Cubic bifunctional adsorption material and preparation method and application thereof

Abstract

This invention discloses a cubic bifunctional adsorbent material, its preparation method, and its applications. The preparation method includes the following steps: calcining a zeolite imidazole framework at a temperature above 800°C under an inert atmosphere to obtain the cubic bifunctional adsorbent material. The cubic bifunctional adsorbent material of this invention can simultaneously adsorb sulfonamide antibiotics and heavy metals. It also possesses a large specific surface area, numerous adsorption sites, abundant pore structure, large pore volume and diameter, and high adsorption capacity. It is a novel bifunctional adsorbent with excellent performance. When used to treat complex wastewater containing sulfonamide antibiotics and heavy metals, it can effectively remove these substances from the wastewater, demonstrating high practical value and promising application prospects. The preparation method of this invention also has advantages such as simple process, convenient operation, low cost, economic safety, and ease of promotion. It plays a significant role in promoting the large-scale preparation and industrial application of cubic bifunctional adsorbent materials.

Description

Technical Field

[0001] This invention belongs to the field of environmental functional materials application and environmental protection technology, and relates to a cubic bifunctional adsorbent material, its preparation method and application. Background Technology

[0002] Chemical oxidation and chemical precipitation are common methods for treating organic and heavy metal pollution, respectively. However, these methods suffer from drawbacks such as large chemical reagent consumption, potential secondary pollution, and reduced performance of subsequent anaerobic digestion. In contrast, adsorption technology offers advantages such as simple operation, energy efficiency, and minimal secondary pollution. The adsorbent is crucial for the successful application of adsorption technology. However, existing conventional adsorbents typically exhibit high selectivity, limiting their application to the removal of only one type or type of pollutant, making them unsuitable for treating complex wastewater containing two or more pollutants. Therefore, developing a bifunctional adsorbent capable of simultaneously adsorbing antibiotics and heavy metals is essential for the effective treatment of complex wastewater containing both. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a cubic bifunctional adsorbent material that can simultaneously adsorb sulfonamide antibiotics and heavy metals, as well as its preparation method and application.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution.

[0005] A method for preparing a cubic bifunctional adsorbent material includes the following steps: calcining a zeolite imidazole framework at a temperature above 800°C under an inert atmosphere to obtain a cubic bifunctional adsorbent material.

[0006] In a further improvement to the above preparation method, the calcination is carried out at a temperature of 800℃ to 1000℃.

[0007] In a further improvement to the above preparation method, the calcination is carried out at a temperature of 900℃~1000℃.

[0008] In a further improvement to the above preparation method, the inert atmosphere is argon; the heating rate during the calcination process is 2℃ / min to 5℃ / min; and the calcination time is 1h to 4h.

[0009] A further improvement to the above preparation method is the preparation method of the zeolite imidazole skeleton, which includes the following steps:

[0010] S1. Under the condition of a rotation speed of 300 rpm to 1000 rpm, the 2-methylimidazole dispersion solution was added to the zinc nitrate dispersion solution, and the reaction was carried out to obtain a white solid.

[0011] S2. The white solid was washed and vacuum dried to obtain the zeolite imidazole skeleton.

[0012] In a further improvement to the above preparation method, in step S1, the dropping rate of the 2-methylimidazole dispersion is 50 mL / h; the 2-methylimidazole dispersion is prepared by mixing 2-methylimidazole with methanol and sonicating to obtain a 2-methylimidazole dispersion; the concentration of 2-methylimidazole in the 2-methylimidazole dispersion is 0.2 mol / L to 0.8 mol / L; the zinc nitrate dispersion is prepared by mixing zinc nitrate with methanol and sonicating to obtain a zinc nitrate dispersion; the concentration of zinc nitrate in the zinc nitrate dispersion is 0.05 mol / L to 0.2 mol / L; and the reaction time is 12 h to 24 h.

[0013] In a further improvement to the above preparation method, in step S2, the washing agent used in the washing process is methanol and water; and the vacuum drying temperature is 50℃~70℃.

[0014] As a general technical concept, the present invention also provides a cubic bifunctional adsorbent material, which is prepared by the above-described preparation method.

