Treating agent applied to organic pollutants and preparation method thereof

Abstract

The invention relates to a treating agent applied to organic pollutants and a preparation method thereof, and the preparation method comprises the following steps: mixing thiourea, ferric salt, cobalt salt and an ethylene glycol aqueous solution, carrying out a hydrothermal method to obtain the treating agent applied to the organic pollutants, and activating persulfate to treat the organic pollutants, due to the addition of sulfur, the catalyst can be used for efficiently treating organic pollutants in wastewater. According to the treating agent applied to the organic pollutants, the preparation method is simple, the raw material cost is low, the prepared treating agent applied to the organic pollutants is applied to degradation of the organic pollutants, the concentration of the organic pollutants in waste water can be effectively reduced, in addition, the treating agent applied to the organic pollutants is easy to operate, and the cost is low. The method can be applied in large scale and has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, specifically relating to a treatment agent for organic pollutants and its preparation method. Background Technology

[0002] Water is one of the essential environments for human survival. With population growth, industrial demands, and improved living standards, the demand for water continues to increase. Currently, water scarcity and water environment safety and quality have become major global concerns. my country faces water scarcity, with per capita water availability currently only one-quarter of the world average, and water pollution is relatively severe. The Yellow River, as one of my country's major water resources, receives up to 923 million cubic meters of various pollutants annually, with the main pollutant inflow amounting to approximately 424,000 tons per year, primarily organic pollutants. Furthermore, these organic pollutants in the aquatic environment typically possess multiple stable benzene ring structures and contain various groups such as hydroxyl, nitro, and halogen groups. They are difficult to degrade in aquatic environments and are highly toxic; organic dyes and antibiotics are typical examples.

[0003] Currently, common methods for treating organic pollutants include physical, chemical, and biological methods. Physical methods, such as adsorption, can quickly remove some pollutants, but they suffer from problems such as the need for regeneration or replacement of adsorbents after saturation and limited treatment efficiency. Biological methods, while having the advantage of being green and environmentally friendly, have long treatment cycles and strong selectivity for pollutants, making them difficult to handle complex and variable organic pollutant systems. Advanced oxidation technologies in chemical methods, such as persulfate-based oxidation systems, have attracted widespread attention due to their strong oxidizing power and wide applicability. However, these systems usually require highly efficient catalysts to activate persulfate to generate strong oxidizing free radicals, thereby achieving the degradation of organic pollutants. But existing catalysts often suffer from drawbacks such as complex preparation processes, expensive raw materials, harsh reaction conditions, low catalytic activity, and difficulty in recycling, which limit their large-scale application and promotion. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a treatment agent for organic pollutants and its preparation method. This treatment agent is prepared through simple steps using common raw materials under mild reaction conditions, and possesses highly efficient catalytic performance and is recyclable and reusable, thus achieving economical, efficient, and environmentally friendly treatment of organic pollutants.

[0005] To achieve the above objectives, the present invention provides the following technical solution: An agent for treating organic pollutants is composed of a porous iron-cobalt sulfide catalyst and persulfate in a mass ratio of 1:10 to 1:62. The porous iron-cobalt sulfide catalyst is prepared by synergistic regulation of iron and cobalt bimetals using thiourea as a bifunctional reagent of "sulfur source-soft template". The total molar ratio of metal elements to thiourea is 4.36 to 5:1, and it has a through-type multi-level pore structure. In the porous iron-cobalt sulfide catalyst, iron is present in the form of Fe. 3+ / Fe 2+ Cobalt exists in both valence states, with Co being the most common. 3+ / Co 2+ Valence states coexist, forming an Fe-Co-S electron transfer network.

