Metal-organic framework-super cross-linked polymer composites, methods of making and applications

Abstract

The application discloses a metal organic framework-ultra-crosslinked polymer composite material, a preparation method and application, and belongs to the field of adsorbent materials. The composite material is composed of a metal organic framework material and an ultra-crosslinked polymer, and the crystal grains of the metal organic framework material are inlaid on the pore wall surface or in the pores of the ultra-crosslinked polymer; raw materials for preparing effective components include metal salts, organic ligands, oleic acid and polystyrene-based ultra-crosslinked polymers. The metal organic framework-ultra-crosslinked polymer composite material provided by the application has strong structural stability, simple and easy-to-operate preparation process, and is suitable for industrial production, and can simply, energy-efficiently and efficiently remove organic impurities in a lithium extraction mother liquor, and improve product purity and yield.

Description

Technical Field

[0001] This invention belongs to the field of adsorbent materials technology, and relates to a metal-organic framework-hypercrosslinked polymer composite material, specifically a metal-organic framework-hypercrosslinked polymer composite material, its preparation method and application. Background Technology

[0002] In recent years, lithium batteries, as a green new energy source, have been widely used in the electric vehicle industry, leading to an exponential increase in global demand for lithium over the past decade. my country is rich in lithium resources from salt lakes, with proven reserves accounting for as much as 80.54%, and the salt lakes of the Qaidam Basin in Qinghai Province, with the richest lithium reserves, have become an important source of raw materials for my country's lithium resources. Solvent extraction is one of the most effective and industrially successful methods for extracting liquid lithium resources from the Qaidam Basin salt lakes. Solvent extraction utilizes the unique extraction properties of organic solvents to achieve lithium extraction. A solvent system with industrial application value uses FeCl3 as the extractant and tributyl phosphate (TBP) as a co-extractant. Companies such as Qinghai Qaidam Xinghua Lithium Salt Co., Ltd., Qinghai Bohua Lithium Industry Co., Ltd., and Qinghai Zhongke Jiexin High-Tech Co., Ltd. all use this method to produce industrial raw material lithium chloride. The industrial application of solvent extraction fully demonstrates the great application value of lithium extraction from salt lakes with high magnesium-to-lithium ratio. However, because this method uses TBP as the extractant and kerosene as the back-extraction agent, the solution after back-extraction (lithium extraction mother liquor) contains organic impurities such as soluble TBP, TBP degradation product DBP, butanol, and soluble kerosene at a content of about 750 mg / L. Among them, TBP and kerosene, which are the most abundant, are difficult to remove after forming a microemulsion phase, which seriously affects the purity of lithium chloride products.

[0003] Currently, the measures taken to address this problem involve a series of complex oil removal processes: constant flow oil separator → micro-nano oil separator → ultrasonic high-energy oxygen oil separator → primary activated carbon oil separator → secondary activated carbon oil separator → automatic regulating tank. This series of complex oil removal procedures reduces product yield and significantly increases production costs. Furthermore, the adsorption effect of activated carbon as an adsorbent is unstable, resulting in fluctuating product purity. Additionally, partial breakage of the activated carbon causes the mother liquor to turn black, potentially failing to meet production requirements and severely impacting the product's value. Therefore, finding a simple, energy-efficient, and highly effective method to remove organic impurities from lithium extraction mother liquor is a pressing technical challenge for enterprises.

[0004] Adsorption is a highly efficient, easy-to-manage, and easy-to-operate method for removing organic matter. The core of adsorption is selecting a suitable adsorbent. Commonly used adsorbents include activated carbon, carbon nanotubes, graphene, and metal-organic frameworks (MOFs). MOFs are a new type of nanocrystalline material possessing both inorganic and organic properties. Due to their high specific surface area, tunable pore structure, and abundant active sites for binding, they have shown promising application prospects as novel adsorbents in the treatment of oily wastewater, catalysis, and gas adsorption / separation. In particular, one-dimensional (1D) MOFs, such as nanotubes, nanorods, and nanowires, effectively combine the excellent mass / charge transfer kinetics and abundant active sites of two-dimensional materials with the unique properties of MOFs' tunable pore structure, making them valuable in industrial oil-water separation. However, the weak metal-ligand coordination bonds make MOFs unstable in water and prone to hydrolysis, limiting their application in industrial oily wastewater. Summary of the Invention

