CN109173746B - Preparation method of composite membrane for efficiently filtering micro-pollutants in water - Google Patents

Preparation method of composite membrane for efficiently filtering micro-pollutants in water Download PDF

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CN109173746B
CN109173746B CN201811038688.7A CN201811038688A CN109173746B CN 109173746 B CN109173746 B CN 109173746B CN 201811038688 A CN201811038688 A CN 201811038688A CN 109173746 B CN109173746 B CN 109173746B
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cyclodextrin
composite membrane
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CN109173746A (en
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朱利平
张斌
方传杰
王章慧
徐又一
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Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

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Abstract

The invention discloses a preparation method of a composite membrane for efficiently filtering micro-pollutants in water. The method comprises the following steps: the functional beta-cyclodextrin is used as a film-making additive, and is dissolved in a solvent with a film-forming polymer, a pore-forming agent and a cross-linking agent according to a set proportion to prepare a film-casting solution, and the composite film capable of efficiently filtering organic micro-pollutants is prepared by moderate in-situ cross-linking of the functional beta-cyclodextrin in the film-casting solution and adopting an immersion precipitation phase conversion method. The composite membrane has high water permeability and high removal rate of micro-pollutants in water. The composite membrane not only can filter and remove pollutants such as plankton, algae, bacteria, protein, colloid, virus and the like, but also can absorb and remove organic micromolecular micropollutants such as antibiotics, hormones, plasticizers and the like. The preparation process of the composite membrane is simple and controllable, has low cost, can be widely applied to the separation fields of household water purification, sewage treatment, water quality purification and the like, is an efficient and stable water treatment material, and has wide application value.

Description

Preparation method of composite membrane for efficiently filtering micro-pollutants in water
Technical Field
The invention relates to a preparation method of a composite membrane for efficiently filtering micro-pollutants in water, relates to adsorption and membrane separation technologies, and belongs to the field of functional membrane materials.
Background
In recent years, human water quality is improved, along with the development of economy and the acceleration of modernization, the human material and culture level are obviously improved, the fineness of life is improved, and the requirements of people on water quality, including drinking water and domestic water, are higher and higher. Therefore, the demand for water treatment is also remarkably increased, and water treatment technology is urgently needed to be improved. At present, the water treatment technology mainly comprises a flocculation precipitation method, a membrane separation method, a centrifugal separation method and the like. The flocculation precipitation method needs to be kept stand for precipitation and then separated to realize water purification, is only suitable for water with higher pollutant concentration, and is a water treatment method with lower efficiency and low separation fineness; the centrifugal separation method is a separation method which requires a large amount of energy consumption in the separation process and has low separation precision, high energy consumption and low precision. The membrane separation technology mainly realizes separation through the screening effect of the self-aperture of the membrane, does not need extra energy consumption, has controllable separation precision, and is a high-efficiency and simple-operation separation technology widely applied at present.
With the aggravation of environmental pollution, a large amount of organic micro-pollutants such as polycyclic aromatic hydrocarbons, residual pesticides, plasticizers, antibiotics, hormones and the like are contained in the water body. These organic micropollutants can cause serious harm to human body, including causing endocrine disturbance, destroying immune mechanism, causing cancer, teratogenesis, and pathogenesis, generating reproductive diseases, affecting children development, causing precocious puberty, mental retardation, liver damage, and cardiovascular diseases. For the removal of such organic micropollutants in water, the traditional membrane separation technology cannot effectively cope with the problem, and although the reverse osmosis membrane can remove the organic micropollutants through pore size screening filtration, the efficiency of practical application is seriously affected by extremely small water flux and the requirement of additional high pressure. Compared with the traditional membrane chromatography technology for separating and purifying protein, the water purification membrane chromatography technology is a high-efficiency water purification technology combining membrane separation and adsorption separation, and realizes quick and efficient water purification by utilizing the dual functions of filtering large-size pollutants by utilizing the pore size screening effect of the traditional membrane and adsorbing organic micro-pollutants by the membrane chromatography. The core of the water purification membrane chromatography technology is a membrane chromatography medium, namely a separation membrane material, which depends on an adsorption ligand in a separation membrane to a great extent, and whether the water can efficiently adsorb and remove organic micro-pollutants in water depends on an adsorption group in the water. Therefore, it is very critical to find an adsorbing material which can be used as an adsorbing group in a separation membrane, and whether the adsorbing group can be effectively fixed in the separation membrane to perform an efficient adsorption function is a difficult problem to be solved by researchers.
