CN108159893B - Metal organic framework composite ultrafiltration membrane material and preparation and application thereof - Google Patents
Metal organic framework composite ultrafiltration membrane material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework composite ultrafiltration membrane material and preparation and application thereof, belonging to the technical field of water treatment. Aiming at the problems that various tetroxide radical inorganic anions in the current industrial production discharged water are difficult to purify and the existing adsorbing material has defects, the invention firstly synthesizes a metal organic framework polymer with special selectivity on tetroxide radical anions with a regular tetrahedron structure, and simultaneously creates a preparation method of the novel environment functional composite membrane material-metal organic framework composite ultrafiltration membrane material4 ‑、PO4 3‑、TcO4 ‑、CrO4 ‑、AsO4 3‑And (3) one-step separation of the tetroxide anion pollutants with the tetrahedral structure.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a metal organic framework composite ultrafiltration membrane material, and preparation and application thereof.
Background
The metal organic framework coordination polymer is a novel porous coordination polymer material, has been paid extensive attention by researchers in the past decade since the beginning, and has made important progress from the initial structural branch which is keen on synthesizing a variety of structures to the application which is mainly in the environmental field at present. Because of some self advantages of the metal organic framework coordination polymer, such as large specific surface area, many active sites and easy regulation and control of crystal structure, the metal organic framework coordination polymer is widely applied to storage, separation and catalysis of energy gas; meanwhile, due to the defect of low water stability, the water environment pollution treatment research direction is relatively backward, and the water environment pollution treatment material is gradually applied to water pollution treatment as a novel environment functional material until recent years. Generally, metal-organic framework coordination polymers have great advantages over other adsorbent materials for the removal of ionic contaminants from water bodies if their water stability is not compromised. Firstly, the huge specific surface area and a large number of active sites can efficiently enrich ionic pollutants in water; secondly, the characteristic of easy regulation and control of the structure can make the water fully exert the selection advantage on the target pollutants in the water; finally, when the water environment is complicated and changeable, the target pollutant, especially the low concentration ionic pollutant with smaller hydration radius, the metal organic framework coordination polymer can realize the high-efficiency enrichment capture of the target ion (Fei H, Rogow D L, over SR. conversion exchange and catalytic properties of two cationic metal-organic framework base Cu (I) and Ag (I) [ J H].Journal of the AmericanChemical Society,2010,132(20):7202-7209；HonghanFei,Latisha Paw U,DavidL.Rogow,etc.Synthesis,Characterization,and Catalytic Application of aCationic Metal-Organic Framework:Ag2(4,4′-bipy)2(O3SCH2CH2SO3)[J]Chemistry of materials,2010,22(6), 2027-. Therefore, how to improve the stability of the metal organic framework coordination polymer in the water body becomes the first priority for vigorously developing the novel environment functional materialAnd (4) a target.
The load is taken as a common method for synthesizing a new material in the environmental field, so that various unrelated substances can be mutually coordinated to form a unified whole and can play respective environmental functions in an assisted manner, and therefore, the load of the metal organic framework coordination polymer on the surface of the membrane to form the composite membrane becomes a hotspot of current research. The functional material and the membrane are compounded, so that the removal effect of the metal organic framework coordination polymer on target pollutants can be exerted, the one-step separation of water pollutants can be realized, and secondary treatment is not needed. Meanwhile, the problem of water stability of the metal organic framework coordination polymer can be solved. In combination, the preparation of such composite membranes has achieved several research results: chinese patent 201510446599.6, published 2015, 12, month and 9, discloses a method for preparing a reverse-diffusion in-situ self-assembled MOFs nanofiltration membrane, wherein a MOFs/polymer hybrid separation layer is formed in situ on the surface of a base membrane, and the concentration and diffusion time of solutions on both sides of the base membrane are controlled to regulate and control the structure of the separation layer, so that a MOFs nano hybrid membrane is formed and successfully applied to dye removal, but the MOFs membrane obtained by the method through in-situ growth relatively lacks uniformity in growth; chinese patent 201710371618.2, published as 2017, 8 and 8, introduces a novel preparation method of MOFs-PVDF composite membrane, which solves the problems of poor membrane hydrophilicity, nanoparticle agglomeration and low mechanical strength in a partial membrane modification method, but the method has various operation steps and is difficult to apply.