[0005] The purpose of this invention is to provide a metal-organic framework-hypercrosslinked polymer composite material to solve the problem of poor adsorption of organic impurities in existing lithium extraction mother liquor, resulting in low product purity;

[0006] Another object of the present invention is to provide a method for preparing the metal-organic framework-hypercrosslinked polymer composite material, so as to achieve a simple and easy-to-operate method for preparing the composite material;

[0007] Another objective of this invention is to provide applications of the metal-organic framework-hypercrosslinked polymer composite material to solve the problems of complex methods, low yields, and low product purity in existing methods for removing organic impurities from lithium extraction mother liquor.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A metal-organic framework-hypercrosslinked polymer composite material is composed of a metal-organic framework material and a hypercrosslinked polymer, wherein the grains of the metal-organic framework material are embedded in the pore walls or pores of the hypercrosslinked polymer.

[0010] As a limitation, the raw materials for its active ingredients include metal salts, organic ligands, oleic acid, and polystyrene-based hypercrosslinked polymers.

[0011] As a further limitation, the metal salt is a zinc salt or a cobalt salt, and the organic ligand is imidazole and / or 2-methylimidazole.

[0012] This invention also provides a method for preparing the above-mentioned metal-organic framework-hypercrosslinked polymer composite material, comprising the following steps:

[0013] S1. Mix 5 molar amounts of metal salt with water to obtain aqueous phase A;

[0014] S2. Dissolve 0.4 mol of organic ligand in 3.19 mol of oleic acid, add polystyrene-based hypercrosslinked polymer, mix well, and obtain oil phase B with a hypercrosslinked polymer concentration of 60 mg / ml;

[0015] S3. Add 1 volume part of oil phase B to 5 volume parts of aqueous phase A to carry out an oil-water interface combination reaction to obtain product C;

[0016] S4. Wash, dry and grind product C to obtain the metal-organic framework-hypercrosslinked polymer composite material.

[0017] As a limitation, the polystyrene-based hypercrosslinked polymer is prepared by the following steps:

[0018] 1 part by weight of polystyrene, 0.85 parts by weight of dimethoxymethane and 30 parts by weight of 1,2-dichloroethane were mixed evenly, and 2.54 parts by weight of trifluoromethanesulfonic acid were added. The mixture was reacted at 50°C for 1.5 h, filtered, washed and dried to obtain the polystyrene-based hypercrosslinked polymer.

[0019] As another limitation, the oil-water interface reaction is carried out at 25-30℃ for 12-24 hours and at 40-60℃ for 12-48 hours.

[0020] As a third limitation, the solvent used for washing in step S4 is methanol, ethanol, N,N-dimethylformamide, or acetone.

[0021] As a fourth limitation, the drying process in step S4 is carried out at a temperature of 50-100℃ for 12-48 hours.

[0022] The present invention also provides the application of the above-mentioned metal-organic framework-hypercrosslinked polymer composite material, which is used to adsorb organic impurities in lithium extraction mother liquor.

[0023] As a limitation, the adsorption time is 24-48 hours and the temperature is 25-45°C;

[0024] The pH of the lithium extraction mother liquor was adjusted to 6-8 before adsorption.

[0025] By adopting the above technical solution, the technical progress achieved by this invention compared with the prior art is as follows:

[0026] ① The metal-organic framework-hypercrosslinked polymer composite material provided by this invention mainly adsorbs TBP in lithium extraction mother liquor. After modification by introducing oleic acid molecules with a molecular weight equivalent to kerosene, the metal-organic framework material fixes the oleic acid molecules, significantly enhancing the adsorption effect on kerosene. It can remove multiple organic impurities in lithium extraction mother liquor in one go without introducing other impurities, thus greatly purifying the lithium extraction mother liquor. Moreover, the composite material is a solid substance and can be separated by simple filtration.

[0027] ② The metal-organic framework-hypercrosslinked polymer composite material provided by the present invention has metal-organic framework material grains embedded in the pore wall surface or pores of the hypercrosslinked polymer, which enhances the structural stability of the metal-organic framework material. The zeolite imidazole ester framework structure material (ZI Fs) prepared by combining zinc salt / cobalt salt with imidazole / 2-methylimidazole has excellent hydrophobic and oleophilic properties and is not easily hydrolyzed in water.