The adsorption separation membrane combines two characteristics of pore size screening and specific adsorption, and is used for purifying water bodies, and related patents report. In patent 200910230074.3, a sulfonic acid resin-based heavy metal ion selective adsorption polymer material is prepared by a phase inversion method, and is used for removing heavy metal ions in water or enriching and recovering precious metals, and can be regenerated and recycled after acid washing. In patent No. 201510907970.4, a resin composite adsorption membrane is prepared, which can be used for efficient extraction of bromine from seawater by controlling adsorption capacity and membrane strength through the content of resin. In patent No. 201410689361.1, a porous adsorption film is prepared by a sol-gel method, which can be used for treating wastewater containing heavy metals and organic matters, and exhibits excellent adsorption effect and high saturated adsorption capacity. Although these materials have a high saturated adsorption capacity for heavy metal ions and the like, in practical application, not only the saturated adsorption capacity but also the adsorption rate need to be considered, that is, both the static adsorption performance and the dynamic adsorption performance need to be high, so that the organic micro-pollutants can be efficiently adsorbed and separated. Therefore, the novel composite membrane is constructed by selecting the adsorbent, and the novel composite membrane has important significance for the research of efficiently adsorbing and removing organic micro-pollutants.
At present, many documents report adsorbent materials for water purification, including clay minerals, industrial residues, organisms, activated carbon, resins, and the like, wherein the clay minerals, organisms, and activated carbon are the most common. Marino et al use phase conversion method to dope kaolin particles into polyether sulfone bulk material, and prepare the product by regulating the content of kaolinA series of composite Membranes for Arsenic ion adsorption Removal show excellent adsorption performance [ Tiziana Marino, France sca Russo, Lina Rezzouk, et al. PES-Kaolin Mixed Matrix Membranes for Arsenic Removal from Water.2017.7.57](ii) a Habiba et al prepared chitosan and zeolite doped polyvinyl alcohol nanofibers by electrospinning for adsorption of chromium, iron and nickel ions with 100% adsorption removal at a concentration of 10-20mg/L and excellent stability [ Habiba, Umma, ethyl, chitosan/(polyvinyl alcohol)/zeolite electron composite membrane for adsorption of Cr6+,Fe3+and Ni2+.Journal of hazardous materials 322(2017):182-194.](ii) a Bolisetty et al dope activated carbon into protein amyloid fibers to prepare hybrid membranes for adsorption and removal of heavy metal ions and radioactive wastes in water, maintain high-efficiency level for simultaneous treatment of various ions, and can be used for recovery of valuable precious metals [ Bolisetty S, mezzeng R].Nature nanotechnology,2016,11(4):365.]. However, these adsorbents have a low adsorption removal rate or a low adsorption removal rate for organic micro-pollutants, and are rarely used for adsorption removal of organic micro-pollutants in water, and it is an ongoing effort of researchers to find a material having an excellent adsorption effect for organic micro-pollutants. Beta-cyclodextrin has excellent adsorption properties, and exhibits excellent adsorption capacity to both heavy metal ions and organic micropollutants, which has attracted much attention.
