CN103084081B - Preparation method of large-flux amphiprotic nano-filtration membrane - Google Patents

Preparation method of large-flux amphiprotic nano-filtration membrane Download PDF

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CN103084081B
CN103084081B CN201310018806.9A CN201310018806A CN103084081B CN 103084081 B CN103084081 B CN 103084081B CN 201310018806 A CN201310018806 A CN 201310018806A CN 103084081 B CN103084081 B CN 103084081B
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amphoteric
nanofiltration membrane
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CN103084081A (en
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薛立新
刘富
马碧荣
鲁华锋
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

本发明涉及一种大通量两性纳滤膜的制备方法。传统纳滤膜的制备方法主要分为相转化法和复合法,但很难得到通量很大的膜。该方法是超滤膜用乙醇和去离子水洗涤,然后浸泡于烯烃类阳离子单体溶液中,100~600W紫外灯下辐照3~120分钟,得到阳离子纳滤膜;阳离子纳滤膜用去离子水洗涤,然后浸泡于两性烯烃类单体溶液中,100~600W紫外灯下辐照2~40min,得到两性纳滤膜;最后两性纳滤膜用去离子水洗涤。本发明方法制备的两性纳滤膜在0.5MPa下水通量为55~200L/m2h,对氯化钠、MgCl2、MgSO4截留率分别为40~85﹪、80~97﹪、60~93﹪。本发明方法制备工艺简单可靠,适用于工业化。The invention relates to a preparation method of a large flux amphoteric nanofiltration membrane. Traditional nanofiltration membrane preparation methods are mainly divided into phase inversion method and composite method, but it is difficult to obtain a membrane with a large flux. The method is that the ultrafiltration membrane is washed with ethanol and deionized water, then soaked in an olefinic cationic monomer solution, and irradiated under a 100-600W ultraviolet lamp for 3-120 minutes to obtain a cationic nanofiltration membrane; Washing with ionized water, soaking in amphoteric olefin monomer solution, and irradiating with 100-600W ultraviolet lamp for 2-40 minutes to obtain amphoteric nanofiltration membrane; finally, amphoteric nanofiltration membrane is washed with deionized water. The amphoteric nanofiltration membrane prepared by the method of the present invention has a water flux of 55 to 200 L/m 2 h at 0.5 MPa, and a rejection rate of 40 to 85%, 80 to 97%, and 60 to 40% for sodium chloride, MgCl 2 and MgSO 4 , respectively. 93%. The preparation process of the method of the invention is simple and reliable, and is suitable for industrialization.

Description

一种大通量两性纳滤膜的制备方法A kind of preparation method of large flux amphoteric nanofiltration membrane

技术领域 technical field

本发明属于膜分离技术领域,涉及一种大通量两性纳滤膜的制备方法。 The invention belongs to the technical field of membrane separation, and relates to a preparation method of a large-flux amphoteric nanofiltration membrane.

背景技术 Background technique

纳滤膜是一种性能介于超滤和反渗透之间的压力驱动膜。纳滤膜具有以下几个特点:截留分子量在200~1000Da之间,适于除去大约1nm左右的溶解组分;操作压力低,比反渗透所要求的压力低,因此也称为“低压反渗透膜”;具有离子选择性,纳滤膜的一个很大的特征是膜本体带有电荷,通过静电相互作用,可以除去水溶液中的二价及多价离子,对二价及多价离子的截留率在90﹪以上,对一价离子的截留率小于80﹪,因此可实现不同价态离子的分离。由于纳滤膜具有以上特点,因此已被广泛应用于环保、水资源、食品、医药、和化工等各个行业。 Nanofiltration membrane is a pressure-driven membrane with properties between ultrafiltration and reverse osmosis. The nanofiltration membrane has the following characteristics: the molecular weight cut-off is between 200 and 1000Da, which is suitable for removing dissolved components of about 1nm; the operating pressure is lower than that required by reverse osmosis, so it is also called "low pressure reverse osmosis". "Membrane"; with ion selectivity, a major feature of nanofiltration membranes is that the membrane body is charged, and through electrostatic interaction, divalent and multivalent ions in aqueous solution can be removed, and the interception of divalent and multivalent ions The rejection rate of monovalent ions is less than 80%, so the separation of ions of different valence states can be realized. Due to the above characteristics, nanofiltration membranes have been widely used in various industries such as environmental protection, water resources, food, medicine, and chemical industry.

