CN-117696006-B - Cube type double-function adsorption material and preparation method and application thereof

CN117696006BCN 117696006 BCN117696006 BCN 117696006BCN-117696006-B

Abstract

The invention discloses a cube type double-function adsorption material, a preparation method and application thereof, wherein the preparation method comprises the following steps: and heating the zeolite imidazole skeleton to above 800 ℃ under inert atmosphere to calcine, thus obtaining the cubic double-function adsorption material. The cubic dual-functional adsorption material can adsorb sulfonamide antibiotics and heavy metals simultaneously, has the advantages of large specific surface area, multiple adsorption sites, rich pore structure, large pore volume and pore diameter and high adsorption capacity, is a novel dual-functional adsorbent with excellent performance, and can effectively remove the sulfonamide antibiotics and the heavy metals in the wastewater when being used for treating the composite wastewater containing the sulfonamide antibiotics and the heavy metals, and has high use value and good application prospect. The preparation method also has the advantages of simple process, convenient operation, low cost, economy, safety, easy popularization and the like, and has important promotion effect on realizing the large-scale preparation and industrial application of the cubic double-function adsorption material.

Inventors

WU XIN
YANG CHUNPING
LIN YAN
ZOU JUNCONG
DAI MEI
WU SHAOHUA
LI XIANG
LI XIANG
ZHONG YUANYUAN

Assignees

广东石油化工学院

Dates

Publication Date: 20260505
Application Date: 20231205

Claims (8)

1. A preparation method of a cubic bifunctional adsorption material for treating composite wastewater containing sulfonamide antibiotics and heavy metals is characterized by comprising the following steps of heating a zeolite imidazole skeleton to above 800 ℃ under an inert atmosphere, and calcining for 1-4 hours to obtain the cubic bifunctional adsorption material, wherein the cubic bifunctional adsorption material is a porous carbon material containing nitrogen vacancies and zinc vacancies, the particle size of the cubic bifunctional adsorption material is 100-200 nm, the pore volume is 0.4 cm 3 ·g -1 ～0.5 cm 3 ·g -1 , the pore size is 2.0-3.0 nm, and the specific surface area is 1000 m 2 ·g -1 ～3000 m 2 ·g -1 ; the preparation method of the zeolite imidazole skeleton comprises the following steps: S1, adding a 2-methylimidazole dispersion solution into a zinc nitrate dispersion solution under the condition of the rotating speed of 300-1000 rpm, and reacting for 12-24 hours to obtain a white solid, wherein the dropping rate of the 2-methylimidazole dispersion solution is 50 mL/h; S2, washing and vacuum drying the white solid to obtain the zeolite imidazole skeleton.
2. The method according to claim 1, wherein the calcination is performed at a temperature of 800 ℃ to 1000 ℃.
3. The method according to claim 2, wherein the calcination is performed at a temperature of 900 ℃ to 1000 ℃.
4. The method according to claim 3, wherein the inert atmosphere is argon, and the temperature rising rate in the calcination process is 2-5 ℃.
5. The preparation method of the zinc nitrate dispersion solution is characterized in that the 2-methylimidazole dispersion solution is prepared by mixing 2-methylimidazole with methanol, performing ultrasonic treatment to obtain a 2-methylimidazole dispersion solution, wherein the concentration of 2-methylimidazole in the 2-methylimidazole dispersion solution is 0.2 mol/L-0.8 mol/L, and the zinc nitrate dispersion solution is prepared by mixing zinc nitrate with methanol, performing ultrasonic treatment to obtain a zinc nitrate dispersion solution, and the concentration of zinc nitrate in the zinc nitrate dispersion solution is 0.05 mol/L-0.2 mol/L; in the step S2, the detergents adopted in the washing process are methanol and water, and the temperature of the vacuum drying is 50-70 ℃.
6. A cubic type bifunctional adsorbing material, which is characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. Use of the cubic dual-function adsorption material according to claim 6 for treating composite wastewater containing sulfonamide antibiotics and heavy metals.
8. The application according to claim 7, wherein the application comprises the steps of mixing cubic bifunctional adsorption material, sulfonamide-containing antibiotic and heavy metal composite wastewater for oscillation adsorption, and completing treatment of sulfonamide-containing antibiotic and heavy metal composite wastewater; The mass ratio of the cube-type bifunctional adsorption material to the pollutants in the composite wastewater containing the sulfonamide antibiotics and the heavy metal is 2:1-5:1, the composite wastewater containing the sulfonamide antibiotics and the heavy metal is livestock and poultry breeding wastewater, the concentration of the sulfonamide antibiotics in the composite wastewater containing the sulfonamide antibiotics and the heavy metal is 0.5 mg/L-20 mg/L, the concentration of the heavy metal is 0.5. 0.5 mg/L-5 mg/L, the sulfonamide antibiotics comprise at least one of sulfamethoxazole, sulfadiazine and sulfamethoxydiazine, the heavy metal comprises at least one of zinc ions, copper ions and iron ions, and the oscillation adsorption time is 3-5 h.