Tetroxide anions of regular tetrahedral structure, such as: ClO4 -、PO4 3-、TcO4 -、CrO4 -、AsO4 3-The water-soluble organic fertilizer is a common anionic pollutant in natural water, most salts of the water-soluble organic fertilizer have good water solubility and are difficult to volatilize or naturally degrade, and meanwhile, the water-soluble organic fertilizer has high diffusion speed in surface or underground water environment, long retention time and biological accumulation. Along with the production activities of human beings, more and more of the anionic pollutants enter natural water bodies through industrial discharge and participate in the material circulation of the nature, thereby causing serious harm to the ecological environment over time. Once these anions are onFood enters a human body through the environment, and then circulates to each organ from body fluid, and the food is enriched to a certain concentration to cause functional disorder and organ damage of the human body, and can seriously cause poisoning, carcinogenesis or death directly.
Currently, common treatment methods for such contaminants are: adsorption, precipitation, chemical/electrical reduction, biodegradation. Because the pollutants have strong stability and chemical inertness, high solubility and high toxicity, common physical methods such as precipitation and the like are basically ineffective; the chemical/electric reduction treatment efficiency is not high, and the energy consumption is high; although biodegradation reduction has a certain treatment effect, the requirement on environmental conditions is high, and microorganisms are difficult to acclimate. Therefore, the adsorption method is the most suitable method for treating the water body pollution at present, however, because the concentration of the anion in the natural water body is not high, and meanwhile, the water also has many other common inorganic anion interferences, such as chloride ion, sulfate ion, nitrate ion, fluoride ion and the like. Therefore, the competitive action of the coexisting ions is also a major factor affecting the treatment effect, and it is critical to find an efficient, highly selective adsorbent which is not affected by the environment.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the purification of various tetroxide inorganic anions in the discharged water of the current industrial production is difficult to process and the existing adsorption material has defects, the invention provides a metal organic framework composite ultrafiltration membrane material, and correspondingly provides a preparation method of the composite ultrafiltration membrane, which can efficiently realize the ClO in the water body4 -、PO4 3-、TcO4 -、CrO4 -、AsO4 3-And (3) one-step separation of the tetroxide anion pollutants with the tetrahedral structure.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a metal organic framework composite ultrafiltration membrane material takes polyvinylidene fluoride as a membrane carrier, takes a metal organic framework coordination polymer as a load, and combines the polyvinylidene fluoride and the metal organic framework coordination polymer through hydroxyl;
the metal-organic framework coordination polymer takes bipy-Cu-bipy as a basic chain structure, and the bipy is 2, 2' -bipyridine.
Furthermore, the metal organic framework composite ultrafiltration membrane material is used for treating the water body polluted by the regular tetrahedron structure tetroxide anions, wherein the regular tetrahedron structure tetroxide anions comprise ClO4 -、PO4 3-、TcO4 -、CrO4 -、AsO4 3、MnO4 -One or more than one of (a).
The preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water are mixed according to the weight ratio of (0.9-1.2): (1-1.1): (1.05-1.35): (510-550), reacting under certain conditions after mixing and dissolving in a molar ratio, repeatedly washing the obtained mixed product with water and ethanol, separating out a solid product, and drying to obtain a metal organic framework coordination polymer;
(2) butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of (0.3-0.6): (7.5-10.7): (36-40), stirring and reacting under certain conditions, pouring the casting solution on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for a period of time to generate a polyvinylidene fluoride membrane, and soaking the generated polyvinylidene fluoride membrane in alkali liquor for a period of time;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in a benzyl chloride/n-heptane solution for a period of time, and then soaking the polyvinylidene fluoride membrane in a 5-50 wt% metal-organic framework coordination polymer/n-hexane mixed solution to obtain the metal-organic framework composite ultrafiltration membrane material with the load of 5-50 wt%.
Furthermore, the reaction temperature in the step (1) is 160-190 ℃, the reaction time is 3-5 days, and the reaction device is a high-pressure reaction kettle.