纳滤膜的制备方法可分为相转化法和复合法两种。相转化法制备纳滤膜操作简单、易行,但选取合适的膜材料至关重要,传统的高分子膜材料较难直接制得小孔径的膜。复合法制备纳滤膜主要包括两步:第一步是微孔基膜的制备;第二步是超薄表层的制备,主要方法有涂敷法,界面聚合法,热、光、辐射交联固化法,等离子体聚合法等。其中,涂敷法的关键是选择与基膜相匹配的复合液,但复合液与基膜是物理吸附作用,在清洗时复合液会流失,失去纳滤的功能。界面聚合法是用两种反应活性很高的单体,在两个互不相容的界面处发生聚合反应,从而在多空支撑体上形成薄层。利用该法中国专利(CN102423643A)利用丝胶蛋白水溶液与含芳香多元酰氯的有机溶液之间的界面缩聚法制备得到一种高通量阴离子复合纳滤膜;中国专利(CN1636626A)通过胺端基聚酰胺与聚苯三甲酰氯有机溶液的界面聚合法制得新型纳滤膜,该膜在0.6MPa下水通量在38.3~56.8L/m2h之间,对1000mg/L氯化钠的截留率在41.8~53.8﹪之间;但是该法对基膜的选取和制备,调控两类反应物的分配系数和扩散速度,及优化界面条件,使表层疏松程度合理化等条件要求都比较苛刻。中国专利(CN101766962A)利用过程比较复杂的涂覆与热交联固化法结合来制备荷正电的纳滤膜,该膜在0.6MPa下水通量为12~18L/m2h,对二价阳离子的截留率一般为75~95﹪,对一价阳离子的截留率低于65﹪。与以上各种纳滤膜的制备方法相比较,由于紫外接枝法具有制备工艺简单,反应可控等特点,且只能改变膜的表面性质,不会改变基膜的性质,这种方法制备的亲水性纳滤膜在水中仍有很好的稳定性。其中中国专利(CN102247771A)分别以含磺酸基的烯类单体和含有羟基或羧基的烯类单体为单体采用紫外辐照分步接枝的方法制备了一种荷负电纳滤膜,该膜在0.4MPa下通量为28.3~36.6L/m2h,对硫酸钠的截留率为94.8~97.9﹪,对氯化钠的截留率为60.2~65.3﹪,但是对高价阳离子的盐溶液截留率较低;中国专利(CN101934204A)利用紫外辐照分步接枝法以聚醚醚酮超滤膜为基膜制得两性纳滤膜,该膜对二价阳离子(MgCl2)和二价阴离子(Na2SO4)盐溶液都具有较高的截留率均在90﹪以上,但是该膜的通量比较低,在0.4MPa下通量只有3.2~9.6L/m2h。 The preparation methods of nanofiltration membranes can be divided into phase inversion method and composite method. The preparation of nanofiltration membranes by phase inversion method is simple and easy to operate, but it is very important to select suitable membrane materials. It is difficult to directly produce membranes with small pore diameters from traditional polymer membrane materials. The preparation of nanofiltration membrane by composite method mainly includes two steps: the first step is the preparation of microporous base membrane; the second step is the preparation of ultra-thin surface layer, the main methods are coating method, interfacial polymerization method, heat, light, radiation crosslinking Curing method, plasma polymerization method, etc. Among them, the key of the coating method is to select the composite solution that matches the basement membrane, but the composite solution and the basement membrane are physically adsorbed, and the composite solution will be lost during cleaning, losing the function of nanofiltration. The interfacial polymerization method is to use two highly reactive monomers to polymerize at two mutually incompatible interfaces, thereby forming a thin layer on the porous support. Using this Chinese patent (CN102423643A) to prepare a