Beta-cyclodextrin is a cyclic oligosaccharide compound obtained by hydrolyzing starch, has low price and excellent adsorption performance, is an industrial application material, has a molecular structural formula and a three-dimensional structure shown in figure 1, is a round table spatial configuration, has the characteristics of internal hydrophobicity and external hydrophilicity, and can perform specific adsorption on target molecules through the host-object interaction such as van der waals force, hydrophobic interaction force, hydrogen bond and the like. He and the like adopt beta-cyclodextrin and aromatic monomers to synthesize a mesoporous beta-cyclodextrin high molecular material by copolymerization, the mesoporous beta-cyclodextrin high molecular material has high specific surface area, has excellent adsorption performance on lead ions, copper ions and cadmium ions, and particularly has the strongest adsorption capacity on the lead ions [ Junyong He, Yulian Li, Chengming Wang, et al. Besides excellent adsorption performance on heavy metal ions, the beta-cyclodextrin also has super strong adsorption capacity on organic micro-pollutants. Compared with a non-Porous beta-cyclodextrin material and activated carbon, the mesoporous beta-cyclodextrin high Polymer material synthesized by Alsbaiee and the like has the advantages that the adsorption rate of the mesoporous beta-cyclodextrin high Polymer material on various Organic pollutants such as ethinylestradiol, iprodione, bisphenol A and the like is improved by 15-200 times, and the mesoporous beta-cyclodextrin high Polymer material has a very high adsorption rate [ Alaaeddin Alsbaiee, Brian J.Smith, Leilei Xiao, et al. Rapid Removal of Organic Micropollutants from Water by a Porous beta-cyclodextrin Polymer, Nature.2016.529.190-194 ]. Although β -cyclodextrin has excellent adsorption properties, there are few reports of applying β -cyclodextrin to a polymer bulk material to prepare a separation membrane having excellent adsorption properties. The beta-cyclodextrin is a hydrophilic micromolecule substance, is easy to run off in the process of preparing the membrane by using the beta-cyclodextrin as an additive, and greatly reduces the adsorption effect.
The invention provides a new construction idea of an adsorbent material, and the functional beta-cyclodextrin with excellent adsorption performance is blended with other additives, a cross-linking agent and a membrane body material to prepare a beta-cyclodextrin-based efficient composite membrane which can be used for efficiently removing micropollutants in water. The composite membrane not only has good hydrophilicity and stability, but also has excellent adsorption performance including saturated adsorption capacity and adsorption rate while maintaining good separation performance of the traditional separation membrane. The preparation method of the composite membrane is simple, the operation process is simple and convenient, the composite membrane is suitable for industrial large-scale production, and the composite membrane has wide application prospect in the aspect of water quality purification in the future.
Disclosure of Invention
The invention aims to provide a preparation method of a composite membrane for efficiently filtering micropollutants in water. The composite membrane has extremely high adsorption removal capacity on organic micro-pollutants in a water body, keeps high permeability and high adsorption performance, and has important application value in the fields of domestic water purification, sewage treatment and the like.
The preparation method of the composite membrane for efficiently filtering the micro-pollutants in the water is realized by the following technical scheme, and comprises the following steps:
(1) mixing a film-forming polymer, functionalized beta-cyclodextrin, a pore-forming agent, a crosslinking agent and a solvent according to a certain mass ratio, mechanically stirring and dissolving at 40-100 ℃, reacting for 5-10 hours, and vacuumizing and defoaming to obtain a casting solution; the mass ratio of each component is as follows: 10-30% of film-forming polymer; 1-10% of functionalized beta-cyclodextrin; 10-20% of pore-foaming agent; 0.5-5% of a cross-linking agent; 35-78.5% of a solvent;
(2) coating the membrane casting solution by a membrane scraping machine or extruding the membrane casting solution by a hollow fiber spinneret plate, and immersing the membrane casting solution into a coagulating bath for solidification and forming to form a polymer nascent membrane;
(3) and thoroughly cleaning the polymer primary membrane in deionized water to obtain a composite membrane, and using the composite membrane for filtering and removing micropollutants.
The above components can be specifically selected in the following preferred modes: the film-forming polymer is any one of polyvinylidene fluoride, polyvinyl chloride, polycaprolactam, polyhexamethylene adipamide, polyethylene glycol terephthalate, polyacrylonitrile, polyetherimide, polysulfone and polyethersulfone. The functionalized beta-cyclodextrin comprises one or two of amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl beta-cyclodextrin, allyl beta-cyclodextrin and hydroxybutyl beta-cyclodextrin. The pore-foaming agent is one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol and dextran. The cross-linking agent is one or more of polyethyleneimine, glutaraldehyde, epichlorohydrin, diisocyanate and citric acid. The solvent is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. The coagulating bath is pure water or a mixed solution of the pure water and a solvent, wherein the weight percentage of the pure water is 10-100%, and the weight percentage of the solvent is 0-90%.
