Ionic liquid type material, preparation method thereof and application of ionic liquid type material in reinforced microbial salt-resistant material

Abstract

The invention relates to an ionic liquid type material, a preparation method thereof and an application of the ionic liquid type material in a reinforced microbial salt-resistant material. The preparation method comprises the following steps: (1) preparing a Fe-coated CeO2 core-shell material; (2) preparing metal-based ionic liquid; and (3) preparing a material of Fe (at) CeO2 (at) Et3NHCl-CaCl2, a material of Fe (at) CeO2 (at) Et3NHCl-MgCl2 and a material of Fe (at) CeO2 (at) Et3NHCl-KCl. The method can solve the problems of cell dehydration and mass-wall separation caused by high-salt organic wastewater to anaerobic microorganisms, induction of generation of a large amount of active oxygen in the microorganisms, inhibition of metabolic activity and growth of the microorganisms and the like.

Description

Technical Field

[0001] The invention relates to the field of water pollutant treatment, and in particular to an ionic liquid material and a preparation method thereof and application in strengthening microbial salt-tolerant materials. Background Art

[0002] In industrial fields, such as food processing, pharmaceutical manufacturing and leather processing industries, a large amount of high-salinity organic wastewater (HSOW) is generated. HSOW usually contains high levels of salt (>1.0%) and organic matter (COD>2000mg / L). At present, many physical and chemical methods are used to treat HSOW, such as evaporation, coagulation-flocculation, ion exchange and membrane technology. Although these physical and chemical technologies have the characteristics of fast processing speed and flexible operation, these methods have problems such as high energy consumption, poor system stability and secondary pollution. Therefore, seeking economical and effective treatment methods for high-salinity wastewater has always been the focus of researchers in the field of environment. Biological treatment methods have the characteristics of economic savings and high treatment efficiency, so they have attracted widespread attention. However, the enhanced technology of biological treatment of high-salinity wastewater mainly includes gradient acclimation technology, introduction of halophilic microorganisms and addition of compatible substances. However, the gradient acclimation takes a long time and is difficult to adapt to the impact of high-salinity environment. The growth conditions of halophilic microorganisms are harsh, the functional microbial species are scarce, the metabolic activity is unstable, the synthesis of compatible substances is difficult, and the addition cost is high. These technologies are limited in the actual treatment of high-salinity wastewater.

[0003] In the process of biological treatment of high-salinity organic wastewater, the high-salinity environment will inhibit the physiological activities of anaerobic microorganisms (especially methanogens). The high-salinity environment will cause cell dehydration and plasmolysis. The cell osmotic pressure regulation ability of these microorganisms is limited, which will eventually inhibit their metabolic activities and growth. In addition, the high-salinity environment will cause oxidative damage (ROS) to microorganisms and generate a large number of hydroxyl radicals (OH -. ) and superoxide radicals (O -. ). In addition, affected by salinity and organic load, the ORP of high-salinity organic wastewater fluctuates greatly, which leads to reduced microbial activity, changes in the structure of microbial communities, and poor stability of the anaerobic digestion system under high-salinity conditions. The treatment effect is prone to fluctuations, resulting in unstable treatment process and unsatisfactory wastewater treatment effect.

[0004] Therefore, it is more practical to improve the salt tolerance of microorganisms in bioreactors and enhance the stability of microorganisms in toxic and harmful environments. The preparation of materials that can enhance the salt tolerance of microorganisms is an urgent problem to be solved in the current treatment of high-salinity wastewater. Summary of the invention