[0015] A further improvement to the aforementioned cubic bifunctional adsorbent material is that the cubic bifunctional adsorbent material is a porous carbon material containing nitrogen and zinc vacancies; the particle size of the cubic bifunctional adsorbent material is 100 nm to 200 nm, and the pore volume is 0.4 cm³. 3 ·g -1 ~0.5cm 3 ·g -1 The pore size is 2.0 nm to 3.0 nm, and the specific surface area is 1000 m². 2 ·g -1 ~3000m 2 ·g -1 .

[0016] As a general technical concept, the present invention also provides an application of the above-mentioned cubic bifunctional adsorbent material in the treatment of wastewater containing sulfonamide antibiotics and heavy metals.

[0017] The above-mentioned application, in a further improvement, includes the following steps: mixing cubic bifunctional adsorbent material, sulfonamide antibiotic and heavy metal composite wastewater and performing oscillation adsorption to complete the treatment of sulfonamide antibiotic and heavy metal composite wastewater.

[0018] In a further improvement to the above application, the mass ratio of the cubic bifunctional adsorbent material to the pollutants in the wastewater containing sulfonamide antibiotics and heavy metals is 2:1 to 5:1; the wastewater containing sulfonamide antibiotics and heavy metals is livestock and poultry breeding wastewater; the concentration of sulfonamide antibiotics in the wastewater is 0.5 mg / L to 20 mg / L, and the concentration of heavy metals is 0.5 mg / L to 5 mg / L; the sulfonamide antibiotics include at least one of sulfamethoxazole, sulfadiazine, and sulfamethoxypyrimidine; the heavy metals include at least one of zinc ions, copper ions, and iron ions; and the oscillation adsorption time is 3 h to 5 h.

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

[0020] (1) In view of the shortcomings of existing adsorbents, such as small specific surface area, few adsorption sites, only able to adsorb a certain pollutant, and low adsorption capacity, this invention creatively proposes a method for preparing a cubic bifunctional adsorbent material. The zeolite imidazole framework is calcined under an inert atmosphere and at a temperature above 800℃. The calcination transforms the zeolite imidazole framework into carbon material, which contains a large number of nitrogen and zinc vacancies. By reducing the size of the fine particles, the pore volume and pore size of the fine particles are increased, making it a porous carbon material rich in nitrogen and zinc vacancies. The presence of nitrogen and zinc vacancies provides abundant adsorption sites for adsorbing nitrogen-containing antibiotics such as sulfonamides and heavy metal ions, thus enabling the simultaneous adsorption of antibiotics and heavy metal ions. At the same time, the porous carbon material also has the characteristics of porous structure and large pore volume and pore size, which is conducive to the flow and adsorption of pollutants inside the material, thus exhibiting better adsorption performance. The cubic bifunctional adsorbent prepared by this invention can simultaneously adsorb sulfonamide antibiotics and heavy metals. It also possesses a large specific surface area, numerous adsorption sites, abundant pore structure, large pore volume and diameter, and high adsorption capacity. It is a novel bifunctional adsorbent that can be widely used to achieve synergistic treatment of antibiotics and heavy metals. It can be widely applied to treat complex wastewater containing sulfonamide antibiotics and heavy metals, effectively removing these substances from the wastewater. It has high practical value and promising application prospects. Furthermore, the preparation method of this invention has advantages such as simple process, convenient operation, low cost, economic safety, and ease of promotion, which plays a significant role in promoting the large-scale preparation and industrial application of cubic bifunctional adsorbents.

[0021] (2) This invention also provides an application of cubic bifunctional adsorbent material in the treatment of wastewater containing sulfonamide antibiotics and heavy metals. By mixing the cubic bifunctional adsorbent material with the wastewater containing sulfonamide antibiotics and heavy metals and performing oscillation adsorption, the cubic bifunctional adsorbent material can efficiently adsorb and remove sulfonamide antibiotics and heavy metals from the wastewater. This not only effectively reduces the load of subsequent wastewater treatment, but also reduces the impact of recalcitrant sulfonamide antibiotics and heavy metals on the anaerobic digestion and methanogenesis of microorganisms. This is beneficial for the resource utilization of wastewater in subsequent processes. It has the advantages of simple process, easy operation, excellent pollutant removal performance, high treatment effect, and no secondary pollution. It is of great significance for the treatment and resource utilization of livestock and poultry breeding wastewater that contains both sulfonamide antibiotics and heavy metals. Attached Figure Description

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0023] Figure 1 This is a flowchart illustrating the preparation process of the cubic bifunctional material in Embodiment 1 of the present invention.