Furthermore, the reaction temperature of the step (2) is 40-50 ℃, the stirring time is 6-10 hours, and the reaction environment is an oxygen-insulated environment.
Furthermore, the alkali liquor in the step (2) is one or a mixture of a sodium hydroxide solution and a potassium hydroxide solution, and the concentration of the alkali liquor is 20-23 wt%.
Furthermore, the membrane in the step (2) is soaked in pure water for 5-10 minutes, and soaked in alkaline liquor for 30-50 minutes.
Further, the concentration of the benzyl chloride in the benzyl chloride/n-heptane solution of the step (3) is 0.1 to 0.5 wt%.
Furthermore, the soaking time of the polyvinylidene fluoride membrane in the benzyl chloride/n-heptane solution in the step (3) is 10-30 minutes.
Furthermore, the soaking time of the polyvinylidene fluoride membrane in the metal organic framework coordination polymer/n-hexane mixed solution in the step (3) is 30-60 minutes.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention firstly synthesizes the metal organic framework polymer with special selectivity to the tetroxide anion with the regular tetrahedron structure, and simultaneously provides the preparation method of the novel environment function composite membrane material, the preparation method is simple, and the problems of poor membrane hydrophilicity caused by membrane preparation by a general blending method, poor membrane dispersion of a casting solution caused by polymer particle agglomeration, easy membrane hole blockage, reduced water flux of the metal organic framework composite membrane, low mechanical strength and the like are effectively solved, and the combination mode has better innovation and reference significance for the composition of the same type of substances or the composition of different types of substances;
(2) the metal organic framework coordination polymer is designed aiming at the tetroxide anion with a target tetrahedral structure, has selection specificity on a target object, has good treatment effect, and can still realize advanced treatment and safety control even when the concentration of various coexisting anions is far higher than that of the target anion.
Drawings
FIG. 1 is a schematic diagram of the synthesis and structure of the metal organic framework composite ultrafiltration membrane material of the present invention;
FIG. 2 is a schematic scanning electron microscope of the composite ultrafiltration membrane material of the present invention, wherein a is an SEM image of the original PVDF membrane surface after being magnified 500 times; b is an SEM image of the surface of the metal organic framework composite ultrafiltration membrane with the loading of 30 wt% after being amplified by 500 times;
FIG. 3 is a graph showing the discharge of perchlorate from a 30 wt% loading metal-organic composite ultrafiltration membrane material according to the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water were mixed in a ratio of 0.9: 1: 1.05: 510, reacting for 3 days at 160 ℃ in a high-pressure reaction kettle, repeatedly washing the obtained mixed product with water and ethanol, separating out a solid product, and drying to obtain a metal-organic framework coordination polymer taking bipy-Cu-bipy as a basic chain structure;
(2) mixing butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of 0.3: 7.5: 36, heating and stirring for 6 hours at 40 ℃ under an anaerobic condition, pouring the casting film liquid on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for 5 minutes, and soaking the generated polyvinylidene fluoride film in a sodium hydroxide solution with the concentration of 20 wt% for 30 minutes;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in 0.1 wt% of benzyl chloride/n-heptane solution for 10 minutes, and then soaking the polyvinylidene fluoride membrane in 5 wt% of bipy-Cu-bipy metal organic framework coordination polymer/n-hexane mixed solution for 30 minutes to obtain the metal organic framework composite ultrafiltration membrane material with the load of 5 wt%.
Fig. 1 is a schematic diagram of the synthesis and structure of a metal organic framework composite ultrafiltration membrane material.
Example 2
The preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water were mixed in a ratio of 1.2: 1.1: 1.35: after being mixed and dissolved in a molar ratio of 550, the mixture reacts in a high-pressure reaction kettle at 190 ℃ for 5 days, the obtained mixed product is repeatedly washed by water and ethanol, a solid product is separated out, and the solid product is dried to obtain a metal organic framework coordination polymer taking bipy-Cu-bipy as a basic chain structure;
(2) mixing butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of 0.6: 10.7: 40, heating and stirring for 10 hours at 50 ℃ under the anaerobic condition, pouring the casting film liquid on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for 10 minutes, and soaking the generated polyvinylidene fluoride film in a sodium hydroxide solution with the concentration of 23 wt% for 50 minutes;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in 0.5 wt% of benzyl chloride/n-heptane solution for 30 minutes, and then soaking the polyvinylidene fluoride membrane in 10 wt% of bipy-Cu-bipy metal organic framework coordination polymer/n-hexane mixed solution for 60 minutes to obtain the metal organic framework composite ultrafiltration membrane material with the load of 10 wt%.