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

[0006] Technical solution: A method for preparing an ionic liquid material, comprising the following steps: 1) Fe@CeO 2 Preparation of core-shell material: dissolving iron salt in deoxygenated water, adding chitosan, acetic acid and polyvinyl alcohol in an oxygen-free environment and stirring to form a light yellow solution A, wherein the mass ratio of the iron salt, chitosan, acetic acid and polyvinyl alcohol is 1:(1-10):(1-5):(1-5); dissolving cerium nitrate in deoxygenated water to form solution B, wherein the ratio of cerium nitrate to iron salt is (1-10):1; dropping solution A into 1wt.% NaOH solution to form microspheres, then adding the microspheres into solution B, drying after centrifugation, and calcining at 600-800°C to form Fe@CeO 2 Core-shell materials; 2) Preparation of metal-based ionic liquids: In a nitrogen atmosphere, triethylamine hydrochloride (Et 3 NHCl) are mixed with metal salts, wherein the metal salt is calcium salt, magnesium salt or potassium salt, and the mass ratio of triethylamine hydrochloride to the metal salt is 1:(1-20), stirred and condensed under reflux at 60-120°C for 5-20h, after the reaction is completed, the reaction solution is cooled to room temperature, the reaction solution is collected, and dried at 80°C for 6h to obtain Et 3 NHCl-CaCl 2 , Et 3 NHCl-MgCl 2 , Et 3 NHCl-KCl; 3)Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et 3 NHCl-MgCl 2 and Fe@CeO 2 @Et 3 Preparation of NHCl-KCl materials: The prepared Fe@CeO 2 The core-shell material is placed in the product obtained in step 2 to form Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et3 NHCl-MgCl 2 、Fe@CeO 2 @Et 3 NHCl-KCl material; or, the prepared Fe@CeO 2 The core-shell material, tetraethyl orthosilicate and anhydrous ethanol are mixed and stirred, and heated to 60°C. The product obtained in step 2 is dissolved in anhydrous ethanol, and 1% to 15% 5 mol / L hydrochloric acid is added dropwise. After forming a gel, it is aged at 60°C for 1 to 48 hours, and then dried at 110°C for 4 hours to obtain the desired metal-based ionic liquid material Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et 3 NHCl-MgCl 2 and Fe@CeO 2 @Et 3 NHCl-KCl.

[0007] Preferably, the iron salt is FeCl 3 、FeSO 4 or Fe(NO 3 ) 3 .

[0008] Preferably, the calcium salt is CaCl 2 、CaSO 4 or CaCO 3 .

[0009] Preferably, the magnesium salt is MgCl 2 MgSO 4 .

[0010] Preferably, the potassium salt is KCl.

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

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

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

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

[0015] The application of the above-mentioned ionic liquid type material in a microbial system for enhancing the salt tolerance of microorganisms.

[0016] Beneficial effect: Fe@CeO prepared by the present invention 2 @Et 3 NHCl-CaCl 2、Fe@CeO 2 @Et 3 NHCl-MgCl 2 、Fe@CeO 2 @Et 3 NHCl-KCl material can solve the problems of cell dehydration, plasmolysis, induction of a large amount of active oxygen in microorganisms, inhibition of metabolic activity and growth caused by high-salt organic wastewater on anaerobic microorganisms. On the one hand, this material can + or Mg2 + or Ca 2+ It can bind to specific sites or channels on the microbial cell membrane and competitively block the Na + Binds to these sites or channels, stabilizes the structure of the cell membrane, reduces membrane fluidity and permeability, and thus limits Na + The osmotic pressure of microbial cells is kept stable, thus maintaining the normal growth and reproduction of microorganisms. 2 ) can pass Ce 3+ / Ce 4+ The material can simulate the activity of natural enzymes such as superoxide dismutase (SOD) and catalase (CAT) to reduce the harm of ROS in high-salt wastewater to microorganisms. 0 The corrosion effect of oxygen can be reduced, and the long-term stability of ORP in the anaerobic digestion system can be maintained, thereby ensuring that the anaerobic system has good microbial activity, good microbial community structure and extracellular electron transfer performance, thereby 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Blank group, Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et 3 NHCl-MgCl 2 、Fe@CeO 2 @Et 3 NHCl-KCl microbial phenotypic characteristics at a salinity of 6%.

[0018] Figure 2 Blank group, Fe@CeO 2 @Et 3 NHCl-CaCl 2 The effect diagram of petrochemical wastewater treatment in a petrochemical company when the reactor volume is 100L, the salinity is 6%, and the COD concentration is 10000mg / L.

[0019] Figure 3 Blank group, Fe@CeO 2 @Et 3 NHCl-CaCl 2 This is the effect of microbial biofilm formation in a petrochemical company when the reactor volume is 100L, the salinity is 6%, and the COD concentration is 10000mg / L.

[0020] Figure 4 Blank group, Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et 3 NHCl-MgCl 2 、Fe@CeO 2 @Et 3 NHCl-KCl treated water sample at a petrochemical company when the reactor volume is 100L, the salinity is 6%, and the COD concentration is 10000mg / L.