high-flux anion composite nanofiltration membrane by interfacial polycondensation method between sericin aqueous solution and organic solution containing aromatic polyacyl chloride; Chinese patent (CN1636626A) A new type of nanofiltration membrane was prepared by interfacial polymerization of amide and polyphthaloyl chloride organic solution. The water flux of the membrane was between 38.3 and 56.8 L/m 2 h at 0.6 MPa, and the rejection rate of 1000 mg/L sodium chloride was 41.8 ~53.8%; however, this method has strict requirements on the selection and preparation of the base film, the regulation of the distribution coefficient and diffusion rate of the two types of reactants, the optimization of the interface conditions, and the rationalization of the looseness of the surface. Chinese patent (CN101766962A) uses the combination of complex coating and thermal cross - linking curing method to prepare a positively charged nanofiltration membrane. The rejection rate is generally 75 to 95%, and the rejection rate for monovalent cations is lower than 65%. Compared with the preparation methods of the above various nanofiltration membranes, the ultraviolet grafting method has the characteristics of simple preparation process and controllable reaction, and can only change the surface properties of the membrane without changing the properties of the base membrane. The hydrophilic nanofiltration membrane still has good stability in water. Among them, the Chinese patent (CN102247771A) prepared a negatively charged nanofiltration membrane by step-by-step grafting of sulfonic acid group-containing vinyl monomers and hydroxyl or carboxyl-containing vinyl monomers. The flux of the membrane at 0.4MPa is 28.3-36.6L/m 2 h, the rejection rate of sodium sulfate is 94.8-97.9%, and the rejection rate of sodium chloride is 60.2-65.3%, but the salt solution of high-valent cations The rejection rate is low; the Chinese patent (CN101934204A) uses ultraviolet irradiation step-by-step grafting method to prepare amphoteric nanofiltration membrane with polyether ether ketone ultrafiltration membrane as the base membrane. The anion (Na 2 SO 4 ) salt solution has a high rejection rate above 90%, but the flux of the membrane is relatively low, and the flux is only 3.2-9.6L/m 2 h at 0.4MPa.