[0028] ③ The method for preparing metal-organic framework-hypercrosslinked polymer composite material provided by the present invention directly grows the metal-organic framework material in situ into the pores of the hypercrosslinked polymer through oil-water interface contact, and the reaction conditions are simple.

[0029] ④ The preparation method of the metal-organic framework-hypercrosslinked polymer composite material provided by the present invention is simple and easy to operate, and does not require high temperature and high pressure conditions, saving energy and suitable for industrial production;

[0030] ⑤ The application of the metal-organic framework-hypercrosslinked polymer composite material provided by this invention only requires adjusting the pH value to neutral, directly adding the composite material for adsorption and filtration, which can remove organic impurities in lithium extraction mother liquor. Compared with the existing degreasing process in industry, it is simple to operate, efficient, energy-saving, and does not increase losses, improves product yield, and can generate huge economic benefits.

[0031] The metal-organic framework-hypercrosslinked polymer composite material provided by this invention has strong structural stability, and the preparation process is simple and easy to operate, making it suitable for industrial production. It can simply, energy-savingly, and efficiently remove organic impurities from lithium extraction mother liquor, thereby improving product purity and yield. Attached Figure Description

[0032] Figure 1 This is a flowchart of the composite material preparation method in Example 1;

[0033] Figure 2 Here is a SEM image of the polystyrene-based hypercrosslinked polymer in Example 1;

[0034] Figure 3 The image shows a SEM image of the MOF-HCP-60 prepared in Example 1.

[0035] Figure 4 The image shows a SEM image of the MOF-HCP-50 prepared in Example 2.

[0036] Figure 5 The image shows a SEM image of the MOF-HCP-70 prepared in Example 2.

[0037] Figure 6 The image shows a SEM image of the MOF-HCP-80 prepared in Example 2.

[0038] Figure 7 The image shows a SEM image of the MOF-HCP-90 prepared in Example 2.

[0039] Figure 8 The image shows a SEM image of MOF-HCP-100 prepared in Example 2.

[0040] Figure 9 This is a SEM image of the MOF-HCP-60 prepared in Example 2 after adsorbing organic matter;

[0041] Figure 10 The results are the water contact angle test results of MOF-HCP-60 prepared in Example 2;

[0042] Figure 11 The results are the water contact angle test results for PS-HCP;

[0043] Figure 12 The results are the water contact angle test results for MOF-OA. Detailed Implementation

[0044] The present invention will be further described in detail below through specific embodiments. It should be understood that the described embodiments are only for explaining the present invention and do not limit the present invention.

[0045] Example 1

[0046] This embodiment prepared a metal-organic framework-hypercrosslinked polymer composite material, and the process flow diagram is shown below. Figure 1 As shown, the specific preparation process includes the following steps:

[0047] S1. Weigh 1.5 kg (5 mol) of zinc nitrate hexahydrate and dissolve it in 5 L of deionized water and mix well to obtain aqueous phase A with a concentration of 1 M;

[0048] S2. Weigh 1 kg of polystyrene, 0.85 kg of dimethoxymethane, and 30 kg of 1,2-dichloroethane into a container and mix thoroughly. Add 2.54 kg of trifluoromethanesulfonic acid and react at 50 °C for 1.5 h. After filtration, wash successively with 1 mol / L sodium hydroxide solution, anhydrous ethanol, and deionized water, and dry to obtain the polystyrene-based hypercrosslinked polymer. Scanning electron microscopy (SEM) analysis of the polystyrene-based hypercrosslinked polymer yields the following results: Figure 2 As shown;

[0049] Depend on Figure 2 As can be seen, the morphology of the hypercrosslinked polymer is a porous structure similar to a honeycomb.

[0050] Polystyrene-based hypercrosslinked polymers can also be obtained through other preparation methods or by purchasing.

[0051] Weigh 0.03 kg (0.4 mol) of 2-methylimidazolium and dissolve it in 0.9 kg (3.19 mol) of oleic acid to prepare a 0.4 M 2-methylimidazolium oleic acid solution. Add 0.06 kg of polystyrene-based hypercrosslinked polymer and mix well to obtain an oil phase B with a hypercrosslinked polymer concentration of 60 mg / mL.