Description

Cube type double-function adsorption material and preparation method and application thereof Technical Field The invention belongs to the technical field of environmental functional material application and environmental protection, and relates to a cube type double-functional adsorption material and a preparation method and application thereof. Background Chemical oxidation and chemical precipitation are common methods for treating organic pollution and heavy metal pollution respectively, but the methods have the defects of large chemical reagent consumption, easy secondary pollution, influence on subsequent anaerobic digestion performance and the like. In contrast, the adsorption technology has the advantages of simple operation, economy, energy conservation, difficult secondary pollution generation and the like, wherein the adsorbent is the key of successful application of the adsorption technology. However, the conventional adsorbents generally have high selectivity and can only be used for removing one type or a certain pollutant, so that the conventional adsorbents are difficult to be suitable for treating the composite polluted wastewater containing more than two pollutants. Therefore, the dual-function adsorption material capable of simultaneously adsorbing the antibiotics and the heavy metals is obtained, and has important promotion effect on effectively treating the composite polluted wastewater containing the antibiotics and the heavy metals. Disclosure of Invention The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a cubic dual-function adsorption material capable of simultaneously adsorbing sulfonamide antibiotics and heavy metals, and a preparation method and application thereof. In order to solve the technical problems, the invention adopts the following technical scheme. A process for preparing the cube-type dual-function adsorption material includes such steps as heating zeolite imidazole skeleton to 800 deg.C under inertial atmosphere, calcining, and preparing the said adsorption material. According to the preparation method, further improved, the calcination is carried out at the temperature of 800-1000 ℃. According to the preparation method, further improved, the calcination is carried out at the temperature of 900-1000 ℃. According to the preparation method, the inert atmosphere is argon, the temperature rising rate in the calcining process is 2-5 ℃ per minute, and the calcining time is 1-4 hours. The preparation method of the zeolite imidazole skeleton is further improved, and comprises the following steps of: S1, adding a 2-methylimidazole dispersion solution into a zinc nitrate dispersion solution under the condition that the rotating speed is 300-1000 rpm, and reacting to obtain a white solid; S2, washing and vacuum drying the white solid to obtain the zeolite imidazole skeleton. In the step S1, the dropping rate of the 2-methylimidazole dispersion solution is 50mL/h, the 2-methylimidazole dispersion solution is prepared by mixing 2-methylimidazole with methanol, performing ultrasonic treatment to obtain the 2-methylimidazole dispersion solution, the concentration of 2-methylimidazole in the 2-methylimidazole dispersion solution is 0.2-0.8 mol/L, the zinc nitrate dispersion solution is prepared by mixing zinc nitrate with methanol, performing ultrasonic treatment to obtain the zinc nitrate dispersion solution, the concentration of zinc nitrate in the zinc nitrate dispersion solution is 0.05-0.2 mol/L, and the reaction time is 12-24 h. In the preparation method, in the step S2, the adopted detergents are methanol and water, and the temperature of vacuum drying is 50-70 ℃. As a general technical concept, the invention also provides a cube-type double-function adsorption material prepared by the preparation method. The cubic bifunctional adsorption material is further improved, is a porous carbon material containing nitrogen vacancies and zinc vacancies, has the particle size of 100 nm-200 nm, has the pore volume of 0.4cm 3·g-1～0.5cm3·g-1, has the pore size of 2.0 nm-3.0 nm and has the specific surface area of 1000m 2·g-1～3000m2·g-1. As a general technical conception, the invention also provides application of the cubic double-function adsorption material in treating composite wastewater containing sulfonamide antibiotics and heavy metals. The application is further improved, and the application comprises the following steps of mixing the cubic double-function adsorption material, the sulfonamide antibiotics and the heavy metal-containing composite wastewater for oscillation adsorption, and completing treatment of the sulfonamide antibiotics and heavy metal-containing composite wastewater. According to the application, the quality ratio of the cube-type bifunctional adsorption material to pollutants in the composite wastewater containing the sulfonamide antibiotics and the heavy metal is 2:1-5:1, the composite wastewater containin