Ionic liquid type material, its preparation method and application in salt-tolerant microbial material

Abstract

The application relates to an ionic liquid type material, a preparation method thereof and application thereof in a salt-tolerant microbial material, and comprises the following steps: 1) preparation of a Fe@CeO2 core-shell material; 2) preparation of a metal-based ionic liquid; and 3) preparation of Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl materials. The application can solve the problems of cell dehydration, protoplasmic separation, induction of a large number of active oxygen in the microorganism, inhibition of metabolic activity and growth of the microorganism caused by high-salt organic wastewater.

Description

Technical Field

[0001] This invention relates to the field of water pollutant treatment, specifically to an ionic liquid material, its preparation method, and its application in reinforced microbial salt-tolerant materials. Background Technology

[0002] In industrial sectors such as food processing, pharmaceutical manufacturing, and leather processing, large quantities of high-salinity organic wastewater (HSOW) are generated. HSOW typically contains high levels of salt (>1.0%) and organic matter (COD>2000 mg / L). Currently, many physicochemical methods are used to treat HSOW, such as evaporation, coagulation-flocculation, ion exchange, and membrane technology. While these physicochemical technologies offer advantages such as fast treatment speed and flexible operation, they also suffer from high energy consumption, poor system stability, and secondary pollution. Therefore, finding an economical and effective treatment method for high-salinity wastewater has always been a focus of research in the environmental field. Biological treatment methods are widely recognized for their economic efficiency and high treatment efficiency. However, the main enhanced technologies for biological treatment of high-salinity wastewater include gradient acclimation, the introduction of halophilic microorganisms, and the addition of compatible substances. However, the long acclimation time required for gradient acclimation, the difficulty in adapting to shock-induced high-salinity environments, the demanding growth conditions of halophilic microorganisms, the scarcity of functional microorganisms, unstable metabolic activity, and the difficulty and high cost of synthesizing compatible substances limit the practical application of these technologies in high-salinity wastewater treatment.

[0003] In the biological treatment of high-salt organic wastewater, the high-salt environment inhibits the physiological activities of anaerobic microorganisms, especially methanogens. High salinity leads to cell dehydration and plasmolysis; these microorganisms have limited osmotic pressure regulation capabilities, ultimately inhibiting their metabolic activities and growth. Furthermore, high salinity causes oxidative damage (ROS) to microorganisms, generating large amounts of hydroxyl radicals (OH-). -. ) and superoxide radicals (O -. Furthermore, the ORP of high-salt organic wastewater fluctuates significantly due to the influence of salinity and organic load, which leads to reduced microbial activity, changes in microbial community structure, and poor stability of the anaerobic digestion system under high-salt conditions. This results in fluctuating treatment effects, unstable treatment processes, and unsatisfactory wastewater treatment outcomes.

[0004] Therefore, improving the salt tolerance of microorganisms in bioreactors and enhancing their stability in toxic and harmful environments is of practical significance. Developing materials that can enhance the salt tolerance of microorganisms is a pressing issue in the treatment of high-salt wastewater. Summary of the Invention

[0005] Technical problem to be solved: In order to address the problem of high salinity inhibiting the growth and reproduction of microorganisms in the process of biological treatment of high salinity wastewater, to enhance the resistance of non-halophilic microorganisms to the high salinity environment in high salinity wastewater, and to improve the poor ORP stability of anaerobic digestion systems under high salinity conditions, poor microbial community structure and low abundance of degrading bacteria, and unstable and unsatisfactory wastewater treatment process, this invention provides an ionic liquid material, its preparation method, and its application in enhancing microbial salt tolerance materials.