Example 3
The preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water were mixed in a ratio of 1: 1: 1.3: 535, reacting for 4 days at 180 ℃ in a high-pressure reaction kettle after mixing and dissolving in a molar ratio, repeatedly washing the obtained mixed product with water and ethanol, separating out a solid product, and drying to obtain a metal-organic framework coordination polymer taking bipy-Cu-bipy as a basic chain structure;
(2) mixing butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of 0.5: 8.2: 37, heating and stirring for 7 hours at 45 ℃ under the anaerobic condition, pouring the casting solution on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for 9 minutes, and soaking the generated polyvinylidene fluoride membrane in a sodium hydroxide solution with the concentration of 22 wt% for 45 minutes;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in 0.2 wt% of benzyl chloride/n-heptane solution for 25 minutes, and then soaking the polyvinylidene fluoride membrane in 30 wt% of bipy-Cu-bipy metal organic framework coordination polymer/n-hexane mixed solution for 55 minutes to obtain the metal organic framework composite ultrafiltration membrane material with the load of 30 wt%.
Example 4
The preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water were mixed in a ratio of 1: 1: 1.3: 535, reacting for 4 days at 180 ℃ in a high-pressure reaction kettle after mixing and dissolving in a molar ratio, repeatedly washing the obtained mixed product with water and ethanol, separating out a solid product, and drying to obtain a metal-organic framework coordination polymer taking bipy-Cu-bipy as a basic chain structure;
(2) mixing butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of 0.5: 8.2: 37, heating and stirring for 7 hours at 45 ℃ under the anaerobic condition, pouring the casting solution on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for 9 minutes, and soaking the generated polyvinylidene fluoride film in a potassium hydroxide solution with the concentration of 22 wt% for 45 minutes;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in 0.2 wt% of benzyl chloride/n-heptane solution for 25 minutes, and then soaking the polyvinylidene fluoride membrane in 50 wt% of bipy-Cu-bipy metal organic framework coordination polymer/n-hexane mixed solution for 55 minutes to obtain the metal organic framework composite ultrafiltration membrane material with the load of 50 wt%.
The mechanical tensile test was performed on the common polyvinylidene fluoride membrane and the 4 kinds of metal organic framework composite ultrafiltration membranes with different loading amounts in examples 1 to 4, and the obtained results were 16.4MPa, 18.5MPa, 19.2MPa, 21.6MPa, and 13.6MPa in this order, which indicates that the membrane strength was the best when the loading amount was 30 wt% compared to the composite ultrafiltration membranes with other loading amounts.
The contact angle test is carried out on the common polyvinylidene fluoride membrane and the 4 metal organic framework composite ultrafiltration membranes with different loading amounts in the embodiments 1-4, the obtained results are 87.6 degrees, 57.3 degrees, 41.4 degrees, 39.1 degrees and 36.7 degrees in sequence, and the results show that the hydrophilicity of the membrane is better and better along with the increase of the loading amount and the loading amount of the metal organic framework coordination polymer, so that the application of the membrane material in the actual water treatment is facilitated.
The water flux test was carried out on the common polyvinylidene fluoride membrane and the 4 kinds of metal organic framework composite ultrafiltration membranes with different loading amounts in examples 1 to 4, and the obtained results were 417, 413, 396, 387 and 328L · m in sequence-2h-1bar-1The result shows that the loading of the metal organic framework coordination polymer can block the membrane pores to a certain degree, but when the loading is between 5% and 30%, the water flux change of the membrane is not greatly influenced.