[0006] A method for preparing an agent for treating organic pollutants, comprising the following preparation steps: S1. Dissolve 5 mmol of iron salt and 0.45~1.25 mmol of cobalt salt in 30~60 mL of solvent, and ultrasonically disperse for 10~15 min to form a metal ion mixture; wherein the iron salt is at least one of ferric chloride, ferric sulfate, and ferric nitrate, and the cobalt salt is at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, and the solvent is ethylene glycol; S2. Add a solution containing 1.25 mmol of thiourea to the metal ion mixture and stir for 20-40 min to allow the thiourea to pre-coordinate with the metal ions, thus obtaining the reaction precursor solution; S3. The reaction precursor liquid is placed in a closed reaction vessel and hydrothermally reacted at 160~240℃ for 8~12h. The NH3 and CS2 gases generated by the pyrolysis of thiourea are used to construct a porous template in situ, and iron-cobalt sulfide is generated simultaneously. S4. The hydrothermal product was centrifuged and washed until the supernatant pH was 6.5-7.5, and dried at 60-80℃ for 24-30 h to obtain a porous iron-cobalt sulfide catalyst. S5. The porous iron-cobalt sulfide catalyst is mixed with persulfate at a mass ratio of 1:10 to 1:62 to obtain the organic pollutant treatment agent.

[0007] The preparation of this treatment agent uses thiourea as a soft template agent, which is volatilized and sacrificed during pyrolysis. The decomposition of thiourea provides pore "templates" (gas bubbles or molecular aggregates). Hydrothermal conditions, by regulating reaction kinetics and thermodynamics, ensure that the pores formed by these templates can be stably retained in the material, ultimately forming a porous structure with specific pore size and morphology, and possessing a through-type hierarchical pore structure. The porous iron-cobalt sulfide catalyst increases the specific surface area, providing abundant active sites and enhancing catalytic activity. The pores accelerate the mass transfer of reactants, improving reaction efficiency. The synergistic effect of iron and cobalt optimizes the electronic structure, effectively improving the selectivity of the catalyst.

[0008] Iron salts, as the main active component, provide the basic active sites for the catalytic reaction at a fixed dosage (5 mmol); cobalt salts (0.45~1.25 mmol) regulate electron transfer efficiency by forming a bimetallic system with iron, with iron element taking the form of Fe. 3+ / Fe 2+ Cobalt exists in both valence states, with Co being the most common. 3+ / Co 2+ The valence states coexist, forming an Fe-Co-S electron transfer network. The total metal ion content of both (5.45~6.25 mmol) matches that of thiourea (1.25 mmol), and the sulfur ions (S) of thiourea... 2- ) must satisfy the condition of Fe 3+ / Fe 2+ Co 3+ / Co 2+ The coordination requirements (the molar ratio of metal to sulfur is about 4.36~5:1) are met to ensure the formation of stable iron-cobalt sulfides (such as FeCo2S4, Fe2CoS4, etc.) and to avoid the formation of impurities such as metal hydroxides.

[0009] Meanwhile, the amount of thiourea used (1.25 mmol) needs to be matched with the total amount of metal ions: if there is an excess of metal ions and insufficient thiourea, the sulfurization will be incomplete due to the lack of sulfur source, and the residual free metal ions will block the pores; if there is an excess of thiourea, the excess gas (NH3, CS2) produced by its pyrolysis will destroy the pore structure, and the unreacted thiourea will cover the active sites.

[0010] The catalyst dosage (0.01 g) is designed based on its porous structure and bimetallic synergistic effect. This dosage corresponds to a number of active sites that can efficiently activate 0.1~0.62 g of persulfate to generate sufficient free radicals (·SO4). - 、·OH).

[0011] The dosage range of persulfate (0.1~0.62g) is linked to catalyst activity: when the catalyst exhibits high activity due to its porous structure and bimetallic synergy, a lower persulfate dosage (0.1g) is sufficient to meet the degradation requirements; however, if the persulfate is excessive (exceeding 0.62g), quenching reactions between free radicals (such as SO42-) will occur. - + ·OH →·SO4 2- + H + + O2) reduces efficiency and increases costs. The synergistic combination of the two achieves a highly efficient cycle of "catalyst activation - persulfate decomposition - free radical utilization".

[0012] This is a further improvement on the preparation method of an agent for treating organic pollutants.

[0013] Preferably, in step S2, the stirring speed is 400~600 r / min, and the system temperature is controlled at 25~35℃ during stirring to ensure the reaction of thiourea and Fe. 3+ Co 3+ It forms a stable coordination intermediate, avoiding the formation of metal hydroxide precipitates.

[0014] Preferably, in step S3, the heating rate of the hydrothermal reaction is 2~5℃ / min.

[0015] The present invention also provides an application of an agent for treating organic pollutants.

[0016] A method for applying an agent for treating organic pollutants is as follows: the agent for treating organic pollutants prepared above is added to the organic pollutants simultaneously with persulfate.