[0006] Technical Solution: A method for preparing an ionic liquid material, comprising the following steps: 1) Preparation of Fe@CeO2 core-shell material: Iron salt is dissolved in deoxygenated water, and chitosan, acetic acid, and polyvinyl alcohol are added and stirred in an anaerobic environment to form a pale yellow solution A, wherein the mass ratio of iron salt, chitosan, acetic acid, and polyvinyl alcohol is 1:(1-10):(1-5):(1-5); Cerium nitrate is dissolved in deoxygenated water to form solution B, wherein the ratio of cerium nitrate to iron salt is (1-10):1; Solution A is added dropwise to a 1wt.% NaOH solution to form microspheres, and then the microspheres are added to... 1) Add to solution B, centrifuge and dry, then calcine at 600-800℃ to form Fe@CeO2 core-shell material; 2) Preparation of metal-based ionic liquid: Under a nitrogen atmosphere, triethylamine hydrochloride (Et3NHCl) is mixed with a metal salt, wherein the metal salt is a calcium salt, magnesium salt or potassium salt, and the mass ratio of triethylamine hydrochloride to metal salt is 1:(1~20). The mixture is stirred and refluxed at 60~120℃ for 5~20h. After the reaction is completed, the reaction solution is cooled to room temperature, collected, and dried at 80℃ for 6h to obtain Et3NHCl-CaCl2. Et3NHCl-MgCl2, Et3NHCl-KCl; 3) Preparation of Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl materials: By impregnation method, in a nitrogen atmosphere, the prepared Fe@CeO2 core-shell material is placed in the product obtained in step 2 to form Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2, Fe@CeO2@Et3NHCl-KCl materials. NHCl-KCl material; or, mix and stir the prepared Fe@CeO2 core-shell material, tetraethyl orthosilicate and anhydrous ethanol, and heat to 60°C. Dissolve the product obtained in step 2 in anhydrous ethanol, add 1% to 15% of 5mol / L hydrochloric acid dropwise, and after forming a gel, age at 60°C for 1 to 48 hours, and then dry at 110°C for 4 hours to obtain the desired metal-based ionic liquid materials Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl.

[0007] Preferably, the iron salt is FeCl3, FeSO4 or Fe(NO3)3.

[0008] Preferably, the calcium salt is CaCl2, CaSO4 or CaCO3.

[0009] Preferably, the magnesium salts mentioned above are MgCl2 and MgSO4.

[0010] Preferably, the potassium salt is KCl.

[0011] Preferably, the mass ratio of the above triethylamine hydrochloride to the metal salt is 1:1.2.

[0012] The above-mentioned condensation reflux reaction time is 1 to 48 hours.

[0013] The drying time is 1 to 48 hours.

[0014] The ionic liquid material prepared by the above method.

[0015] The application of the above-mentioned ionic liquid materials in microbial systems that enhance the salt tolerance of microorganisms.

[0016] Beneficial effects: The Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2, and Fe@CeO2@Et3NHCl-KCl materials prepared in this invention can address the problems caused by high-salt organic wastewater on anaerobic microorganisms, such as cell dehydration, plasmolysis, induction of large amounts of reactive oxygen species within microorganisms, and inhibition of their metabolic activities and growth. This material, on the one hand, can utilize K... + or Mg2 + or Ca 2+ It can bind to specific sites or channels on the microbial cell membrane, competitively preventing Na+ from binding. + It binds to these sites or channels, stabilizes the cell membrane structure, reduces membrane fluidity and permeability, thereby limiting Na+ absorption. + Cerium dioxide (CeO2) enters through the channels of CeO2, maintaining the osmotic pressure stability of microbial cells and thus sustaining their normal growth and reproduction. On the other hand, cerium dioxide (CeO2) can pass through CeO2... 3+ / Ce 4+ This material mimics the activity of natural enzymes such as superoxide dismutase (SOD) and catalase (CAT), reducing the harmful effects of ROS on microorganisms in high-salt wastewater. Furthermore, this material can utilize Fe... 0 The corrosive effect maintains the long-term stability of the ORP in the anaerobic digestion system, thereby ensuring that the anaerobic system has good microbial activity, good microbial community structure and extracellular electron transfer performance, thus enhancing the interaction between microorganisms, promoting the conversion of VFA to methane, further enhancing the degradation performance of pollutants, and realizing the resource utilization of wastewater. Attached Figure Description

[0017] Figure 1 The diagram shows the phenotypic characteristics of microorganisms in the blank group, Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2, and Fe@CeO2@Et3NHCl-KCl at a salinity of 6%.

[0018] Figure 2 The diagram shows the treatment effect of Fe@CeO2@Et3NHCl-CaCl2 on petrochemical wastewater in a petrochemical company with a reactor volume of 100L, a salinity of 6%, and a COD concentration of 10000mg / L, serving as the blank group.

[0019] Figure 3 The image shows the microbial biofilm formation effect of Fe@CeO2@Et3NHCl-CaCl2 in a petrochemical company with a reactor volume of 100L, a salinity of 6%, and a COD concentration of 10000mg / L.