[0052] S3. First, add 5 parts by volume of aqueous phase A to a container, then add 1 part by volume of oil phase B, and carry out an oil-water interface reaction (first react at 25℃ for 24h, then react at 50℃ for 48h) to obtain product C.

[0053] S4. Product C was washed with ethanol solution, dried at 50°C for 12 hours, and then ground to obtain the metal-organic framework-hypercrosslinked polymer composite material, denoted as MOF-HCP-60. MOF-HCP-60 was subjected to scanning electron microscopy (SEM) analysis, and the results are as follows: Figure 3 As shown.

[0054] Example 2

[0055] This embodiment provides an application of a metal-organic framework-hypercrosslinked polymer composite material, using it as an adsorbent for the removal of organic impurities, and verifies its adsorption performance. Specifically, it includes the following steps:

[0056] 1. Sample preparation

[0057] Sample 1:

[0058] The preparation process of Sample 1 was basically the same as steps S1-S4 in Example 1, except that the mass of the polystyrene-based hypercrosslinked polymer added in step S2 was different, resulting in an oil phase B with a hypercrosslinked polymer concentration of 50 mg / mL. All other components, amounts, and control parameters were the same as in Example 1. The resulting metal-organic framework-hypercrosslinked polymer composite material was designated MOF-HCP-50, and its scanning electron microscopy results are as follows. Figure 4 As shown.

[0059] Sample 2:

[0060] Sample 2 is the metal-organic framework-hypercrosslinked polymer composite material MOF-HCP-60 prepared in Example 1.

[0061] Sample 3:

[0062] The preparation process of Sample 3 was basically the same as steps S1-S4 in Example 1, except that the mass of the polystyrene-based hypercrosslinked polymer added in step S2 was different, resulting in an oil phase B with a hypercrosslinked polymer concentration of 70 mg / mL. The remaining components, amounts, and other control parameters were the same as in Example 1. The resulting metal-organic framework-hypercrosslinked polymer composite material was designated MOF-HCP-70, and its scanning electron microscopy results are as follows. Figure 5 As shown.

[0063] Sample 4:

[0064] The preparation process of Sample 4 was basically the same as steps S1-S4 in Example 1, except that the mass of the polystyrene-based hypercrosslinked polymer added in step S2 was different, resulting in an oil phase B with a hypercrosslinked polymer concentration of 80 mg / mL. The remaining components, amounts, and other control parameters were the same as in Example 1. The resulting metal-organic framework-hypercrosslinked polymer composite material was designated MOF-HCP-80, and its scanning electron microscopy results are as follows. Figure 6 As shown.

[0065] Sample 5:

[0066] The preparation process of Sample 5 was basically the same as steps S1-S4 in Example 1, except that the mass of the polystyrene-based hypercrosslinked polymer added in step S2 was different, resulting in an oil phase B with a hypercrosslinked polymer concentration of 90 mg / mL. The remaining components, amounts, and other control parameters were the same as in Example 1. The resulting metal-organic framework-hypercrosslinked polymer composite material was designated MOF-HCP-90, and its scanning electron microscopy results are as follows. Figure 7 As shown.

[0067] Sample 6:

[0068] The preparation process of Sample 6 was basically the same as steps S1-S4 in Example 1, except that the mass of the polystyrene-based hypercrosslinked polymer added in step S2 was different, resulting in an oil phase B with a hypercrosslinked polymer concentration of 100 mg / mL. All other components, amounts, and control parameters were the same as in Example 1. The resulting metal-organic framework-hypercrosslinked polymer composite material was designated MOF-HCP-100, and its scanning electron microscopy results are as follows. Figure 8 As shown.

[0069] Depend on Figure 3-8 It can be seen that MOFs are attached to the surface of the hypercrosslinked polymer, indicating that MOFs were successfully embedded in the pore walls of the hypercrosslinked polymer, and the metal-organic framework-hypercrosslinked polymer composite material was successfully prepared. Furthermore, as the concentration of the hypercrosslinked polymer increases, it can be seen that the number of MOFs attached to the surface gradually decreases.