[0017] An agent for treating organic pollutants, with the following operating steps: S21. Weigh the organic pollutant treatment agent dried to constant weight. S22. Add to a solution containing organic pollutants, stir at 25±5℃, and test the concentration of organic pollutants in the solution before and after the reaction.

[0018] The advantages of this invention compared to the prior art are as follows: (1) The preparation process is simple and efficient: the hydrothermal method is combined with simple operations such as ultrasound and stirring, without the need for complex equipment. The reaction conditions are mild (such as temperature 160~240℃ and time 8~12h), and the raw materials are common iron salts, cobalt salts, thiourea, etc., which are inexpensive and easy to produce on a large scale.

[0019] (2) Innovatively, thiourea is used as a bifunctional "sulfur source-template" reagent, simultaneously achieving the following in the hydrothermal process: providing sulfur ions to coordinate with metal ions to form sulfides; and generating NH3, CS2, and other gases in situ from pyrolysis to form bubble templates, inducing the formation of interconnected hierarchical channels. This structure significantly increases the specific surface area of ​​the catalyst, enhances the contact efficiency between pollutants and active sites, and solves the problem of low utilization of active sites in traditional catalysts.

[0020] (3) The traditional process of high-temperature calcination or precious metal doping in catalyst preparation is abandoned. Instead, a one-step hydrothermal synthesis at 160-240℃ is adopted to reduce energy consumption. Moreover, the catalyst in the treatment agent has good stability and can be recovered by centrifugation after the reaction. It can be reused multiple times and still maintain high activity, reducing secondary pollution. It conforms to the concept of green environmental protection and realizes a green closed loop of "preparation-use-recycling".

[0021] (4) A pioneering synergistic activation system for iron-cobalt bimetallic sulfides was developed, which modulates the iron (Fe) 3+ / Fe2+ ) and cobalt (Co) 3+ / Co 2+ By utilizing the valence state of Fe, an efficient electron transfer channel is constructed, namely, in porous iron-cobalt sulfide catalysts, iron is transferred in the form of Fe. 3+ / Fe 2+ Cobalt exists in both valence states, with Co being the most common. 3+ / Co 2+ Valence states coexist, forming an Fe-Co-S electron transfer network. By controlling the electron density of the metal-sulfur bonds, the applicability for the degradation of organic pollutants with different polarities is broadened, enabling it to cope with complex and varied organic pollutant systems. Moreover, the reaction is carried out at room temperature (25±5℃), making it easy to operate and suitable for various wastewater treatment scenarios containing organic pollutants, thus possessing high practical application value. Attached Figure Description

[0022] Figure 1 (a)-(d) are transmission electron microscope images of the treatment agent in Example 1 at different magnifications; Figure 2 XPS image of porous iron-cobalt sulfide in Example 1; Figure 3 This demonstrates the degradation effect of the organic pollutant treatment agent in Example 2, which allows for recycling and reuse. Figure 4 The degradation effect of the organic pollutant treatment agent given in Example 1 on three organic pollutants: Acid Orange 7, Tetracycline Hydrochloride, and Methyl Orange. Detailed Implementation

[0023] To make the above-mentioned objectives, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to examples. The following content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the concept of the invention, they should all fall within the protection scope of the present invention.

[0024] The present invention is further illustrated by the embodiments, but the present invention is not limited to the following embodiments. Example 1

[0025] An agent for treating organic pollutants and its preparation method, the preparation method comprising the following steps: S1. Dissolve 5 mmol of iron salt and 0.45 mmol of cobalt salt in 30 mL of solvent and disperse by ultrasonication for 10 min to form a metal ion mixture; wherein the iron salt is ferric chloride, the cobalt salt is cobalt chloride, and the solvent is ethylene glycol; S2. Add a solution containing 1.25 mmol of thiourea to the metal ion mixture and stir for 20 min to allow the thiourea to pre-coordinate with the metal ions, thus obtaining the reaction precursor solution; S3. The reaction precursor liquid is placed in a closed reaction vessel and hydrothermally reacted at 160°C for 8 hours. The NH3 and CS2 gases generated by the pyrolysis of thiourea are used to construct a porous template in situ, and iron cobalt sulfide is generated simultaneously. S4. The hydrothermal product was centrifuged and washed to obtain the supernatant, and dried at 60°C for 24 hours to obtain the porous iron-cobalt sulfide catalyst. S5. The porous iron-cobalt sulfide catalyst is mixed with persulfate at a mass ratio of 1:10 to obtain the organic pollutant treatment agent.