[0021] Figure 5 Blank group, Fe@CeO 2 @Et 3 NHCl-CaCl 2 ORP changes over 36 days when the reactor volume is 100 L and the salinity is 6%.

[0022] Figure 6 Fe@CeO 2 @Et 3 NHCl-CaCl 2 、Fe@CeO 2 @Et 3 NHCl-MgCl 2 、Fe@CeO 2 @Et 3 The TOC removal effect of NHCl-KCl when the salinity is 6%, the pollutant is terephthalic acid, and the TOC is 3000 mg / L.

[0023] Figure 7 The graphs show the degradation effects of m-lignin in ten embodiments when the salinity is 3%, the pollutant is lignin, and the m-lignin concentration is 10000 mg / L.

[0024] Figure 8 The graphs show the degradation effects of PAHs in ten embodiments when the salinity is 5%, the pollutants are PAHs, and the PAHs concentration is 5000 mg / L. DETAILED DESCRIPTION

[0025] Example 1

[0026] In this embodiment, Co@CeO 2 The specific preparation method of @C core-shell material is as follows:

[0027] (1) 10 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 10 g of chitosan, 10 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 1h to form Fe@CeO 2 Core-shell materials;

[0028] (2) In a nitrogen atmosphere, take 10 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g CaCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-CaCl 2 ;

[0029] (3) The prepared Fe@CeO 2 Placed in metal-based ionic liquid and immersed for 24 h, Fe@CeO 2 @Et 3 NHCl-CaCl 2 Material.

[0030] The prepared Fe@CeO 2 @Et 3 NHCl-CaCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0031] Example 2

[0032] (1) 10 g FeSO 4 Dissolve in 500 mL of deoxygenated water, add 20 g of chitosan, 15 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 1h to form Fe@CeO 2 Core-shell materials;

[0033] (2) In a nitrogen atmosphere, take 10 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g CaCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-CaCl 2 ;

[0034] (3) The prepared Fe@CeO 2 10 mL of ethyl orthosilicate and 50 mL of anhydrous ethanol were placed in a three-necked flask, stirred and heated to 60 ° C, and the temperature was kept constant. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask, and 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After the gel was formed, it 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 Fe@CeO 2 @Et 3 NHCl-CaCl 2 Material.

[0035] The prepared Fe@CeO 2 @Et 3 NHCl-CaCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0036] Example 3

[0037] (1) 15 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 30 g of chitosan, 10 mL of acetic acid, and 20 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 8h. Finally, it was placed in a tube furnace and calcined at 600℃ for 4h to form Fe@CeO 2 Core-shell materials;

[0038] (2) In a nitrogen atmosphere, take 15 g of triethylamine hydrochloride (Et 3 NHCl) and 45 g MgCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-MgCl 2 ;

[0039] (3) The prepared Fe@CeO 2 Placed in metal-based ionic liquid and immersed for 48h, Fe@CeO 2 @Et 3 NHCl-MgCl 2 Material.

[0040] The prepared Fe@CeO 2 @Et 3 NHCl-MgCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0041] Example 4

[0042] (1) 5 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 20 g of chitosan, 10 mL of acetic acid, and 15 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 3h to form Fe@CeO 2 Core-shell materials;

[0043] (2) In a nitrogen atmosphere, take 20 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g KCl were placed in a 100 mL round-bottom flask, stirred and condensed under reflux for 12 h at 100 °C. 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 Et 3 NHCl-KCl;

[0044] (3) The prepared Fe@CeO 2 Placed in metal-based ionic liquid and immersed for 36 h, Fe@CeO 2 @Et 3 NHCl-KCl material.

[0045] The prepared Fe@CeO 2 @Et 3 NHCl-KCl is used to enhance the salt tolerance of microorganisms in microbial systems, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation effects.

[0046] Example 5

[0047] (1) 35 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 40 g of chitosan, 10 mL of acetic acid, and 35 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 1h to form Fe@CeO 2 Core-shell materials;

[0048] (2) In a nitrogen atmosphere, take 35 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g MgCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 18 h to obtain Et 3 NHCl-MgCl 2 ;

[0049] (3) The prepared Fe@CeO 2 Placed in metal-based ionic liquid and immersed for 24 h, Fe@CeO 2 @Et 3 NHCl-MgCl 2 Material.