[0020] Figure 4 The images show water samples after treatment at a petrochemical company, including the blank group, Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2, and Fe@CeO2@Et3NHCl-KCl, with a reactor volume of 100L, a salinity of 6%, and a COD concentration of 10000 mg / L.

[0021] Figure 5 The ORP changes over 36 days for the blank group and Fe@CeO2@Et3NHCl-CaCl2 in a reactor with a volume of 100L and a salinity of 6%.

[0022] Figure 6 The image shows the TOC removal effect of Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2, and Fe@CeO2@Et3NHCl-KCl at a salinity of 6%, with terephthalic acid as the pollutant and a TOC of 3000 mg / L.

[0023] Figure 7 The graph shows the degradation effect of lignin in ten examples at a salinity of 3%, with lignin as the pollutant and a lignin concentration of 10000 mg / L.

[0024] Figure 8 The graph shows the degradation effect of polycyclic aromatic hydrocarbons (PAHs) in ten examples at a salinity of 5%, with PAHs as the pollutant and a PAH concentration of 5000 mg / L. Detailed Implementation

[0025] Example 1

[0026] In this embodiment, the specific preparation method of the Co@CeO2@C core-shell material is as follows:

[0027] (1) Dissolve 10g FeCl3 in 500mL deoxygenated water. In an oxygen-free environment, add 10g chitosan, 10mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 1h to form Fe@CeO2 core-shell material;

[0028] (2) Under a nitrogen atmosphere, 10 g of triethylamine hydrochloride (Et3NHCl) and 10 g of CaCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-CaCl2;

[0029] (3) The prepared Fe@CeO2 was placed in a metal-based ionic liquid and impregnated for 24 hours in a nitrogen atmosphere by impregnation method to form Fe@CeO2@Et3NHCl-CaCl2 material.

[0030] The prepared Fe@CeO2@Et3NHCl-CaCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0031] Example 2

[0032] (1) Dissolve 10g FeSO4 in 500mL deoxygenated water. In an anaerobic environment, add 20g chitosan, 15mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 1h to form Fe@CeO2 core-shell material;

[0033] (2) Under a nitrogen atmosphere, 10 g of triethylamine hydrochloride (Et3NHCl) and 10 g of CaCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-CaCl2;

[0034] (3) Using the sol-gel method, the prepared Fe@CeO2 was placed in a three-necked flask containing 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol. The mixture was stirred and heated to 60 °C and kept at a constant temperature. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask. 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After gel formation, the mixture was aged at 60 °C for 24 h and then dried in a vacuum drying oven at 110 °C for 1 h to finally form the Fe@CeO2@Et3NHCl-CaCl2 material.

[0035] The prepared Fe@CeO2@Et3NHCl-CaCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0036] Example 3

[0037] (1) Dissolve 15g FeCl3 in 500mL deoxygenated water. In an anaerobic environment, add 30g chitosan, 10mL acetic acid, and 20g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 8h. Finally, place in a tube furnace and calcine at 600℃ for 4h to form Fe@CeO2 core-shell material;

[0038] (2) Under a nitrogen atmosphere, 15 g of triethylamine hydrochloride (Et3NHCl) and 45 g of MgCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-MgCl2;

[0039] (3) The prepared Fe@CeO2 was placed in a metal-based ionic liquid in a nitrogen atmosphere by impregnation for 48 hours to form Fe@CeO2@Et3NHCl-MgCl2 material.

[0040] The prepared Fe@CeO2@Et3NHCl-MgCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0041] Example 4

[0042] (1) Dissolve 5g FeCl3 in 500mL deoxygenated water. In an anaerobic environment, add 20g chitosan, 10mL acetic acid, and 15g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 20g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 3h to form Fe@CeO2 core-shell material;

[0043] (2) Under a nitrogen atmosphere, 20 g of triethylamine hydrochloride (Et3NHCl) and 10 g of KCl were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 12 h. After the reaction was completed, the reaction solution was allowed to cool to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-KCl;

[0044] (3) The prepared Fe@CeO2 was placed in a metal-based ionic liquid and impregnated for 36 hours in a nitrogen atmosphere by impregnation method to form Fe@CeO2@Et3NHCl-KCl material.