[0026] In step S2, the stirring speed is 400 r / min, and the system temperature is controlled at 25℃ during stirring to ensure the reaction of thiourea and Fe. 3+ Co 3+ It forms a stable coordination intermediate, avoiding the formation of metal hydroxide precipitates.

[0027] In step S3, the heating rate of the hydrothermal reaction is 2℃ / min.

[0028] application The organic pollutant treatment agent was added to 500 mg / L Acid Orange 7 solution, 200 mg / L Tetracycline Hydrochloride solution, and 200 mg / L Methyl Orange solution, respectively. The mixture was stirred at 25 ± 5 °C on a constant temperature magnetic stirrer for 60 minutes. The concentration of organic pollutants in the solution before and after the reaction was detected by UV-Vis spectrophotometer. After 60 minutes, the degradation rates of Acid Orange 7, Tetracycline Hydrochloride, and Methyl Orange were measured to be 88.95%, 77.42%, and 97.13%, respectively. Example 2

[0029] An agent for treating organic pollutants and its preparation method, the preparation method comprising the following steps: S1. Dissolve 5 mmol of iron salt and 0.85 mmol of cobalt salt in 40 mL of solvent and disperse by ultrasonication for 12 min to form a metal ion mixture; wherein the iron salt is ferric sulfate, the cobalt salt is cobalt sulfate, and the solvent is ethylene glycol; S2. Add a solution containing 1.25 mmol of thiourea to the metal ion mixture and stir for 30 min to allow the thiourea to pre-coordinate with the metal ions, thus obtaining the reaction precursor solution; S3. The reaction precursor liquid is placed in a closed reaction vessel and hydrothermally reacted at 200°C for 10 hours. The NH3 and CS2 gases generated by the pyrolysis of thiourea are used to construct a porous template in situ, and iron-cobalt sulfides are generated simultaneously. S4. The hydrothermal product was centrifuged and washed until the supernatant was nearly neutral, and then dried at 70°C for 26 h to obtain a porous iron-cobalt sulfide catalyst. S5. The porous iron-cobalt sulfide catalyst is mixed with persulfate at a mass ratio of 1:36 to obtain the organic pollutant treatment agent.

[0030] In step S2, the stirring speed is 500 r / min, and the system temperature is controlled at 30℃ during stirring to ensure the reaction of thiourea and Fe. 3+ Co 3+ To form stable coordination intermediates and avoid the formation of metal hydroxide precipitates; In step S3, the heating rate of the hydrothermal reaction is 3℃ / min.

[0031] application The organic pollutant treatment agent was added to 500 mg / L Acid Orange 7 solution, 200 mg / L Tetracycline Hydrochloride solution, and 200 mg / L Methyl Orange solution, respectively. The mixture was stirred at 25±5℃ on a constant temperature magnetic stirrer for 60 minutes. The concentration of organic pollutants in the solution before and after the reaction was detected by UV-Vis spectrophotometer. After 60 minutes, the degradation rates of Acid Orange 7, Tetracycline Hydrochloride, and Methyl Orange were measured to be 86.64%, 75.36%, and 96.39%, respectively. Example 3

[0032] An agent for treating organic pollutants and its preparation method, the preparation method comprising the following steps: S1. Dissolve 5 mmol of iron salt and 1.25 mmol of cobalt salt in 60 mL of solvent and disperse by ultrasonication for 15 min to form a metal ion mixture; wherein the iron salt is ferric nitrate, the cobalt salt is cobalt nitrate, and the solvent is ethylene glycol; S2. Add a solution containing 1.25 mmol of thiourea to the metal ion mixture and stir for 40 min to allow the thiourea to pre-coordinate with the metal ions, thus obtaining the reaction precursor solution; S3. The reaction precursor liquid is placed in a closed reaction vessel and hydrothermally reacted at 240°C for 12 hours. The NH3 and CS2 gases generated by the pyrolysis of thiourea are used to construct a porous template in situ, and iron-cobalt sulfides are generated simultaneously. S4. The hydrothermal product was centrifuged and washed until the supernatant was nearly neutral, and then dried at 80°C for 30 h to obtain a porous iron-cobalt sulfide catalyst. S5. The porous iron-cobalt sulfide catalyst is mixed with persulfate at a mass ratio of 1:62 to obtain the organic pollutant treatment agent.