通过对以上各种纳滤膜的制备方法进行分析,发现利用紫外辐照接枝法制备纳滤膜成为一种具有潜在应用价值的制膜技术,通过紫外辐照接枝法利用改性的大通量聚砜超滤膜作为基膜来制备大通量纳滤膜则没有报道。 Through the analysis of the above preparation methods of various nanofiltration membranes, it is found that the preparation of nanofiltration membranes by ultraviolet irradiation grafting has become a membrane technology with potential application value. Flux polysulfone ultrafiltration membrane as the base membrane to prepare high-flux nanofiltration membrane is not reported.

发明内容 Contents of the invention

本发明的目的针对现有技术的不足,提供了一种大通量两性纳滤膜的制备方法。 The object of the present invention aims at the deficiencies of the prior art, and provides a method for preparing a large-flux amphoteric nanofiltration membrane.

本发明利用超滤膜为基膜,采用紫外辐照接枝法制备大通量两性纳滤膜。 In the invention, the ultrafiltration membrane is used as the base membrane, and the large-flux amphoteric nanofiltration membrane is prepared by an ultraviolet irradiation grafting method.

本发明方法的具体步骤是: The concrete steps of the inventive method are:

步骤(1).将超滤膜用乙醇洗涤1~10次,然后用去离子水洗涤5~20次,去除膜表面杂质; Step (1). Wash the ultrafiltration membrane with ethanol for 1 to 10 times, and then wash it with deionized water for 5 to 20 times to remove impurities on the surface of the membrane;

所述的超滤膜的材质为聚砜(PSF)、聚醚酮(PEK)、聚醚砜(PES)的一种或多种; The material of the ultrafiltration membrane is one or more of polysulfone (PSF), polyetherketone (PEK) and polyethersulfone (PES);

作为优选,超滤膜用乙醇洗涤4~7次; As preferably, the ultrafiltration membrane is washed 4 to 7 times with ethanol;

作为优选,超滤膜用去离子水洗涤10~15次; As preferably, the ultrafiltration membrane is washed 10 to 15 times with deionized water;

步骤(2).将洗涤后的超滤膜浸泡于烯烃类阳离子单体溶液中,超滤膜的膜上表面与烯烃类阳离子单体溶液的液体表面距离为1~5mm,100~600W紫外灯下辐照3~120分钟,超滤膜的膜上表面与紫外灯的距离为5~40cm,得到阳离子纳滤膜; Step (2). Soak the washed ultrafiltration membrane in the olefinic cationic monomer solution, the distance between the upper surface of the ultrafiltration membrane and the liquid surface of the olefinic cationic monomer solution is 1-5mm, 100-600W ultraviolet lamp Under irradiation for 3 to 120 minutes, the distance between the upper surface of the ultrafiltration membrane and the ultraviolet lamp is 5 to 40 cm, and a cationic nanofiltration membrane is obtained;

所述的烯烃类阳离子单体溶液为质量分数为1~65﹪烯烃类阳离子单体的水溶液或甲醇溶液或乙醇溶液; The olefinic cationic monomer solution is an aqueous solution or a methanol solution or an ethanol solution with a mass fraction of 1 to 65% of the olefinic cationic monomer;

所述的烯烃类阳离子单体为含有季铵盐或叔胺基的烯烃; The olefinic cationic monomer is an olefin containing a quaternary ammonium salt or a tertiary amino group;

所述的紫外灯是波长为290~400nm的高压汞灯,在10~30℃下空气中进行反应; The ultraviolet lamp is a high-pressure mercury lamp with a wavelength of 290-400nm, and reacts in the air at 10-30°C;

作为优选,烯烃类阳离子单体溶液中烯烃类阳离子单体的质量含量为5~50﹪; Preferably, the mass content of the olefin cationic monomer in the olefin cationic monomer solution is 5-50%;

作为优选,紫外灯的功率为300~500W,紫外辐照时间为5~30min, 超滤膜的膜上表面与紫外灯的距离为10~30cm; Preferably, the power of the ultraviolet lamp is 300-500W, the ultraviolet irradiation time is 5-30min, and the distance between the upper surface of the ultrafiltration membrane and the ultraviolet lamp is 10-30cm;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤5~10次,除去膜表面残余的烯烃类阳离子单体,然后将洗涤后的阳离子纳滤膜浸泡于两性烯烃类单体溶液中,阳离子纳滤膜的膜上表面与两性烯烃类单体溶液的液体表面距离为1~5mm,100~600W紫外灯下辐照2~40min,阳离子纳滤膜的膜上表面与紫外灯的距离为5~40cm,得到两性纳滤膜; Step (3). Wash the cationic nanofiltration membrane obtained after ultraviolet radiation with deionized water for 5 to 10 times to remove residual olefin cationic monomers on the surface of the membrane, and then soak the washed cationic nanofiltration membrane in amphoteric olefins In the monomer solution, the distance between the upper surface of the cationic nanofiltration membrane and the liquid surface of the amphoteric olefin monomer solution is 1 to 5 mm, and the upper surface of the cationic nanofiltration membrane and the liquid surface of the amphoteric olefin monomer solution are irradiated for 2 to 40 minutes under a 100-600W ultraviolet lamp. The distance of the ultraviolet lamp is 5-40cm, and the amphoteric nanofiltration membrane is obtained;

