysts). From... Figure 6 It can be seen that the W of the present invention 18 O 49 Under conditions of pH values ​​of 3, 5, 5.8 (initial pH), 7, and 10, the removal rates of acetaminophen were 76.3%, 96.9%, 94%, 75.83%, and 68.3%, respectively. 18 O 49 The degradation of acetaminophen was enhanced at pH 5, indicating that acidic conditions were more suitable for the Fenton-like system. However, when the pH continued to decrease to 3, the removal rate of acetaminophen was partially inhibited, because hydrogen peroxide captured excess hydrogen ions (H₂O). + H3O2 is formed + This inhibits the normal decomposition of hydrogen peroxide; in addition, hydrogen peroxide reacts with H+. +The water generated in the reaction also consumes some •OH, hindering the oxidative degradation of acetaminophen. However, the degradation efficiency of acetaminophen is above 68% within the pH range of this invention, indicating that the monoclinic W phase in this invention... 18 O 49 catalyst and Fe 3+ The degradation system constructed with / H2O2 has a wide applicable pH range.

[0062] Example 5

[0063] Examining the monoclinic phase W in this invention 18 O 49 The effect of catalyst-co-catalyst-based Fenton systems on iron cycling includes the following steps:

[0064] Weigh out two 30mg portions of monoclinic phase W from Example 1. 18 O 49 The catalyst was added to 100 mL of deionized water, and the temperature was maintained at 25 °C using a low-temperature circulating water device. The mixture was stirred for 30 min to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to make the concentration of H₂O₂ in the system 1 mM and Fe₂(SO₄)₃... 3+ The concentration was 0.5 mM, and the catalytic reaction was carried out for 5 min.

[0065] During the catalytic reaction, 2 mL of reaction solution was taken at time points of 0 min (adsorption 30 min), 0.5 min, 1 min, 2 min, 3 min, 4 min, and 5 min. The solution was filtered through a 0.22 μm filter and added to colorimetric tubes. The concentration of ferrous ions (Fe2+) in the solution was detected using a UV spectrophotometer. 2+ ) and iron ions (Fe 3+ The concentration of ).

[0066] Figure 7 In Example 5, the single-clinic phase W 18 O 49 In the process of catalyst-co-catalysis, iron ions (Fe) are involved in Fenton-like processes. 3+ The consumption rate of ). Figure 7 It can be known that Fe 3+ The H2O2 system only consumed approximately 20% of the Fe. 3+ And joining W 18 O 49 After that, Fe 3+ After being rapidly consumed to about 70%, it tends to stabilize, indicating that the monoclinic phase W... 18 O 49 Catalysts participate in Fe 2+ / Fe 3+ A cyclical process.

[0067] Figure 8In Example 5, the single-clinic phase W 18 O 49 In the process of catalyst-co-catalysis similar to Fenton, ferrous ions (Fe) 2+ The generation rate of ). From Figure 8 It can be seen that W 18 O 49 / Fe 3+ The H2O2 system rapidly generated ~50% Fe within 0.5 min. 2+ It is Fe 3+ The W / H2O2 system is more than 4 times larger, which indicates that the monoclinic phase W 18 O 49 The addition of the catalyst effectively promoted the regeneration of ferrous ions and ensured the Fe... 2 + / Fe 3+ Stable operation of the cycle.

[0068] Example 6

[0069] Examining the monoclinic phase W in this invention 18 O 49 The valence state change of metallic tungsten before and after the catalytic reaction includes the following steps:

[0070] Weigh 30 mg of monoclinic phase W from Example 1 18 O 49 The catalyst was added to 100 mL of a 5 mg / L acetaminophen solution with an initial pH of 5.8. The temperature was maintained at 25°C using a low-temperature circulating water system, and the mixture was stirred for 30 min to reach adsorption-desorption equilibrium. Then, hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) were added to achieve a H₂O₂ concentration of 1 mM and a Fe₂(SO₄)₃ concentration of 1 mM. 3+ The concentration was 0.5 mM, and the catalytic degradation reaction was carried out for 5 minutes to complete the degradation of acetaminophen in the water. The resulting monoclinic phase W... 18 O 49 The catalyst was filtered, washed, and dried. The dried product was then ground to obtain the monoclinic phase W after the reaction. 18 O 49 catalyst.