[0033] In step S2, the stirring speed is 600 r / min, and the system temperature is controlled at 35℃ during stirring to ensure the reaction of thiourea and Fe. 3+Co 3+ It forms a stable coordination intermediate, avoiding the formation of metal hydroxide precipitates.

[0034] In step S3, the heating rate of the hydrothermal reaction is 5℃ / min.

[0035] application The organic pollutant treatment agent was added to 500 mg / L Acid Orange 7 solution, 200 mg / L Tetracycline Hydrochloride solution, and 200 mg / L Methyl Orange solution, respectively. The mixture was stirred at 25±5℃ on a constant temperature magnetic stirrer for 60 minutes. The concentration of organic pollutants in the solution before and after the reaction was detected by UV-Vis spectrophotometer. After 60 minutes, the degradation rates of Acid Orange 7, Tetracycline Hydrochloride, and Methyl Orange were measured to be 87.58%, 72.36%, and 96.69%, respectively.

[0036] Figure 1 Images (a)-1(d) show the transmission electron microscope (TEM) images of the treatment agent in Example 1 at different magnifications. The images clearly show the material exhibiting a distinct porous structure. These interconnected hierarchical channels were induced by bubble templates formed in situ during the hydrothermal process, acting as a bifunctional "sulfur source-template" reagent, thiourea. This ultimately results in a porous structure with specific pore sizes and morphologies, possessing an interconnected hierarchical channel structure. This porous structure significantly increases the specific surface area of ​​the material, providing abundant active sites and accelerating the mass transfer efficiency of reactants, thus providing a solid structural support for the efficient catalytic degradation of organic pollutants by the treatment agent.

[0037] Figure 2 This is the XPS image of the porous iron-cobalt sulfide from Example 1. Analysis of the spectral peaks in the image clearly shows that iron is mainly present as Fe. 3+ / Fe 2+ Cobalt exists in various valence states, primarily as Co. 3+ / Co 2+ The valence state exists, and sulfur forms stable metal-sulfur bonds with iron and cobalt, forming an Fe-Co-S electron transfer network. This result confirms the existence of a synergistic electronic structure basis in iron-cobalt bimetallic sulfides, where iron (Fe... 3+ / Fe 2+ ) and cobalt (Co) 3+ / Co 2+ The regulation of valence states between ions constructs an efficient electron transfer channel, meaning that in porous iron-cobalt sulfide catalysts, iron is transferred in the form of Fe. 3+ / Fe 2+ Cobalt exists in both valence states, with Co being the most common. 3+ / Co 2+The coexistence of valence states forms an Fe-Co-S electron transfer network. This helps to improve the activation efficiency of persulfate, thereby enhancing the degradation capacity of organic pollutants.

[0038] Figure 3 The degradation effect of the organic pollutant treatment agent in Example 2 is shown to be recyclable and reusable. The results show that after multiple cycles of use, the degradation rate of organic pollutants remains at a high level. This indicates that the porous iron-cobalt sulfide catalyst in the treatment agent has good stability and can be recovered by simple methods such as centrifugation after the reaction, achieving multiple reuses, reducing secondary pollution, conforming to the green environmental protection concept, and demonstrating the green closed-loop advantage of "preparation-use-recycling".

[0039] Figure 4 The degradation effect of the organic pollutant treatment agent given in Example 1 on three organic pollutants: Acid Orange 7, tetracycline hydrochloride, and methyl orange. As can be clearly seen from the figure, the treatment agent exhibits high degradation rates for these three different types of organic pollutants (representing azo dyes, antibiotics, and basic dyes, respectively) within 60 minutes. Specifically, the degradation rate for Acid Orange 7 reaches 88.95%, for tetracycline hydrochloride 77.42%, and for methyl orange 97.13%. This fully demonstrates that by regulating the electron density of metal-sulfur bonds, the treatment agent broadens its applicability to the degradation of organic pollutants of different polarities, effectively addressing complex and varied organic pollutant systems, and showing its broad application potential in practical wastewater treatment.