[0024] Figure 2 This is a SEM image of the cubic bifunctional adsorbent material prepared in Example 1 of the present invention.

[0025] Figure 3 This is an elemental analysis and proportion diagram of the powdered fine particles prepared in Example 1 of the present invention.

[0026] Figure 4 This is an elemental analysis and proportion diagram of the cubic bifunctional adsorbent material prepared in Example 1 of the present invention.

[0027] Figure 5 This is a diagram showing the adsorption effect of the cubic bifunctional adsorbent material on sulfamethoxazole antibiotic in livestock and poultry breeding wastewater in Example 2 of the present invention.

[0028] Figure 6 This is a diagram showing the adsorption effect of the cubic bifunctional adsorbent material on zinc ions in livestock and poultry breeding wastewater in Embodiment 2 of the present invention.

[0029] Figure 7 The graph shows the adsorption effect of the cubic bifunctional adsorbent material in Comparative Example 1 on sulfamethoxazole antibiotic in livestock and poultry breeding wastewater.

[0030] Figure 8 The graph shows the adsorption effect of the cubic bifunctional adsorbent material on zinc ions in livestock and poultry breeding wastewater in Comparative Example 1. Detailed Implementation

[0031] 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.

[0032] Example 1

[0033] A method for preparing a cubic bifunctional material, the process flow diagram of which is shown below. Figure 1 As shown, it includes the following steps:

[0034] (1) Weigh 1.90g of zinc nitrate and disperse it in 100mL of methanol solution. Sonicate for 5min to obtain a zinc nitrate dispersion with a molar concentration of 0.1mol / L.

[0035] (2) Weigh 3.24g of 2-methylimidazole and disperse it in 100mL of methanol solution. Sonicate for 5min to obtain a 2-methylimidazole dispersion with a molar concentration of 0.4mol / L.

[0036] (3) At a speed of 500 rpm, the 2-methylimidazole dispersion was mixed with the zinc nitrate dispersion at a dropping rate of 50 mL / h and reacted for 16 h. The resulting white solid was then collected.

[0037] (4) The collected white solid was washed three times with methanol solution and pure water, and then dried in a vacuum drying oven at 65°C. After drying, it was ground into fine powder particles.

[0038] (5) The powdered fine particles are placed in a tube furnace and heated to 950°C at a heating rate of 5°C / min in an argon atmosphere. The mixture is then calcined for 2 hours to obtain a cubic porous carbon material containing nitrogen and zinc vacancies, which is the cubic bifunctional adsorbent material of the present invention.

[0039] Figure 2 This is a SEM image of the cubic bifunctional adsorbent material prepared in Example 1 of this invention. Figure 2 It can be seen that the cubic bifunctional adsorbent material prepared in Example 1 of the present invention has a particle size of 100nm to 200nm (average particle size of 150nm) and a rough surface, which provides favorable conditions for the adsorption of pollutants.

[0040] Figure 3 This is an elemental analysis and proportion diagram of the powdered fine particles prepared in Example 1 of the present invention. Figure 4 This is an elemental analysis and composition diagram of the cubic bifunctional adsorbent material prepared in Example 1 of the present invention. Figure 3 and Figure 4As can be seen, compared with powdered fine particles, the cubic bifunctional adsorbent material prepared by calcination in Example 1 of this invention has a significantly reduced content of nitrogen and zinc elements. Specifically, the cubic bifunctional adsorbent material contains 91.7% carbon, 7.7% nitrogen, and only 0.6% zinc by mass. Therefore, the cubic bifunctional adsorbent material prepared by this invention forms a large number of nitrogen and zinc vacancies.

[0041] Furthermore, testing revealed that the cubic bifunctional adsorbent material prepared in Example 1 of this invention is a porous carbon material containing nitrogen and zinc vacancies, with an average size (particle diameter) of 150 nm and a pore volume of 0.45 cm³. 3 ·g -1 The pore size is 2.6 nm, and the specific surface area is 1280 m². 2 ·g -1 .