[0050] The prepared Fe@CeO 2 @Et 3 NHCl-MgCl 2It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0051] Example 6

[0052] (1) 10 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 10 g of chitosan, 10 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80°C for 6h. Finally, it was placed in a tube furnace and calcined at 800°C for 2h to form Fe@CeO 2 Core-shell materials;

[0053] (2) In a nitrogen atmosphere, take 25 g of triethylamine hydrochloride (Et 3 NHCl) and 30g KCl were placed in a 100mL round-bottom flask, stirred and condensed under reflux at 100°C for 18h. 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 6h to obtain Et 3 NHCl-KCl;

[0054] (3) The prepared Fe@CeO 2 Place in Et 3 After immersion in NHCl-KCl metal-based ionic liquid for 12 h, Fe@CeO 2 @Et 3 NHCl-KCl material.

[0055] The prepared Fe@CeO 2 @Et 3 NHCl-KCl is used to enhance the salt tolerance of microorganisms in microbial systems, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability, and pollutant degradation effects.

[0056] Example 7

[0057] (1) 25 g FeSO 4 Dissolve in 500 mL of deoxygenated water, add 15 g of chitosan, 10 mL of acetic acid, and 30 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 2h to form Fe@CeO 2 Core-shell materials;

[0058] (2) In a nitrogen atmosphere, take 15 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g CaCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-CaCl 2 ;

[0059] (3) The prepared Fe@CeO 2 10 mL of ethyl orthosilicate and 50 mL of anhydrous ethanol were placed in a three-necked flask, stirred and heated to 60 ° C, and the temperature was kept constant. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask, and 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After the gel was formed, it 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 Fe@CeO 2 @Et 3 NHCl-CaCl 2 Material.

[0060] The prepared Fe@CeO 2 @Et 3 NHCl-CaCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0061] Example 8

[0062] (1) 20 g FeSO 4 Dissolve in 500 mL of deoxygenated water, add 20 g of chitosan, 10 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 3h to form Fe@CeO 2 Core-shell materials;

[0063] (2) In a nitrogen atmosphere, take 10 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g MgCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-MgCl 2 ;

[0064] (3) The prepared Fe@CeO 2 10 mL of ethyl orthosilicate and 50 mL of anhydrous ethanol were placed in a three-necked flask, stirred and heated to 60 ° C, and the temperature was kept constant. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask, and 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After the gel was formed, it 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 Fe@CeO 2 @Et 3 NHCl-MgCl 2 Material.

[0065] The prepared Fe@CeO 2 @Et 3 NHCl-MgCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0066] Example 9

[0067] (1) 20 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 10 g of chitosan, 10 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80℃ for 6h. Finally, it was placed in a tube furnace and calcined at 600℃ for 1h to form Fe@CeO 2 Core-shell materials;

[0068] (2) In a nitrogen atmosphere, take 10 g of triethylamine hydrochloride (Et 3 NHCl) and 30 g CaCl 2In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 12 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-CaCl 2 ;

[0069] (3) The prepared Fe@CeO 2 10 mL of ethyl orthosilicate and 50 mL of anhydrous ethanol were placed in a three-necked flask, stirred and heated to 60 ° C, and the temperature was kept constant. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask, and 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After the gel was formed, it 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 Fe@CeO 2 @Et 3 NHCl-CaCl 2 Material.

[0070] The prepared Fe@CeO 2 @Et 3 NHCl-CaCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0071] Example 10

[0072] (1) 10 g FeCl 3 Dissolve in 500 mL of deoxygenated water, add 20 g of chitosan, 30 mL of acetic acid, and 10 g of polyvinyl alcohol and stir vigorously in an oxygen-free environment to form a light yellow solution A. 3 ) 3 Dissolved in deoxygenated water to form solution B. Then solution A was added dropwise to 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B for reaction, centrifuged and placed in a vacuum drying oven at 80°C for 8h. Finally, it was placed in a tube furnace and calcined at 800°C for 2h to form Fe@CeO 2 Core-shell materials;

