CN-121991371-A - Preparation method and application of zirconium-based metal organic gel material

Abstract

The invention discloses a preparation method and application of a zirconium-based metal organic gel material, which comprises the steps of (1) adding zirconium oxychloride into distilled water, stirring and dissolving at room temperature to obtain a zirconium oxychloride solution, (2) adding trimesic acid into absolute ethyl alcohol, stirring and dissolving at room temperature to obtain a trimesic acid solution, step (3) mixing the zirconium oxychloride solution and the trimesic acid solution at room temperature, continuously stirring to obtain a mixed solution, and step (4) carrying out hydrothermal reaction on the mixed solution, naturally cooling to room temperature after the reaction is finished, and freeze-drying to obtain the zirconium-based metal organic gel material. The zirconium-based metal organic gel material prepared by the method is used for treating pulp wastewater with pH of 2-12 and containing lignin and/or humic acid organic matters, and the problem that the pH application range of the existing metal organic gel material is narrow when the pulp wastewater is treated can be solved.

Inventors

• MU JINCHENG
• WU CHANGSHENG
• Nie Zhifei
• MA XUDONG
• ZHANG RUI
• MA LONGJIAN
• OU MING
• ZHAO JIANBO
• XU CHUNBO
• SU ZHONGYANG

Assignees

• 塔里木大学

Dates

Publication Date

20260508

Application Date

20260202

Claims (10)

1. 1. The preparation method of the zirconium-based metal organic gel material is characterized by comprising the following steps of: Adding zirconium oxychloride into distilled water, stirring and dissolving at room temperature to obtain a zirconium oxychloride solution; step (2), adding trimesic acid into absolute ethyl alcohol, stirring and dissolving at room temperature to obtain trimesic acid solution; Step (3), mixing the zirconium oxychloride solution and the trimesic acid solution at room temperature, and continuously stirring to obtain a mixed solution; and (4) carrying out hydrothermal reaction on the mixed solution, naturally cooling to room temperature after the reaction is finished, and freeze-drying to obtain the zirconium-based metal organic gel material.
2. 2. The method for producing a zirconium-based metal organic gel material as claimed in claim 1, wherein in the step (1), the stirring time is 10 to 20 minutes, and the mass concentration of the zirconium oxychloride solution is 0.3 to 0.8mol/L.
3. 3. The method for producing a zirconium-based metal organic gel material as claimed in claim 1, wherein in the step (2), the stirring time is 15 to 25 minutes, and the mass concentration of the trimesic acid solution is 0.1 to 0.2mol/L.
4. 4. The method for preparing a zirconium-based metal organic gel material as claimed in claim 1, wherein in the step (3), the stirring time is 15-30min, and the volume ratio of trimesic acid solution to zirconium oxychloride solution is 1 (0.5-1.0).
5. 5. The method according to claim 4, wherein in the step (3), the stirring time is 20min, and the volume ratio of trimesic acid solution to zirconium oxychloride solution is 1:0.75.
6. 6. The method for preparing a zirconium-based metal organic gel material as claimed in claim 1, wherein in the step (4), the hydrothermal reaction condition is that the reaction temperature is 130-150 ℃ and the reaction time is 1-3 hours, and the freeze-drying is carried out by setting the freezing temperature of a freeze dryer to be-50 ℃ to-40 ℃ and taking out after freeze-drying for 20-28 hours.
7. 7. The method for producing a zirconium-based metal organic gel material as claimed in claim 6, wherein in the step (4), the hydrothermal reaction condition is a reaction temperature of 140 ℃ and a reaction time of 2 hours, and wherein in the freeze-drying, the freeze-dryer is set to a freezing temperature of-50 ℃ and the mixture is taken out after freeze-drying for 24 hours.
8. 8. The method for preparing a zirconium-based metal organic gel material according to claim 1, wherein in the step (1), the stirring time is 15min, the mass concentration of the zirconium oxychloride solution is 0.6mol/L, in the step (2), the stirring time is 20min, the mass concentration of the trimesic acid solution is 0.1665mol/L, in the step (3), the stirring time is 20min, the volume ratio of the trimesic acid solution to the zirconium oxychloride solution is 1:0.75, in the step (4), the hydrothermal reaction condition is that the reaction temperature is 140 ℃, the reaction time is 2h, in the freeze drying, the freezing temperature is set to be-50 ℃ by a freeze dryer, and the mixture is taken out after freeze drying for 24 h.
9. 9. Use of a zirconium-based metal organic gel material, characterized in that the zirconium-based metal organic gel material prepared by the method for preparing a zirconium-based metal organic gel material according to any one of claims 1 to 8 is used for the treatment of pulp waste water having a pH of 2 to 12 and containing lignin-type and/or humic acid-type organic substances.
10. 10. The use of the zirconium-based metal organic gel material as claimed in claim 9, wherein when the zirconium-based metal organic gel material is used for treating pulp waste water, the dilution factor of the pulp waste water is 15-25 times, the adding amount of the zirconium-based metal organic gel material is 0.8-1.3wt% of the mass of the diluted pulp waste water, the treatment temperature is 20-35 ℃, and the standing time is 10-15h.