The anti-fouling test is carried out on a common polyvinylidene fluoride membrane and 4 metal organic framework composite ultrafiltration membranes with different loading amounts in the embodiments 1-4, the retention rates of the obtained membrane materials to pollutants are 43%, 45%, 46%, 51% and 89% in sequence, and the result shows that the greater the loading amount is, the better the pollutant retention effect is, and meanwhile, the easier the pollution is.
Scanning electron microscope tests are carried out on a common polyvinylidene fluoride membrane and 4 kinds of metal organic framework composite ultrafiltration membranes with different loading amounts in examples 1 to 4, and as shown in SEM pictures before and after loading of a metal organic framework shown in figure 2, it can be seen that metal organic framework coordination polymers are uniformly dispersed on the surface of the polyvinylidene fluoride membrane, so that a complete metal organic framework composite ultrafiltration membrane material is formed.
The tensile strength, hydrophilicity, water flux, dirt resistance and the test result of a scanning electron microscope are comprehensively considered, and the loading capacity of the 30 wt% metal organic framework coordination polymer is most suitable for practical application.
Example 5
With perchlorate (ClO)4 -) As a representative of tetroxide anion with a tetrahedral structure, 3 groups of coexisting anion mixed liquor (chlorine ion/perchlorate ion, bromine ion/perchlorate ion, nitrate ion/perchlorate ion) with the volume of 100mL and the perchlorate concentration of 50mg/L are configured, the concentration ratio of each group of coexisting ion to perchlorate is set to be 0-20, a composite membrane material with the load of 30 wt% is put into the mixed liquor, after 50 hours of reaction, the anion concentration in each group is sampled and analyzed, and the perchlorate removal rate of each group is shown in Table 1.
Table 1 perchlorate removal rates of composite film materials for perchlorate coexisting anion mixed solutions of different kinds and concentration ratios
The data in table 1 show that under the interference of various coexisting anions, even if the coexisting anions have higher concentration, the actual treatment effect on the composite membrane material is less influenced, and the selectivity of the metal-organic framework composite ultrafiltration membrane material of the invention on the anions of the tetroxide represented by perchlorate is generally better than that of the anions of other structural forms (such as Cl)-、Br-And NO3 -) The ultrafiltration membrane material of the invention is proved to have selective specificity to the tetroxide anion.
Example 6
Prepared with 25L of perchlorate (ClO) with the concentration of 10mg/L4 -) And (3) solution. An ultrafiltration cup is taken as a reaction device, an ultrafiltration membrane loaded by 30 wt% of active carbon and a composite ultrafiltration membrane containing the metal organic framework coordination polymer with the content of 30 wt% are respectively placed in the ultrafiltration cup, and a solution membrane passing experiment is carried out. The perchlorate ion efflux curve shown in FIG. 3 was obtained by testing the perchlorate ion concentration in the effluent, so that the treatment capacity for reducing the perchlorate concentration to a range of 2mg/L was about 800BV, while the treatment capacity for reducing the perchlorate concentration to a range of 2mg/L was about 30BV in comparison with the activated carbon-supported ultrafiltration membrane.
Example 7
Preparing 25L phosphate radical (PO) with concentration of 10mg/L4 3-) And (3) solution. An ultrafiltration cup is taken as a reaction device, an ultrafiltration membrane loaded by 30 wt% of active carbon and a composite ultrafiltration membrane containing the metal organic framework coordination polymer with the content of 30 wt% are respectively placed in the ultrafiltration cup, and a solution membrane passing experiment is carried out. The throughput for reducing the phosphate concentration to within 2mg/L was approximately 650BV by testing the phosphate ion concentration in the effluent, while the throughput for reducing the phosphate concentration to within 2mg/L was approximately 250BV for the comparative activated carbon-supported ultrafiltration membrane.
Example 8
Preparing 25L of high manganese acid radical (MnO) with concentration of 10mg/L4 -) And (3) solution. An ultrafiltration cup is taken as a reaction device, an ultrafiltration membrane loaded by 30 wt% of active carbon and a composite ultrafiltration membrane containing the metal organic framework coordination polymer with the content of 30 wt% are respectively placed in the ultrafiltration cup, and a solution membrane passing experiment is carried out. The throughput for reducing the permanganate concentration to the 2mg/L range was about 430BV by testing the concentration of permanganate ions in the effluent, while the throughput for reducing the permanganate concentration to the 2mg/L range was about 195BV by comparison with an activated carbon-loaded ultrafiltration membrane.