[0070] Comparison Sample 1:

[0071] Comparative sample 1 is the polystyrene-based hypercrosslinked polymer prepared in step S2 of Example 1, denoted as PS-HCP;

[0072] Comparison Sample 2:

[0073] The preparation process of Comparative Sample 2 is basically the same as steps S1-S4 in Example 1. The only difference is that polystyrene-based hypercrosslinked polymer is not added in step S2. The other components, dosages and other control parameters are the same as in Example 1. The product obtained is denoted as MOF-OA.

[0074] 2. Simulated organic solution adsorption performance testing

[0075] Weigh 0.5 kg of kerosene and 0.5 kg of tributyl phosphate and dissolve them in deionized water, mixing thoroughly to prepare a simulated organic solution with an organic matter concentration of 100 mg / L. Adjust the pH to 7 and divide the solution into 8 equal portions. Add 3 g of samples 1-6 and control samples 1-2 to 10 kg of the simulated organic solution, respectively. Adsorption is carried out at 25℃ for 24 h. Samples are taken before and after adsorption, and the concentration of the simulated organic solution is measured using a chemical oxygen demand (COD) analyzer via the potassium dichromate method. The COD removal rate is calculated using the following formula, and the results are shown in Table 1.

[0076] COD removal rate = (Initial organic matter concentration - Residual organic matter concentration after adsorption) / Initial organic matter concentration × 100%

[0077] Table 1. Results of organic matter removal rates for each adsorbent simulating organic solvents.

[0078]

[0079]

[0080] As shown in Table 1, the removal efficiency of the composite material for organic matter (COD removal rate) first increases and then decreases with the increase of the concentration of the hypercrosslinked polymer. The composite material prepared with a hypercrosslinked polymer doping concentration of 60 mg / ml has the best removal efficiency for organic matter.

[0081] The adsorbed sample 2 was examined by scanning electron microscopy, and the results are as follows: Figure 9 As shown;

[0082] Depend on Figure 9 and Figure 3 The comparison shows that the morphology of the composite material changed before and after adsorption. Organic aggregates can be seen on its surface, indicating that the metal-organic framework-hypercrosslinked polymer composite material successfully adsorbed organic impurities in the simulated organic solution.

[0083] The poor removal effect of organic matter in the comparison sample 2 may be due to the unstable structure of the metal-organic framework material, which is prone to hydrolysis in water, resulting in a poorer adsorption effect. The removal effect of organic matter in the comparison sample 1 is already very good. The adsorption rate decreased after the addition of MOFs. This may be because adding too much MOFs will block the pores of the hypercrosslinked polymer and reduce the adsorption effect of TBP, while adding too little MOFs will not achieve effective adsorption of kerosene.

[0084] Industrially, the removal rate of organic matter in lithium extraction mother liquor is required to reach 70% or above. The simulated effects of samples 2, 3 and control sample 1 can all meet the requirements. However, the lithium extraction mother liquor in actual industrial production contains a large number of metal ions and other impurities, which will affect the adsorption effect of the material. Therefore, it is necessary to verify the adsorption of lithium extraction mother liquor with materials that meet the requirements.

[0085] 3. Application in lithium extraction mother liquor

[0086] 3g of sample 2, sample 3, and control sample 1 were added to 10kg of lithium extraction mother liquor (the lithium extraction mother liquor was produced by Qinghai Chaidamu Xinghua Lithium Salt Co., Ltd.). Adsorption was carried out at 25℃ for 24h. Samples were taken before and after adsorption, and the concentration of the simulated organic solution was determined by a chemical oxygen demand (COD) analyzer using the potassium dichromate method. The calculation results are shown in Table 2.

[0087] Table 2 Results of organic matter removal rates in lithium extraction mother liquor for each adsorbent

[0088]

[0089]

[0090] Table 2 shows that the organic matter removal rates of all adsorbents decreased in the actual lithium extraction mother liquor. This is because the actual lithium extraction mother liquor contains various metal ions and other impurities, which affect the adsorption process. The removal rates of organic matter in the lithium extraction mother liquor by MOF-HCP-70 and PS-HCP decreased to 60.37% and 59.2%, respectively, failing to meet industrial requirements. In contrast, the composite material MOF-HCP-60 achieved the highest organic matter removal rate of 70.13%, still meeting the industrial requirement of 70% or higher. Therefore, although the improvement in organic matter removal rate in the lithium extraction mother liquor by the composite material MOF-HCP-60 is not significant compared to PS-HCP, it represents a qualitative leap in industrial applications.