所述的两性烯烃类单体溶液为质量分数为1~30﹪两性烯烃类单体的水溶液或甲醇溶液或乙醇溶液; The amphoteric olefin monomer solution is an aqueous solution or methanol solution or ethanol solution with a mass fraction of 1 to 30% amphoteric olefin monomer;

所述的两性烯烃类单体为含有两性基团的烯烃;两性烯烃类单体中阴性基团为磺酸基、羧基的一种或两种,阳性基团为季铵盐、叔胺基的一种或两种; The amphoteric olefin monomers are olefins containing amphoteric groups; the negative groups in the amphoteric olefin monomers are one or both of sulfonic acid groups and carboxyl groups, and the positive groups are quaternary ammonium salts and tertiary amino groups. one or two;

作为优选,两性烯烃类单体溶液中两性烯烃类单体的质量含量为5~20﹪; Preferably, the mass content of the amphoteric olefinic monomer in the amphoteric olefinic monomer solution is 5-20%;

作为优选,紫外灯的功率为300~500W,紫外辐照时间为10~30min,阳离子纳滤膜的膜上表面与紫外灯的距离为10~30cm; Preferably, the power of the ultraviolet lamp is 300-500W, the ultraviolet irradiation time is 10-30min, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 10-30cm;

步骤(4).将得到的两性纳滤膜用去离子水洗涤10~20次,除去膜表面残余的两性烯烃类单体。 Step (4). Washing the obtained amphoteric nanofiltration membrane with deionized water for 10 to 20 times to remove residual amphoteric olefin monomers on the surface of the membrane.

所述的膜上表面到紫外灯的距离和紫外灯的功率是用来控制辐射强度的。 The distance from the upper surface of the film to the ultraviolet lamp and the power of the ultraviolet lamp are used to control the radiation intensity.

本发明所制备的两性纳滤膜的性能是通过改变辐照时间、单体浓度及辐射强度来进行控制的。通过改变接枝单体的种类来控制纳滤膜表面的电荷种类,使两性纳滤膜的性质在较大的范围内变化,得到对高价阳离子和高价阴离子都有很高截留率的两性荷电纳滤膜。 The performance of the amphoteric nanofiltration membrane prepared by the invention is controlled by changing the irradiation time, monomer concentration and radiation intensity. By changing the type of grafted monomer to control the type of charge on the surface of the nanofiltration membrane, the properties of the amphoteric nanofiltration membrane can be changed in a large range, and the amphoteric charge with a high rejection rate for high-valent cations and high-valent anions can be obtained. Nanofiltration.

通过本发明方法制备得到的两性纳滤膜在0.5MPa下水通量为55~200L/m2h,对氯化钠的截留率为40~85﹪,对MgCl2的截留率为80~97﹪,对MgSO4的截留率为60~93﹪。 The amphoteric nanofiltration membrane prepared by the method of the present invention has a water flux of 55-200 L/m h at 0.5 MPa, a rejection rate of 40-85% to sodium chloride, and a rejection rate of 80-97% to MgCl , the rejection rate of MgSO 4 is 60-93%.

本发明方法制备工艺简单可靠,适用于工业化生产。 The preparation process of the method of the invention is simple and reliable, and is suitable for industrial production.

具体实施方式 Detailed ways

下面结合实施例对本发明作进一步的分析。 The present invention is further analyzed below in conjunction with embodiment.

实施例1. Example 1.