[0073] (2) In a nitrogen atmosphere, take 10 g of triethylamine hydrochloride (Et 3 NHCl) and 10 g MgCl 2 In a 100 mL round-bottom flask, stir and condense under reflux at 100 °C for 10 h. After the reaction is completed, the reaction solution is cooled to room temperature. The reaction solution is collected and transferred to a vacuum drying oven and dried at 80 °C for 6 h to obtain Et 3 NHCl-MgCl 2 ;

[0074] (3) The prepared Fe@CeO 2 10 mL of ethyl orthosilicate and 50 mL of anhydrous ethanol were placed in a three-necked flask, stirred and heated to 60 ° C, and the temperature was kept constant. The ionic liquid was dissolved in anhydrous ethanol and added to the three-necked flask, and 10 mL of 5 mol / L hydrochloric acid was slowly added dropwise. After the gel was formed, it 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 Fe@CeO 2 @Et 3 NHCl-MgCl 2 Material.

[0075] The prepared Fe@CeO 2 @Et 3 NHCl-MgCl 2 It is used in microbial systems to enhance the salt tolerance of microorganisms, improve the biological system's resistance to high-salt environments, microbial community structure, abundance, ORP stability and pollutant degradation effects.

[0076] The present invention is not limited to the above-mentioned embodiments. For ordinary technicians in this technical field, after knowing the contents recorded in the present invention, they can make several equivalent changes and substitutions without departing from the principle of the present invention. These equivalent changes and substitutions should also be regarded as belonging to the protection scope of the present invention.

Claims

1. A method for preparing an ionic liquid material, characterized in that: The following steps are involved: 1) Preparation of Fe@CeO2 core-shell material: dissolve iron salt in deoxygenated water, add chitosan, acetic acid and polyvinyl alcohol in an oxygen-free environment and stir to form a light yellow solution A, wherein the mass ratio of the iron salt, chitosan, acetic acid and polyvinyl alcohol is 1:(1-10):(1-5):(1-5); dissolve cerium nitrate in deoxygenated water to form a solution B, wherein the ratio of cerium nitrate to iron salt is (1-10):1; Solution A was added dropwise to a 1wt.% NaOH solution to form microspheres, and then the microspheres were added to solution B, dried after centrifugation, and calcined at 600-800°C to form Fe@CeO2 core-shell materials; 2) Preparation of metal-based ionic liquids: In a nitrogen atmosphere, triethylamine hydrochloride (Et3NHCl) was mixed with metal salts, wherein the metal salts were calcium salts, magnesium salts or potassium salts, and the mass ratio of triethylamine hydrochloride to metal salts was 1: (1-20). The mixture was stirred and condensed under reflux at 60-120°C for 5-20 h. After the reaction was completed, the reaction solution was cooled to room temperature, the reaction solution was collected, and dried at 80°C for 6 h. h, 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: by impregnation, in a nitrogen atmosphere, placing the prepared Fe@CeO2 core-shell material in the product obtained in step 2 to form Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@ Et3NHCl-MgCl2, and Fe@CeO2@Et3NHCl-KCl materials; or, mixing the prepared Fe@CeO2 core-shell material, tetraethyl orthosilicate, and anhydrous ethanol, and heating to 60°C, dissolving the product obtained in step 2 in anhydrous ethanol, and dropping 1%~15% 5mol / L hydrochloric acid to form a gel, and aging at 60°C for 1~48 h, and then dried at 110 °C for 4 h to obtain the desired metal-based ionic liquid materials Fe@CeO2@Et3NHCl-CaCl2, Fe@CeO2@ Et3NHCl-MgCl2 and Fe@CeO2@Et3NHCl-KCl.

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 salt is MgCl2 or MgSO4.

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

6. The method for preparing the ionic liquid material according to claim 1, characterized in that: The mass ratio of the triethylamine hydrochloride to the metal salt is 1:1.

2.

7. The method for preparing the ionic liquid material according to claim 1, characterized in that: The condensation reflux reaction time is 1 to 48 h.

8. The method for preparing the ionic liquid material according to claim 1, characterized in that: The drying time is 1 to 48 hours.

9. The ionic liquid material obtained by the method according to any one of claims 1 to 8.

10. Use of the ionic liquid material according to claim 9 in a microbial system for enhancing the salt tolerance of microorganisms.

Images