The material of the invention well solves the problems that other materials have low treatment efficiency on the tetroxide anion with the tetrahedral structure in water, have poor selectivity and are easily influenced by coexisting ions, thus being more suitable for the advanced treatment of the polluted water body.
Claims (9)
1. A metal organic framework composite ultrafiltration membrane material is characterized in that polyvinylidene fluoride is used as a membrane carrier, a metal organic framework coordination polymer is used as a load, and the polyvinylidene fluoride and the metal organic framework coordination polymer are combined through hydroxyl;
the metal-organic framework coordination polymer takes bipy-Cu-bipy as a basic chain structure, and the bipy is 2, 2' -bipyridine;
the preparation method of the metal organic framework composite ultrafiltration membrane material comprises the following steps:
(1) bipyridine, copper nitrate, sodium oxalate and water are mixed according to the weight ratio of (0.9-1.2): (1-1.1): (1.05-1.35): (510-550), reacting under certain conditions after mixing and dissolving in a molar ratio, repeatedly washing the obtained mixed product with water and ethanol, separating out a solid product, and drying to obtain a metal organic framework coordination polymer;
(2) butyrolactone, polyvinylidene fluoride and dimethylacetamide according to the weight ratio of (0.3-0.6): (7.5-10.7): (36-40), stirring and reacting under certain conditions, pouring the casting solution on a smooth and flat glass plate, leveling, placing the glass plate in pure water for soaking for a period of time to generate a polyvinylidene fluoride membrane, and soaking the generated polyvinylidene fluoride membrane in alkali liquor for a period of time;
(3) and (3) soaking the polyvinylidene fluoride membrane obtained in the step (2) in a benzyl chloride/n-heptane solution for a period of time, and then soaking the polyvinylidene fluoride membrane in a 5-50 wt% metal-organic framework coordination polymer/n-hexane mixed solution to obtain the metal-organic framework composite ultrafiltration membrane material.
2. The metal-organic framework composite ultrafiltration membrane material of claim 1, wherein the metal-organic framework composite ultrafiltration membrane material is used for treatment of water polluted by regular tetrahedron-structured tetraalkoxide anions comprising C1O4 -、PO4 3-、TcO4 -、CrO4 -、AsO4 3、MnO4 -One or more than one of (a).
3. The metal-organic framework composite ultrafiltration membrane material as claimed in claim 1, wherein the reaction temperature in the step (1) is 160-190 ℃, the reaction time is 3-5 days, and the reaction device is a high-pressure reaction kettle.
4. The metal-organic framework composite ultrafiltration membrane material according to claim 1 or 3, wherein the reaction temperature in the step (2) is 40-50 ℃, the stirring time is 6-10 hours, and the reaction environment is an anaerobic environment.
5. The metal-organic framework composite ultrafiltration membrane material of claim 4, wherein the alkali solution in the step (2) is one or a mixture of a sodium hydroxide solution and a potassium hydroxide solution, and the concentration of the alkali solution is 20-23 wt%.
6. The metal-organic framework composite ultrafiltration membrane material according to claim 1 or 5, wherein the membrane in the step (2) is soaked in pure water for 5-10 minutes and in alkaline solution for 30-50 minutes.
7. The metal-organic framework composite ultrafiltration membrane material according to claim 1 or 5, wherein the concentration of the benzyl chloride in the benzyl chloride/n-heptane solution of step (3) is 0.1-0.5 wt%.
8. The metal-organic framework composite ultrafiltration membrane material of claim 7, wherein the soaking time of the polyvinylidene fluoride membrane in the benzyl chloride/n-heptane solution in the step (3) is 10-30 minutes.
9. The metal-organic framework composite ultrafiltration membrane material according to claim 1 or 8, wherein the soaking time of the polyvinylidene fluoride membrane in the metal-organic framework coordination polymer/n-hexane mixed solution in the step (3) is 30-60 minutes.
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