The shape of the composite membrane prepared by the method is flat or hollow fiber; the aperture of the composite membrane is between 0.01 and 5 microns.
The invention relates to a preparation method of a composite membrane for efficiently filtering micro-pollutants in water, which is characterized in that functional beta-cyclodextrin is used as a self-assembly adsorbent and is effectively fixed in a membrane-forming polymer to obtain the composite membrane for efficiently removing organic micro-pollutants. The composite membrane has good hydrophilicity and stability while maintaining the separation performance of the traditional separation membrane, has excellent filtering performance on micropollutants, can not only filter and remove large-size micropollutants such as plankton, algae, suspended particulate matters and bacteria, but also remove small-size micropollutants such as macromolecules, colloids and viruses, and can specifically and efficiently adsorb and remove organic micromolecular micropollutants such as antibiotics, hormones and plasticizers. The composite membrane has the advantages of simple preparation process, low cost and high application value, and can be effectively used in the fields of household water purification, sewage treatment and the like.
Drawings
The invention relates to a molecular structure expression and a prepared product of a composite membrane for efficiently filtering micro-pollutants in water, wherein the attached drawings are used for illustration only, and:
FIG. 1 is a schematic representation of the molecular structural formula and three-dimensional structure of beta-cyclodextrin;
FIG. 2 is a scanning electron microscope cross-sectional view of a composite membrane for efficiently filtering micropollutants in water according to different formulations.
Detailed Description
Specific examples of the present invention will be described below, but the present invention is not limited to the examples. All variations that come within the meaning and range of equivalency of the disclosure are to be considered within the scope of the invention.
A preparation method of a composite membrane for efficiently filtering micro-pollutants in water comprises the following steps:
(1) mixing a film-forming polymer, functionalized beta-cyclodextrin, a pore-forming agent, a cross-linking agent and a solvent according to a certain mass ratio, mechanically stirring and dissolving at 40-100 ℃, reacting for 5-10 hours, vacuumizing and defoaming to obtain a casting solution. The mass ratio of each component is as follows: 10-30% of film-forming polymer; 1-10% of functionalized beta-cyclodextrin; 10-20% of pore-foaming agent; 0.5-5% of a cross-linking agent; 35-78.5% of a solvent;
(2) coating the membrane casting solution by a membrane scraping machine or extruding the membrane casting solution by a hollow fiber spinneret plate, and immersing the membrane casting solution into a coagulating bath for solidification and forming to form a polymer nascent membrane;
(3) and thoroughly cleaning the polymer primary membrane in deionized water to obtain a composite membrane, and using the composite membrane for adsorbing and removing micropollutants in water.
The above components can be specifically selected in the following preferred modes: the film-forming polymer is any one of polyvinylidene fluoride, polyvinyl chloride, polycaprolactam, polyhexamethylene adipamide, polyethylene glycol terephthalate, polyacrylonitrile, polyetherimide, polysulfone and polyethersulfone. The functionalized beta-cyclodextrin comprises one or two of amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl beta-cyclodextrin, allyl beta-cyclodextrin and hydroxybutyl beta-cyclodextrin. The pore-foaming agent is one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol and dextran. The cross-linking agent is one or more of polyethyleneimine, glutaraldehyde, epichlorohydrin, diisocyanate and citric acid. The solvent is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. The coagulating bath is pure water or a mixed solution of the pure water and a solvent, wherein the weight percentage of the pure water is 10-100%, and the weight percentage of the solvent is 0-90%. The shape of the composite membrane is flat or hollow fiber; the aperture of the composite membrane is between 0.01 and 5 microns.
The invention discloses a structure and performance characterization method of a composite membrane for efficiently filtering micropollutants in water, which comprises the following steps:
surface morphology and structure: and (3) shearing a proper amount of sample, observing the cross section structure of the composite film by using a field emission scanning electron microscope as shown in figure 2, and recording.