[0042] Example 2:

[0043] An application of a cubic bifunctional adsorbent material in the treatment of wastewater containing sulfonamide antibiotics and heavy metals, specifically, using the cubic bifunctional adsorbent material prepared in Example 1 to treat sulfamethoxazole and zinc ions in livestock and poultry breeding wastewater, includes the following steps:

[0044] Accurately weigh 50 mg of the cubic bifunctional adsorbent material prepared in Example 1, add it to 1000 mL of livestock and poultry breeding wastewater with sulfamethoxazole and heavy metal zinc ion concentrations of 10 mg / L and 5 mg / L, respectively, and shake the adsorption reaction for 5 h at a stirring speed of 500 rpm to complete the treatment of livestock and poultry breeding wastewater.

[0045] During the reaction, 2 mL of the reaction solution was taken at regular intervals and filtered through a 0.45 μm aqueous filter to determine the concentrations of sulfamethoxazole and zinc ions in the water. The results are as follows: Figure 5 and Figure 6 As shown.

[0046] Figure 5 This image shows the adsorption effect of the cubic bifunctional adsorbent material in Example 2 of the present invention on sulfamethoxazole antibiotic in livestock and poultry breeding wastewater. Figure 5 It can be seen that the cubic bifunctional adsorbent material prepared in Example 1 has good adsorption performance for the antibiotic sulfamethoxazole in livestock and poultry breeding wastewater. In the first hour of the reaction, it can adsorb and remove 62% of the sulfamethoxazole in the wastewater. Subsequently, the adsorption rate becomes slow and finally reaches adsorption equilibrium in 5 hours, with a removal efficiency of 90% for sulfamethoxazole.

[0047] Figure 6This image shows the adsorption effect of the cubic bifunctional adsorbent material on zinc ions in livestock and poultry breeding wastewater in Example 2 of the present invention. Figure 6 It can be seen that the cubic bifunctional adsorbent material prepared in Example 1 also has good adsorption performance for zinc ions in livestock and poultry breeding wastewater. In the first hour of the reaction, the adsorption rate of zinc ions is very fast, and the removal efficiency reaches 79%. Subsequently, the adsorption rate becomes slow, and finally reaches adsorption equilibrium in 5 hours, with the zinc ion removal efficiency reaching 98%.

[0048] Comparative Example 1:

[0049] The application of a cubic bifunctional adsorbent material in the treatment of wastewater containing sulfonamide antibiotics and heavy metals is basically the same as that in Example 2, except that the cubic bifunctional adsorbent material used in Comparative Example 1 is prepared at a temperature of 700°C, and the other conditions of the preparation process are the same as those in Example 1.

[0050] The removal efficiency of sulfamethoxazole and zinc ions in livestock and poultry breeding wastewater in Comparative Example 1 was tested, as shown in the following figures. Figure 7 and Figure 8 As shown.

[0051] Figure 7 This is a graph showing the adsorption effect of the cubic bifunctional adsorbent material in Comparative Example 1 on sulfamethoxazole antibiotic in livestock and poultry wastewater. Figure 7 It can be seen that the cubic bifunctional adsorbent material obtained by calcination at 700℃ has a poorer adsorption performance for the antibiotic sulfamethoxazole in livestock and poultry breeding wastewater than that of Example 2. In the first hour of the reaction, it adsorbed and removed 40% of the sulfamethoxazole in the wastewater. Subsequently, the adsorption rate became slow and reached adsorption equilibrium at 8 hours. The removal efficiency of sulfamethoxazole was only 61%.

[0052] Figure 8 This is a graph showing the adsorption effect of the cubic bifunctional adsorbent material in Comparative Example 1 on zinc ions in livestock and poultry breeding wastewater. Figure 8 It can be seen that the adsorption performance of the cubic bifunctional adsorbent material obtained by calcination at 700℃ for zinc ions in livestock and poultry breeding wastewater is also lower than that in Example 2. In the first hour of the reaction, the removal efficiency of zinc ions reached 55%, and then the adsorption rate became slow. Finally, the adsorption equilibrium was reached at 8h, but the removal efficiency of zinc ions was only 76%.