[0091] 4. Hydrophobicity test

[0092] Sample 2, control sample 1, and control sample 2 were tested for water contact angle using the droplet angle measurement method. The results are as follows: Figure 10-12 As shown;

[0093] Depend on Figure 10-12 It can be seen that the water contact angle of the metal-organic framework-hypercrosslinked polymer composite material is larger than that of control sample 1 and control sample 2. It can be seen that control sample 1 and control sample 2 have good hydrophobicity, while the composite material has better hydrophobicity than the two. This indicates that the composite material has successfully improved the hydrophobicity of the material. In simulated wastewater treatment, the better the hydrophobicity of the material, the better the water stability of the material. This is an important evaluation criterion for the performance of the material. Moreover, the better the hydrophobicity of the material, the more conducive it is to adsorb organic matter in the simulated wastewater.

[0094] Example 3

[0095] This embodiment prepares a metal-organic framework-hypercrosslinked polymer composite material and applies it to the adsorption of organic impurities in lithium extraction mother liquor. The specific preparation process includes the following steps:

[0096] S1. Weigh 1.5 kg (5 mol) of cobalt nitrate hexahydrate and dissolve it in 5 L of deionized water and mix well to obtain aqueous phase A with a concentration of 1 M;

[0097] S2. Weigh 1 kg of polystyrene, 0.85 kg of dimethoxymethane and 30 kg of 1,2-dichloroethane into a container and mix them evenly. Add 2.54 kg of trifluoromethanesulfonic acid and react at 50 °C for 1.5 h. After filtration, wash with 1 mol / L sodium hydroxide solution, anhydrous ethanol and deionized water in sequence, and dry to obtain polystyrene-based hypercrosslinked polymer.

[0098] Weigh 0.03 kg (0.4 mol) of 2-methylimidazole and dissolve it in 0.9 kg (3.19 mol) of oleic acid to prepare an imidazole oleic acid solution with a concentration of 0.4 M. Add 60 g of polystyrene-based hypercrosslinked polymer and mix well to obtain an oil phase B with a hypercrosslinked polymer concentration of 60 mg / mL.

[0099] S3. First, add 5 parts by volume of aqueous phase A to a container, then add 1 part by volume of oil phase B, and carry out an oil-water interface reaction (first react at 30℃ for 12h, then react at 40℃ for 12h) to obtain product C.

[0100] S4. Wash product C with acetone solution, dry at 100°C for 48 hours, and then grind to obtain the metal-organic framework-hypercrosslinked polymer composite material.

[0101] Adjust the pH of the lithium extraction mother liquor to 6, add the metal-organic framework-hypercrosslinked polymer composite material, adsorb at 30°C for 28 hours, and filter to effectively remove organic impurities from the lithium extraction mother liquor.

[0102] Example 4

[0103] This embodiment prepares a metal-organic framework-hypercrosslinked polymer composite material and applies it to the adsorption of organic impurities in lithium extraction mother liquor. The specific preparation process includes the following steps:

[0104] S1. Weigh 1.5 kg (5 mol) of zinc nitrate hexahydrate, dissolve it in deionized water and mix well to prepare aqueous phase A with a concentration of 1 M;

[0105] S2. Weigh 1 kg of polystyrene, 0.85 kg of dimethoxymethane and 30 kg of 1,2-dichloroethane into a container and mix them evenly. Add 2.54 kg of trifluoromethanesulfonic acid and react at 50 °C for 1.5 h. After filtration, wash with 1 mol / L sodium hydroxide solution, anhydrous ethanol and deionized water in sequence, and dry to obtain polystyrene-based hypercrosslinked polymer.

[0106] Weigh 0.02 kg (0.29 mol) imidazole and 0.009 kg (0.11 mol) 2-methylimidazolium and dissolve them in 0.9 kg (3.19 mol) oleic acid to prepare an imidazole-2-methylimidazolium oleic acid solution with a concentration of 0.4 M. Add 0.06 kg of polystyrene-based hypercrosslinked polymer and mix well to obtain an oil phase B with a hypercrosslinked polymer concentration of 60 mg / mL.