[0071] Figure 9 The monoclinic phase W in Embodiments 1 and 6 of this invention 18 O 49 XPS spectra of W4f before and after the catalyst reaction. Figure 9 It can be seen that W after the reaction 18 O 49 Belongs to W 4+ The peak intensities of the two peaks decreased significantly, indicating that Fe 3+ Reduced to Fe 2+ At the same time W 4+ Oxidized to W 6+ Subsequently, hydrogen peroxide further... 6+ Restore to W 4+ This ensured W 18 O 49 Cyclic co-catalysis. Furthermore, compared to traditional tungsten co-catalysts, in W... 18 O 49 W participating in the reaction 6+ Not only from W 4+ The oxidation process also comes from W 18 O 49 It contains a large amount of W 6+ This promoted W 4+ The regeneration of the system accelerates the entire system's cycle.

[0072] In summary, the present invention utilizes a single-clinic phase W 18 O 49 The method of using catalyst-assisted Fenton degradation of acetaminophen in water has the advantages of simple process, convenient operation, high treatment efficiency, wide pH range, good reusability, and environmental friendliness. It can achieve efficient removal of acetaminophen from water, has high application value, and good application prospects.

[0073] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the spirit and technical essence of the present invention. Therefore, any simple modifications, equivalent substitutions, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention shall still fall within the protection scope of the technical solutions of the present invention.

Claims

1. A method utilizing a monoclinic phase W 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... The steps include: converting the single-clinch phase W... 18 O 49 A catalyst and a Fenton-like system are added to water containing acetaminophen to catalytically degrade the acetaminophen in the water. The Fenton-like system is composed of hydrogen peroxide and iron ions, wherein the iron ions are ferric ions or a mixture of ferric and ferrous ions. The monoclinic phase W... 18 O 49 The catalyst is prepared by heat treatment of a mixture of tungsten chloride and anhydrous ethanol at a temperature of 150℃ to 300℃, and the initial pH of the water containing acetaminophen is 3 to 10. The monoclinic phase W 18 O 49 The catalyst preparation process includes the following steps: S1. Mix tungsten chloride and anhydrous ethanol, and sonicate to obtain a mixture; S2. The above mixture is subjected to heat treatment at a temperature of 180℃~220℃ to obtain monoclinic phase W. 18 O 49 ; The method specifically includes the following steps: ... (The sentence is incomplete and requires more context to translate accurately. It appears to be discussing the steps of a single-clamp phase W.) 18 O 49 The catalyst was added to the water containing acetaminophen, and the reaction temperature was controlled at 20℃~30℃. After the adsorption-desorption equilibrium was reached, a Fenton-like system was added to carry out the catalytic degradation reaction, thereby achieving the degradation of acetaminophen in the water. The dual driving force behind the enhanced oxidation activity is W 4+ / W 6+ Fe of change control 2+ / Fe 3+ Accelerated cycling and the stabilization of intermediate •OH by oxygen vacancies promote the generation of more free radicals resulting from the breaking of OO bonds in H2O2.

2. The method of utilizing a monoclinic phase W according to claim 1 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... In step S1, the ratio of tungsten chloride to anhydrous ethanol is 0.3g to 0.5g: 40mL to 70mL, and the ultrasonication time is 5min to 15min.

3. The method of utilizing a monoclinic phase W according to claim 1 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... In step S2, the heat treatment time is 8h to 12h.

4. The method of using a monoclinic phase W according to any one of claims 1 to 3 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... The monoclinic phase W 18 O 49 The ratio of catalyst to the water containing acetaminophen is 0.2g to 0.4g:1L, the ratio of hydrogen peroxide to the water containing acetaminophen is 0.5mmol to 5mmol:1L, and the ratio of iron ions to the water containing acetaminophen is 0.1mmol to 2mmol:1L.

5. The method of using a monoclinic phase W according to any one of claims 1 to 3 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... The sources of the ferric ions include ferric sulfate and / or ferric chloride.

6. The method of using a monoclinic phase W according to any one of claims 1 to 3 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... The temperature of the catalytic degradation reaction is 20℃~30℃, and the time of the catalytic degradation reaction is 5min~10min.

7. The method of using a monoclinic phase W according to any one of claims 1 to 3 18 O 49 A method for the Fenton-assisted degradation of acetaminophen in water, characterized in that... The initial concentration of acetaminophen in the water containing acetaminophen is 2.5 mg / L to 10 mg / L.

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