And (3) flux testing: cutting standard size membrane, fixing in ultrafiltration cup, pre-pressing with deionized water at 0.1MPa for 30min, and placing in a vacuum containerMeasuring pure water flux (L/m) at the same pressure2h)。
Micro-pollutant retention rate: prepressing with 1.0g/L micro-pollutant solution under 0.1MPa for 30min, collecting 20mL of filtrate, measuring absorbance with an ultraviolet spectrophotometer, and measuring the retention rate of the micro-pollutant (fixed molecular weight) solution with pH of 7.4 by contrasting with a standard curvometer.
And (3) micro-pollutant adsorption test: and respectively scanning the ultraviolet-visible absorption spectrograms of different micro-pollutant solutions within 200-800nm by adopting an ultraviolet-visible absorption spectrometer to determine the characteristic peak positions of the solutions. Preparing a solution of micro-pollutants with a certain concentration, and measuring the absorbance value A of the solution0. Filtering the pollutant solution at 0.1MPa, and measuring the absorbance A corresponding to the filtratet。
(1) Dynamic adsorption: and (3) carrying out dynamic adsorption test on the porous membrane by using a flux test device, calculating the real-time adsorption rate until the adsorption rate is lower than 90%, and recording the total treatment capacity Q (mL) of the micro-pollutant solution.
Figure BDA0001791552950000061
(2) Static adsorption: shearing a proper amount of sample, and putting the sample into the micro-pollutant solution for stirring. Sampling at the same time, and detecting the absorbance value of the solution by using an ultraviolet spectrophotometer. After the absorbance value of the solution is unchanged, taking out the membrane, drying and weighing the membrane, and obtaining the equilibrium adsorption capacity q of the sample according to a formulae(mg/g)。
Figure BDA0001791552950000071
In the formula: a. the∞The ultraviolet absorbance of the solution at equilibrium; m is0Is the initial mass (mg) of BPA in solution.
Example 1:
mixing polyvinylidene fluoride, amino beta-cyclodextrin, polyethylene glycol, polyethyleneimine and N, N-dimethylacetamide according to the concentration requirements of the corresponding numbers in the following table 1.1, mechanically stirring for 5 hours, fully dissolving, defoaming, filtering to obtain a casting solution, and standing for 30 min. And coating the casting solution by a film scraping machine, immersing the casting solution into a mixed coagulating bath of pure water and N, N-dimethylacetamide for solidification and forming, washing with water at 25 ℃ to obtain a flaky composite film, further fully washing with deionized water, standing in air and drying to obtain the composite film with the aperture of 10 nm. The water flux, BSA retention, was tested. The adsorption performance of the organic micropollutants bisphenol A (BPA) and dinaphthol (2-NO) is tested.
Table 1.1: preparation condition of composite film for efficiently adsorbing organic micro-pollutants by polyvinylidene fluoride/amino beta-cyclodextrin
Figure BDA0001791552950000072
Table 1.2: composite membrane performance data of polyvinylidene fluoride/amino beta-cyclodextrin for efficiently adsorbing organic micro-pollutants
Figure BDA0001791552950000073
Figure BDA0001791552950000081
Example 2:
mixing polyvinyl chloride, carboxyl beta-cyclodextrin, polyvinylpyrrolidone, glutaraldehyde and N, N-dimethylformamide according to the concentration requirements of the corresponding numbers in the following table 2.1, mechanically stirring for 6 hours, fully dissolving, defoaming, filtering to obtain a casting solution, and standing for 30 min. Extruding the casting solution through a hollow fiber spinneret plate, immersing the casting solution into a mixed coagulating bath of pure water and N, N-dimethylformamide for solidification and forming, washing with water at 25 ℃ to obtain a hollow fibrous composite membrane, further fully washing with deionized water, and standing and airing in air to obtain the composite membrane with the aperture of 1 mu m. The water flux and the Escherichia coli retention rate of the strain are tested. The adsorption performance of the compound on dichlorophenol (2,4-DCP) and 4,4' -dihydroxy diphenyl sulfone (BPS), which are organic micropollutants, is tested.