[0107] S3. First, add 5 parts by volume of aqueous phase A to a container, then add 1 part by volume of oil phase B, and carry out an oil-water interface reaction (first react at 28℃ for 20h, then react at 60℃ for 24h) to obtain product C.

[0108] S4. The product C is washed with N,N-dimethylformamide solution, dried at 80°C for 16 hours, and then ground to obtain the metal-organic framework-hypercrosslinked polymer composite material.

[0109] Adjust the pH of the lithium extraction mother liquor to 8, add the metal-organic framework-hypercrosslinked polymer composite material, adsorb at 45°C for 48 hours, and filter to effectively remove organic impurities from the lithium extraction mother liquor.

Claims

1. A metal-organic framework-hypercrosslinked polymer composite material, characterized in that, It is composed of metal-organic framework materials and hypercrosslinked polymers, with the grains of the metal-organic framework material embedded in the pore walls or pores of the hypercrosslinked polymer; The raw materials used to make its active ingredient include metal salts, organic ligands, oleic acid, and polystyrene-based hypercrosslinked polymers; The metal salt is a zinc salt or a cobalt salt, and the organic ligand is imidazole and / or 2-methylimidazole; A method for preparing metal-organic framework-hypercrosslinked polymer composites includes the following steps: S1. Mix 5 molar amounts of metal salt with water to obtain aqueous phase A; S2. Dissolve 0.4 mol of the organic ligand in 3.19 mol of oleic acid, add the polystyrene-based hypercrosslinked polymer, mix well, and obtain oil phase B with a hypercrosslinked polymer concentration of 60 mg / ml; S3. Add 1 volume part of oil phase B to 5 volume parts of aqueous phase A to carry out an oil-water interface combination reaction to obtain product C; S4. Wash, dry and grind product C to obtain the metal-organic framework-hypercrosslinked polymer composite material.

2. The method for preparing a metal-organic framework-hypercrosslinked polymer composite material according to claim 1, characterized in that, Includes the following steps: S1. Mix 5 molar amounts of metal salt with water to obtain aqueous phase A; S2. Dissolve 0.4 mol of the organic ligand in 3.19 mol of oleic acid, add the polystyrene-based hypercrosslinked polymer, mix well, and obtain oil phase B with a hypercrosslinked polymer concentration of 60 mg / ml; S3. Add 1 volume part of oil phase B to 5 volume parts of aqueous phase A to carry out an oil-water interface combination reaction to obtain product C; S4. Wash, dry and grind product C to obtain the metal-organic framework-hypercrosslinked polymer composite material.

3. The method for preparing the metal-organic framework-hypercrosslinked polymer composite material according to claim 2, characterized in that, The polystyrene-based hypercrosslinked polymer is prepared by the following steps: 1 part by weight of polystyrene, 0.85 parts by weight of dimethoxymethane and 30 parts by weight of 1,2-dichloroethane were mixed evenly, and 2.54 parts by weight of trifluoromethanesulfonic acid were added. The mixture was reacted at 50°C for 1.5 h, filtered, washed and dried to obtain the polystyrene-based hypercrosslinked polymer.

4. The method for preparing the metal-organic framework-hypercrosslinked polymer composite material according to claim 2, characterized in that, The oil-water interface reaction is carried out at 25-30℃ for 12-24 hours and at 40-60℃ for 12-48 hours.

5. The method for preparing the metal-organic framework-hypercrosslinked polymer composite material according to any one of claims 2-4, characterized in that, The solvent used for washing in step S4 is methanol, ethanol, N,N-dimethylformamide, or acetone.

6. The method for preparing the metal-organic framework-hypercrosslinked polymer composite material according to any one of claims 2-4, characterized in that, In step S4, the drying process is carried out at a temperature of 50-100℃ for 12-48 hours.

7. The application of the metal-organic framework-hypercrosslinked polymer composite material according to claim 1, characterized in that, This composite material is used to adsorb organic impurities in lithium extraction mother liquor.

8. The application of the metal-organic framework-hypercrosslinked polymer composite material according to claim 7, characterized in that, The adsorption process takes 24-48 hours and occurs at a temperature of 25-45°C. The pH of the lithium extraction mother liquor was adjusted to 6-8 before adsorption.

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