[0053] The results above show that the cubic bifunctional adsorbent prepared by this invention can simultaneously adsorb sulfonamide antibiotics and heavy metals. It also possesses a large specific surface area, numerous adsorption sites, abundant pore structure, large pore volume and diameter, and high adsorption capacity. It is a novel bifunctional adsorbent that can be widely adopted and achieves synergistic treatment of antibiotics and heavy metals. When used to treat complex wastewater containing sulfonamide antibiotics and heavy metals, it can efficiently adsorb and remove these substances, effectively reducing the load on subsequent wastewater treatment and mitigating the impact of recalcitrant sulfonamide antibiotics and heavy metals on methanogenesis through anaerobic digestion. This facilitates the resource utilization of wastewater in subsequent processes. It has advantages such as simple process, easy operation, excellent pollutant removal performance, high treatment efficiency, and no secondary pollution. It is of great significance for the treatment and resource utilization of livestock and poultry breeding wastewater containing both sulfonamide antibiotics and heavy metals.

[0054] 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 for preparing a cubic bifunctional adsorbent material for treating complex wastewater containing sulfonamide antibiotics and heavy metals, characterized in that, Includes the following steps: Under an inert atmosphere, the zeolite imidazole framework was calcined at above 800℃ for 1-4 hours to obtain a cubic bifunctional adsorbent material. The cubic bifunctional adsorbent material is a porous carbon material containing nitrogen and zinc vacancies. The particle size of the cubic bifunctional adsorbent material is 100 nm-200 nm, and the pore volume is 0.4 cm³. 3 ·g -1 ~0.5 cm 3 ·g -1 The pore size is 2.0 nm to 3.0 nm, and the specific surface area is 1000 m². 2 ·g -1 ~3000m 2 ·g -1 ; The preparation method of the zeolite imidazole skeleton includes the following steps: S1. Under the condition of 300 rpm to 1000 rpm, the 2-methylimidazole dispersion solution is added to the zinc nitrate dispersion solution, and the reaction is carried out for 12 h to 24 h to obtain a white solid; the dropping rate of the 2-methylimidazole dispersion solution is 50 mL / h. S2. The white solid was washed and vacuum dried to obtain the zeolite imidazole skeleton.

2. The preparation method according to claim 1, characterized in that, The calcination is carried out at a temperature of 800℃ to 1000℃.

3. The preparation method according to claim 2, characterized in that, The calcination is carried out at a temperature of 900℃ to 1000℃.

4. The preparation method according to claim 3, characterized in that, The inert atmosphere is argon; the heating rate during the calcination process is 2℃ / min to 5℃ / min.

5. The preparation method according to any one of claims 1 to 4, characterized in that... The 2-methylimidazole dispersion was prepared by mixing 2-methylimidazole with methanol and then sonicating to obtain a 2-methylimidazole dispersion; the concentration of 2-methylimidazole in the 2-methylimidazole dispersion was 0.2 mol / L to 0.8 mol / L. The zinc nitrate dispersion was prepared by mixing zinc nitrate with methanol and then sonicating to obtain a zinc nitrate dispersion; the concentration of zinc nitrate in the zinc nitrate dispersion was 0.05 mol / L to 0.2 mol / L. In step S2, the detergent used in the washing process is methanol and water; the temperature of the vacuum drying is 50℃~70℃.

6. A cubic bifunctional adsorbent material, characterized in that, The cubic bifunctional adsorbent material is prepared by the preparation method according to any one of claims 1 to 5.

7. The application of the cubic bifunctional adsorbent material as described in claim 6 in the treatment of complex wastewater containing sulfonamide antibiotics and heavy metals.

8. The application according to claim 7, characterized in that, The application includes the following steps: mixing cubic bifunctional adsorbent material, sulfonamide antibiotics and heavy metal composite wastewater and performing oscillation adsorption to complete the treatment of sulfonamide antibiotics and heavy metal composite wastewater; The mass ratio of the cubic bifunctional adsorbent material to the pollutants in the wastewater containing sulfonamide antibiotics and heavy metals is 2:1 to 5:1; the wastewater containing sulfonamide antibiotics and heavy metals is livestock and poultry breeding wastewater; the concentration of sulfonamide antibiotics in the wastewater is 0.5 mg / L to 20 mg / L, and the concentration of heavy metals is 0.5 mg / L to 5 mg / L; the sulfonamide antibiotics include at least one of sulfamethoxazole, sulfadiazine, and sulfamethoxypyrimidine; the heavy metals include at least one of zinc ions, copper ions, and iron ions; the oscillation adsorption time is 3 h to 5 h.

Images