Description

Preparation method and application of zirconium-based metal organic gel material Technical Field The invention relates to the technical field of pulp wastewater treatment. In particular to a preparation method and application of a zirconium-based metal organic gel material. Background Pulp waste water is industrial waste water produced by cotton textile industry. At present, pulp wastewater is mainly treated by adopting technologies such as a physical method, a chemical method, a biological method, membrane separation, advanced oxidation and the like. The chemical coagulation method is one of the main processes for pulp wastewater treatment, however, the technology has the problems of high energy consumption, high operation cost, limited removal efficiency of complex pollutants and the like, and the requirements of pulp wastewater advanced treatment and water resource recycling are difficult to meet. Therefore, in order to reduce pollutants and realize wastewater reclamation, the development of efficient, low-cost and environmentally-friendly flocculants has become a key target of research in the field at the present stage. In recent years, metal-Organic Gels (MOGs) are used as an emerging material, have the characteristics of diversity, adjustable pores, large specific surface area, rich surface functional groups and the like, are widely used in the fields of adsorption separation, catalysis and the like, and are wastewater treatment materials with huge potential. The prior research adopts an organic ligand H 6 TPBTM containing amido and Zr 4+ to assemble, successfully synthesizes a zirconium-based metal-organic gel material (HNU-G6) with stable structure, the rich amido and carboxyl functional groups in the gel material have good adsorption performance on U (VI) and Pb (II), the adsorption capacity respectively reaches 604.3 mg G -1 and 453.2 mg G -1 under the condition of pH=5, and the gel material still maintains excellent adsorption performance and cycle stability in high salinity complex water. Researches report that Cu (II) metal-organic gel (Cu-MOG) has high adsorption capacity of 650.32 mg.g -1 to cationic dye and good recycling performance. The Al/Fe bimetallic-organic gel (JLUE-MOG-4) has also been successfully synthesized, and has good adsorption performance on chlortetracycline, and the adsorption quantity is 1600 mg/g -1. In conclusion, the metal organic gel material has good treatment effect on wastewater containing metal ions, dyes and organic matters, and has wide application prospect. However, the existing metal organic gel materials such as HNU-G6 and MOG-Al/Fe have the defect of narrow pH application range when being used for pulp wastewater treatment, and when the pH change range of pulp wastewater is large, especially the treatment of extreme pH pulp wastewater, the treatment of the metal organic gel materials cannot achieve the expected treatment effect. Therefore, there is a need for further improvements to existing metal organic gel materials to enable them to meet the application requirements of pulp wastewater treatment over a wider pH range. Disclosure of Invention Therefore, the technical problem to be solved by the invention is to provide a preparation method and application of a zirconium-based metal organic gel material, so as to solve the problem that the existing metal organic gel material has a narrower pH application range when treating pulp wastewater. In order to solve the technical problems, the invention provides the following technical scheme: A preparation method of a zirconium-based metal organic gel material comprises the following steps: adding zirconium oxychloride into distilled water, stirring and dissolving at room temperature to obtain a zirconium oxychloride solution, wherein compared with absolute ethyl alcohol, DMF and other polar solvents, the zirconium oxychloride solution prepared by using distilled water as a solvent is easier to form zirconium-based metal organic gel with stable pulp wastewater treatment effect under a wider pH value in the subsequent hydrothermal reaction with a trimesic acid solution with a specific proportion; Compared with distilled water, the use of the absolute ethyl alcohol as the solvent of the trimesic acid can ensure that the trimesic acid with the required concentration is uniformly and stably dispersed and dissolved into the solvent at room temperature, and on the other hand, zirconium-based metal organic gel with wider pH application range can be more easily formed in the hydrothermal reaction of the trimesic acid solution prepared by using the absolute ethyl alcohol as the solvent and the zirconium oxychloride solution prepared by using the distilled water as the solvent; Step (3), mixing the zirconium oxychloride solution and the trimesic acid solution at room temperature, and continuously stirring to obtain a mixed solution; and (4) carrying out hydrothermal reaction on the mixed solution, naturally cooling to room te