Table 2.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polyvinyl chloride/carboxyl beta-cyclodextrin
Figure BDA0001791552950000082
Table 2.2: composite membrane performance data of polyvinyl chloride/carboxyl beta-cyclodextrin for efficiently adsorbing organic micro-pollutants
Figure BDA0001791552950000083
Example 3:
mixing polycaprolactam, carboxymethyl beta-cyclodextrin, polyvinyl alcohol, epichlorohydrin and N-methyl pyrrolidone according to the concentration requirement of the corresponding number in the following table 3.1, mechanically stirring for 8 hours, fully dissolving, defoaming, filtering to obtain a casting solution, and standing for 30 min. Coating the casting solution by a film scraper, immersing the casting solution into a mixed coagulating bath of pure water and N-methylpyrrolidone for curing and forming, washing with water at 25 ℃ to obtain a sheet-shaped composite film, further fully washing with deionized water, standing in air and drying to obtain the composite film with the aperture of 5 mu m, wherein the 3-2 formula section structure is shown in figure 2 a. The water flux and the dinoflagellate retention rate of the compound are tested. The adsorption performance of the compound on dichlorophenol (2,4-DCP) as an organic micro-pollutant and dioctyl phthalate (DEHP) is tested.
Table 3.1: preparation condition of composite membrane for efficiently adsorbing organic micro-pollutants by polycaprolactam/carboxymethyl beta-cyclodextrin
Figure BDA0001791552950000091
Table 3.2: composite membrane performance data of polycaprolactam/carboxymethyl beta-cyclodextrin for efficiently adsorbing organic micro-pollutants
Figure BDA0001791552950000092
Example 4:
according to the concentration requirement of the corresponding number in the following table 4.1, polyhexamethylene adipamide, allyl beta-cyclodextrin, dextran, diisocyanate and N, N-dimethylacetamide are mixed, mechanically stirred for 10 hours, fully dissolved, defoamed, filtered to obtain a casting solution, and the casting solution is kept stand for 30 min. Extruding the casting solution through a hollow fiber spinneret plate, immersing the casting solution into a mixed coagulating bath of pure water and N, N-dimethylacetamide for solidification and molding, washing with water at 25 ℃ to obtain a hollow fibrous composite membrane, further fully washing with deionized water, standing in air and drying to obtain the composite membrane with the aperture size of 2 microns. The water flux and the gold alga retention rate of the product are tested. The adsorption performance of the compound on organic micropollutants 4,4' -dihydroxydiphenyl sulfone (BPS) and erythromycin is tested.
Table 4.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polyhexamethylene adipamide/allyl beta-cyclodextrin
Figure BDA0001791552950000101
Table 4.2: composite membrane performance number for efficiently adsorbing organic micro-pollutants by polyhexamethylene adipamide/allyl beta-cyclodextrin
According to
Figure BDA0001791552950000102
Example 5:
mixing polyethylene terephthalate, hydroxybutyl beta-cyclodextrin, glucan, citric acid and N-methylpyrrolidone according to the concentration requirements of the corresponding numbers in the following table 5.1, mechanically stirring for 6 hours, fully dissolving, defoaming, filtering to obtain a casting solution, and standing for 30 min. Coating the casting solution by a film scraper, soaking the casting solution into a mixed coagulating bath of pure water and N-methylpyrrolidone for curing and forming, washing with water at 25 ℃ to obtain a flaky composite film, further fully washing with deionized water, standing in air and drying to obtain the composite film with the aperture size of 2 mu m, wherein the 5-2 section structure is shown in figure 2 b. The water flux, BSA retention, was tested. The adsorption performance of the compound on dichlorophenol (2,4-DCP) as an organic micropollutant and bis-p-chlorophenyl trichloroethane (DDT) as a plasticizer is tested.