[0040] Comparative Example 1 Preparation method: The process is basically the same as in Example 1, except that the amount of cobalt salt is adjusted to 2.0 mmol (which is outside the range of 0.45~1.25 mmol in this invention), while the other parameters (5 mmol of iron salt, 1.25 mmol of thiourea, 40 mL of solvent, hydrothermal conditions, etc.) remain unchanged. A porous iron-cobalt sulfide catalyst is prepared, and then a treatment agent is prepared according to the ratio of 0.01 g catalyst + 0.1 g persulfate.

[0041] application: Degradation effect on 500 mg / L Acid Orange 7 solution: The degradation rate was only 52.3% after 60 minutes.

[0042] Cause analysis: Excess cobalt salt (2.0 mmol) leads to an imbalance in the ratio of total molar metal ions (5 + 2 = 7 mmol) to thiourea (1.25 mmol) (metal:sulfur = 5.6:1, far exceeding the 4.36~5:1 of this invention): 1. Due to a relative insufficiency of sulfur source, some cobalt ions cannot coordinate with sulfur, forming free Co. 3+ / Co 2+ During the hydrothermal process, they agglomerate and block the channels; 2. An imbalance in the iron-cobalt ratio disrupts the Fe... 3+ / Fe 2+ With Co 3+ / Co 2+ The electron transfer balance is disrupted, the activation efficiency of persulfate decreases, and ultimately the degradation performance deteriorates significantly.

Claims

1. A treatment agent for organic pollutants, characterized in that, It is composed of porous iron-cobalt sulfide catalyst and persulfate in a mass ratio of 1:10 to 1:62; the porous iron-cobalt sulfide catalyst is prepared by synergistic regulation of iron and cobalt bimetals using thiourea as a "sulfur source-soft template" bifunctional reagent. The total molar ratio of metal elements to thiourea is 4.36 to 5:1, and it has a through-type multi-level pore structure. In the porous iron-cobalt sulfide catalyst, iron is present in the form of Fe. 3+ / Fe 2+ Cobalt exists in both valence states, with Co being the most common. 3+ / Co 2+ Valence states coexist, forming an Fe-Co-S electron transfer network.

2. A method for preparing the organic pollutant treatment agent according to claim 1, characterized in that, Includes the following steps: S1. Dissolve 5 mmol of iron salt and 0.45~1.25 mmol of cobalt salt in 30~60 mL of solvent, and ultrasonically disperse for 10~15 min to form a metal ion mixture; wherein the iron salt is at least one of ferric chloride, ferric sulfate, and ferric nitrate, and the cobalt salt is at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, and the solvent is ethylene glycol; S2. Add a solution containing 1.25 mmol of thiourea to the metal ion mixture and stir for 20-40 min to allow the thiourea to pre-coordinate with the metal ions, thus obtaining the reaction precursor solution; S3. The reaction precursor liquid is placed in a closed reaction vessel and hydrothermally reacted at 160~240℃ for 8~12h. The NH3 and CS2 gases generated by the pyrolysis of thiourea are used to construct a porous template in situ, and iron-cobalt sulfide is generated simultaneously. S4. The hydrothermal product was centrifuged and washed until the supernatant pH was 6.5-7.5, and dried at 60-80℃ for 24-30 h to obtain a porous iron-cobalt sulfide catalyst. S5. The porous iron-cobalt sulfide catalyst is mixed with persulfate at a mass ratio of 1:10 to 1:62 to obtain the organic pollutant treatment agent.

3. The preparation method according to claim 2, characterized in that, In step S2, the stirring speed is 400~600 r / min, and the system temperature is controlled at 25~35℃ during stirring to ensure the reaction of thiourea and Fe. 3+ Co 3+ It forms a stable coordination intermediate, avoiding the formation of metal hydroxide precipitates.

4. The preparation method according to claim 2, characterized in that, In step S3, the heating rate of the hydrothermal reaction is 2~5℃ / min.

5. A method for applying the organic pollutant treatment agent according to claim 1, characterized in that, The treatment agent is added to a solution containing organic pollutants and stirred at 25±5°C.

6. The application according to claim 5, characterized in that, The organic pollutants include at least one of Acid Orange 7, tetracycline hydrochloride, and methyl orange.

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