[0045] The prepared Fe@CeO2@Et3NHCl-KCl was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0046] Example 5

[0047] (1) Dissolve 35g FeCl3 in 500mL deoxygenated water. In an anaerobic environment, add 40g chitosan, 10mL acetic acid, and 35g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 1h to form Fe@CeO2 core-shell material;

[0048] (2) Under a nitrogen atmosphere, 35 g of triethylamine hydrochloride (Et3NHCl) and 10 g of MgCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 18 h to obtain Et3NHCl-MgCl2;

[0049] (3) The prepared Fe@CeO2 was placed in a metal-based ionic liquid and impregnated for 24 hours in a nitrogen atmosphere by impregnation method to form Fe@CeO2@Et3NHCl-MgCl2 material.

[0050] The prepared Fe@CeO2@Et3NHCl-MgCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0051] Example 6

[0052] (1) Dissolve 10g FeCl3 in 500mL deoxygenated water. In an oxygen-free environment, add 10g chitosan, 10mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 30g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 800℃ for 2h to form Fe@CeO2 core-shell material;

[0053] (2) Under a nitrogen atmosphere, 25 g of triethylamine hydrochloride (Et3NHCl) and 30 g of KCl were placed in a 100 mL round-bottom flask and stirred and refluxed at 100 °C for 18 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-KCl;

[0054] (3) The prepared Fe@CeO2 was placed in Et3NHCl-KCl metal-based ionic liquid under a nitrogen atmosphere by impregnation method and impregnated for 12h to form Fe@CeO2@Et3NHCl-KCl material.

[0055] The prepared Fe@CeO2@Et3NHCl-KCl was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0056] Example 7

[0057] (1) Dissolve 25g FeSO4 in 500mL deoxygenated water. In an anaerobic environment, add 15g chitosan, 10mL acetic acid, and 30g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 2h to form Fe@CeO2 core-shell material;

[0058] (2) Under a nitrogen atmosphere, 15 g of triethylamine hydrochloride (Et3NHCl) and 10 g of CaCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was allowed to cool to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-CaCl2;

[0059] (3) Using the sol-gel method, the prepared Fe@CeO2 was placed in a three-necked flask containing 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol. The mixture was stirred and heated to 60 °C and kept at a constant temperature. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask. 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After gel formation, the mixture was aged at 60 °C for 24 h and then dried in a vacuum drying oven at 110 °C for 1 h to finally form the Fe@CeO2@Et3NHCl-CaCl2 material.

[0060] The prepared Fe@CeO2@Et3NHCl-CaCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0061] Example 8

[0062] (1) Dissolve 20g FeSO4 in 500mL deoxygenated water. In an oxygen-free environment, add 20g chitosan, 10mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 3h to form Fe@CeO2 core-shell material;

[0063] (2) Under a nitrogen atmosphere, 10 g of triethylamine hydrochloride (Et3NHCl) and 10 g of MgCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-MgCl2;

[0064] (3) Using the sol-gel method, the prepared Fe@CeO2 was placed in a three-necked flask containing 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol. The mixture was stirred and heated to 60 °C and kept at a constant temperature. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask. 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After gel formation, the mixture was aged at 60 °C for 48 h and then dried in a vacuum drying oven at 110 °C for 2 h to finally form the Fe@CeO2@Et3NHCl-MgCl2 material.

[0065] The prepared Fe@CeO2@Et3NHCl-MgCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0066] Example 9

[0067] (1) Dissolve 20g FeCl3 in 500mL deoxygenated water. In an oxygen-free environment, add 10g chitosan, 10mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 10g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 6h. Finally, place in a tube furnace and calcine at 600℃ for 1h to form Fe@CeO2 core-shell material;

[0068] (2) Under a nitrogen atmosphere, 10 g of triethylamine hydrochloride (Et3NHCl) and 30 g of CaCl2 were placed in a 100 mL round-bottom flask, and the mixture was stirred and refluxed at 100 °C for 12 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-CaCl2;

[0069] (3) Using the sol-gel method, the prepared Fe@CeO2 was placed in a three-necked flask containing 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol. The mixture was stirred and heated to 60 °C and kept at a constant temperature. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask. 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After gel formation, the mixture was aged at 60 °C for 18 h and then dried in a vacuum drying oven at 110 °C for 2 h to finally form the Fe@CeO2@Et3NHCl-CaCl2 material.