Table 5.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polyethylene glycol terephthalate/hydroxybutyl beta-cyclodextrin
Figure BDA0001791552950000111
Table 5.2: composite membrane performance data of polyethylene glycol terephthalate/hydroxybutyl beta-cyclodextrin for efficiently adsorbing organic micropollutants
Figure BDA0001791552950000112
Example 6:
mixing polyacrylonitrile, amino beta-cyclodextrin, carboxyl beta-cyclodextrin (equal mass ratio), polyvinyl alcohol, citric acid and dimethyl sulfoxide according to the concentration requirements of the corresponding numbers in the following table 6.1, mechanically stirring for 8 hours, defoaming after fully dissolving, filtering to obtain a casting solution, and standing for 30 min. Extruding the casting solution through a hollow fiber spinneret plate, immersing the casting solution into a mixed coagulating bath of pure water and dimethyl sulfoxide for solidification and molding, washing with water at 30 ℃ to obtain a hollow fibrous composite membrane, further fully washing with deionized water, standing in air and drying to obtain the composite membrane with the aperture size of 2 mu m, wherein the 6-2 section structure is shown in figure 2 c. The water flux and the colloid retention rate of the composite material are tested. The adsorption performance of the compound on dichlorophenol (2,4-DCP) and erythromycin, which are organic micropollutants, is tested.
Table 6.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polyacrylonitrile/multi-group beta-cyclodextrin
Figure BDA0001791552950000121
Table 6.2: : composite membrane performance data of polyacrylonitrile/multi-group beta-cyclodextrin for efficiently adsorbing organic micro-pollutants
Figure BDA0001791552950000122
Example 7:
according to the concentration requirement of the corresponding number in the following table 7.1, polyetherimide, carboxymethyl beta-cyclodextrin, polyvinyl alcohol, glucan (equal mass ratio), epichlorohydrin and N, N-dimethylacetamide are mixed, mechanically stirred for 8 hours, fully dissolved, defoamed, filtered to obtain a casting solution, and the casting solution is kept stand for 30 min. Extruding the casting solution through a hollow fiber spinneret plate, immersing the casting solution into a mixed coagulating bath of pure water and N, N-dimethylacetamide for solidification and molding, washing with water at 25 ℃ to obtain a hollow fibrous composite membrane, further fully washing with deionized water, standing in air and drying to obtain the composite membrane with the aperture size of 2 microns. The water flux, BSA retention, was tested. The adsorption performance of the compound on organic micropollutant plasticizers, namely bis-p-chlorophenyl trichloroethane (DDT) and erythromycin, is tested.
Table 7.1: preparation condition of composite membrane for efficiently adsorbing organic micro-pollutants by polyetherimide/carboxymethyl beta-cyclodextrin
Figure BDA0001791552950000123
Figure BDA0001791552950000131
Table 7.2: composite membrane performance data of polyetherimide/carboxymethyl beta-cyclodextrin efficient adsorption of organic micropollutants
Figure BDA0001791552950000132
Example 8:
according to the concentration requirement of the corresponding number in the following table 8.1, polysulfone, allyl beta-cyclodextrin, polyvinylpyrrolidone, polyethyleneimine and citric acid (equal mass ratio) are mixed with N, N-dimethylformamide, mechanically stirred for 8 hours, fully dissolved, defoamed, filtered to obtain a casting solution, and kept stand for 30 min. Coating the casting solution by a film scraping machine, immersing the casting solution into a mixed coagulating bath of pure water and N, N-dimethylformamide for solidification and forming, washing with water at 30 ℃ to obtain a flaky composite film, further fully washing with deionized water, and standing and airing in the air to obtain the composite film with the aperture size of 1 mu m. The water flux and the Escherichia coli retention rate of the strain are tested. The adsorption performance of the catalyst on organic micro-pollutants dinaphthol (2-NO) and dioctyl phthalate (DEHP) is tested.
Table 8.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polysulfone/allyl beta-cyclodextrin
Figure BDA0001791552950000133
Figure BDA0001791552950000141
Table 8.2: : composite membrane performance data of polysulfone/allyl beta-cyclodextrin for efficiently adsorbing organic micro-pollutants
Figure BDA0001791552950000142
Example 9:
according to the concentration requirements of the corresponding numbers in the following table 9.1, polyether sulfone, hydroxybutyl beta-cyclodextrin, polyvinyl alcohol, citric acid and dimethyl sulfoxide are mixed, mechanically stirred for 8 hours, fully dissolved, defoamed and filtered to obtain a casting solution, and the casting solution is kept stand for 30 min. Extruding the casting solution through a hollow fiber spinneret plate, immersing the casting solution into a mixed coagulating bath of pure water and dimethyl sulfoxide for solidification and molding, washing with water at 25 ℃ to obtain a hollow fibrous composite membrane, further fully washing with deionized water, standing in air and drying to obtain the composite membrane with the aperture size of 2 mu m, wherein the 9-2 section structure is shown in figure 2 d. The water flux and the dinoflagellate retention rate of the compound are tested. The adsorption performance of the composite adsorbent on organic micropollutant plasticizers, namely bis-p-chlorophenyl trichloroethane (DDT) and dinaphthol (2-NO) is tested.
Table 9.1: preparation condition of composite membrane for efficiently adsorbing organic micropollutants by polyether sulfone/hydroxybutyl beta-cyclodextrin
Figure BDA0001791552950000143
Table 9.2: performance data of composite membrane for efficiently adsorbing organic micropollutants by polyether sulfone/hydroxybutyl beta-cyclodextrin
Figure BDA0001791552950000151
The above embodiments show that the composite membrane for removing organic micro-pollutants has a high flux, and simultaneously has a very superior adsorption removal effect on organic micro-pollutants in a water body, such as residual pesticides, antibiotics, hormones, polycyclic aromatic hydrocarbons, plasticizers and the like, and has very excellent performance in both adsorption rate and saturated adsorption capacity. Therefore, the composite membrane can be used for efficiently removing organic micro-pollutants in a water body, and is an efficient and stable separation membrane with great application value. The preparation method of the composite membrane is simple and convenient, is easy for industrial production, has low cost and high application value, and can be effectively used in the fields of household water purification, sewage treatment and the like.

Claims (3)

1. A preparation method of a composite membrane for efficiently filtering micro-pollutants in water is characterized by comprising the following steps:
(1) mixing a film-forming polymer, functionalized beta-cyclodextrin, a pore-forming agent, a crosslinking agent and a solvent according to a certain mass ratio, mechanically stirring and dissolving at 40-100 ℃, reacting for 5-10 hours, and vacuumizing and defoaming to obtain a casting solution; the mass ratio of each component is as follows: 10-30% of film-forming polymer; 1-10% of functionalized beta-cyclodextrin; 10-20% of pore-foaming agent; 0.5-5% of a cross-linking agent; 35-78.5% of a solvent;
(2) coating the membrane casting solution by a membrane scraping machine or extruding the membrane casting solution by a hollow fiber spinneret plate, and immersing the membrane casting solution into a coagulating bath for solidification and forming to form a polymer nascent membrane;
(3) putting the polymer primary membrane into deionized water for thorough cleaning to obtain a composite membrane, and applying the composite membrane to filtering and removing micropollutants in water;
the film-forming polymer is any one of polyvinylidene fluoride, polyvinyl chloride, polycaprolactam, polyhexamethylene adipamide, polyethylene glycol terephthalate, polyacrylonitrile, polyetherimide, polysulfone and polyethersulfone; the functionalized beta-cyclodextrin is one or two of amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl beta-cyclodextrin, allyl beta-cyclodextrin and hydroxybutyl beta-cyclodextrin; the pore-foaming agent is one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol and glucan; the cross-linking agent is one or more of polyethyleneimine, glutaraldehyde, epichlorohydrin, diisocyanate and citric acid; the coagulating bath is pure water or a mixed solution of the pure water and a solvent, the weight percentage of the pure water is 10-100%, and the weight percentage of the solvent is 0-90%; the solvent is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
2. A composite membrane for efficiently filtering micropollutants in water, prepared according to the method of claim 1, wherein the composite membrane is in the shape of a flat plate or a hollow fiber.
3. The composite membrane for efficiently filtering micropollutants in water according to claim 2, wherein the pore size of the composite membrane is between 0.01 and 5 micrometers.
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