[0070] The prepared Fe@CeO2@Et3NHCl-CaCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0071] Example 10

[0072] (1) Dissolve 10g FeCl3 in 500mL deoxygenated water. In an anaerobic environment, add 20g chitosan, 30mL acetic acid, and 10g polyvinyl alcohol, and stir vigorously to form a pale yellow solution A. Dissolve 15g Ce(NO3)3 in deoxygenated water to form solution B. Then, add solution A dropwise to 1wt.% NaOH solution to form microspheres. Add the microspheres to solution B to react, centrifuge, and place in a vacuum drying oven to dry at 80℃ for 8h. Finally, place in a tube furnace and calcine at 800℃ for 2h to form Fe@CeO2 core-shell material;

[0073] (2) Under a nitrogen atmosphere, 10 g of triethylamine hydrochloride (Et3NHCl) and 10 g of MgCl2 were placed in a 100 mL round-bottom flask and stirred and refluxed at 100 °C for 10 h. After the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et3NHCl-MgCl2;

[0074] (3) Using the sol-gel method, the prepared Fe@CeO2 was placed in a three-necked flask containing 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol. The mixture was stirred and heated to 60 °C and kept at a constant temperature. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask. 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After gel formation, the mixture was aged at 60 °C for 24 h and then dried in a vacuum drying oven at 110 °C for 1 h to finally form the Fe@CeO2@Et3NHCl-MgCl2 material.

[0075] The prepared Fe@CeO2@Et3NHCl-MgCl2 was used in a microbial system to enhance the salt tolerance of microorganisms, thereby improving the system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation efficiency.

[0076] This invention is not limited to the above-described embodiments. For those skilled in the art, after learning the contents described in this invention, several equivalent modifications and substitutions can be made without departing from the principle of this invention, and these equivalent modifications and substitutions should also be considered to fall within the protection scope of this invention.

Claims

1. A method for preparing an ionic liquid material, characterized in that, Includes the following steps: 1) Preparation of Fe@CeO2 core-shell material: Iron salt was dissolved in deoxygenated water, and chitosan, acetic acid, and polyvinyl alcohol were added and stirred in an anaerobic environment to form a pale yellow solution A. The mass ratio of iron salt, chitosan, acetic acid, and polyvinyl alcohol was 1:(1~10):(1~5):(1~5); Cerium nitrate was dissolved in deoxygenated water to form solution B. The mass ratio of cerium nitrate to iron salt was (1~10):

1. Solution A was added dropwise to a 1 wt.% NaOH solution to form microspheres. The microspheres were then added to solution B, centrifuged, dried, and calcined at 600-800℃ to form Fe@CeO2 core-shell material. 2) Preparation of metal-based ionic liquids: Under a nitrogen atmosphere, triethylamine hydrochloride (Et3NHCl) was mixed with a metal salt, wherein the metal salt was a calcium salt, magnesium salt or potassium salt, and the mass ratio of triethylamine hydrochloride to metal salt was 1:(1~20). The mixture was stirred and refluxed at 60~120℃ for 5~20h. After the reaction was completed, the reaction solution was cooled to room temperature, collected, and dried at 80℃ for 6h to obtain Et3NHCl-CaCl2, Et3NHCl-MgCl2, and Et3NHCl-KCl. 3) Preparation of Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl materials: The prepared Fe@CeO2 core-shell material was placed in the product obtained in step 2 by impregnation in a nitrogen atmosphere to form Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl materials.

2. The method for preparing the ionic liquid material according to claim 1, characterized in that, The iron salt is FeCl3, FeSO4, or Fe(NO3)3.

3. The method for preparing the ionic liquid material according to claim 1, characterized in that, The calcium salt is CaCl2, CaSO4, or CaCO3.

4. The method for preparing the ionic liquid material according to claim 1, characterized in that, The magnesium salts are MgCl2 and MgSO4.

5. The method for preparing the ionic liquid material according to claim 1, characterized in that, The potassium salt is KCl.

6. An ionic liquid material prepared by any one of the methods described in claims 1-5.

7. The application of the ionic liquid material of claim 6 in a microbial system for enhancing the salt tolerance of microorganisms.

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