步骤(1).将聚砜超滤膜用乙醇洗涤1次,然后用去离子水洗涤8次,去除膜表面杂质; Step (1). The polysulfone ultrafiltration membrane is washed once with ethanol, and then washed eight times with deionized water to remove impurities on the surface of the membrane;

步骤(2).将洗涤后的聚砜超滤膜浸泡于质量分数为1﹪ 4-乙烯基吡啶的水溶液中,聚砜超滤膜的膜上表面与质量分数为1﹪ 4-乙烯基吡啶的水溶液液体表面距离为1mm,100W紫外灯下辐照120分钟,聚砜超滤膜的膜上表面与紫外灯的距离为5cm,得到阳离子纳滤膜; Step (2). The polysulfone ultrafiltration membrane after washing is soaked in the aqueous solution that mass fraction is 1% 4-vinylpyridine, and the membrane upper surface of polysulfone ultrafiltration membrane and mass fraction are 1% 4-vinylpyridine The distance between the liquid surface of the aqueous solution is 1 mm, irradiated for 120 minutes under a 100W ultraviolet lamp, and the distance between the film upper surface of the polysulfone ultrafiltration membrane and the ultraviolet lamp is 5 cm, and a cationic nanofiltration membrane is obtained;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤5次,除去膜表面残余的4-乙烯基吡啶,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为1﹪ 2-乙烯基吡啶丙基磺酸盐的水溶液中,阳离子纳滤膜的膜上表面与质量分数为1﹪ 2-乙烯基吡啶丙基磺酸盐的水溶液液体表面距离为1mm,100W紫外灯下辐照40min,阳离子纳滤膜的膜上表面与紫外灯的距离为5cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 5 times with deionized water to remove residual 4-vinylpyridine on the surface of the membrane, and then the washed cationic nanofiltration membrane is soaked in a 1% mass fraction In the aqueous solution of 2-vinylpyridinepropylsulfonate, the distance between the upper surface of the cationic nanofiltration membrane and the liquid surface of the aqueous solution with a mass fraction of 1% 2-vinylpyridinepropylsulfonate is 1mm, under a 100W ultraviolet lamp Irradiate for 40min, the distance between the membrane upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 5cm, and obtain the amphoteric nanofiltration membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤10次,除去膜表面残余的2-乙烯基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 10 times with deionized water to remove residual 2-vinylpyridinepropylsulfonate on the surface of the membrane.

实施例1制备得到的两性纳滤膜在0.5MPa下水通量为200L/m2h,对氯化钠的截留率为40﹪,对MgCl2的截留率为80﹪,对MgSO4的截留率为60﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 1 is 200L/m h at 0.5MPa, the rejection rate to sodium chloride is 40%, the rejection rate to MgCl is 80%, and the rejection rate to MgSO is 60%.

实施例2. Example 2.

步骤(1).将聚醚酮超滤膜用乙醇洗涤2次,然后用去离子水洗涤10次,去除膜表面杂质; Step (1). Wash the polyetherketone ultrafiltration membrane twice with ethanol, and then wash it 10 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚醚酮超滤膜浸泡于质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的水溶液中,聚醚酮超滤膜的膜上表面与质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的水溶液液体表面距离为1.5mm,150W紫外灯下辐照110分钟,聚醚酮超滤膜的膜上表面与紫外灯的距离为8cm,得到阳离子纳滤膜; Step (2). Soak the polyetherketone ultrafiltration membrane after washing in the aqueous solution of 5% 3-methacrylamidopropyltrimethylammonium in mass fraction, the film upper surface of polyetherketone ultrafiltration membrane and The distance between the liquid surface of the aqueous solution with a mass fraction of 5% 3-methacrylamidopropyltrimethylammonium is 1.5mm, and the 150W ultraviolet lamp is irradiated for 110 minutes. The distance is 8cm, and the cationic nanofiltration membrane is obtained;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤6次,除去膜表面残余的3-甲基丙烯酰胺基丙基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为5﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的水溶液中,阳离子纳滤膜的膜上表面与质量分数为5﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的水溶液液体表面距离为1.5mm,150W紫外灯下辐照38min,阳离子纳滤膜的膜上表面与紫外灯的距离为8cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 6 times with deionized water to remove residual 3-methacrylamidopropyltrimethylammonium on the membrane surface, and then the washed cationic nanofiltration The membrane is soaked in an aqueous solution with a mass fraction of 5% m-vinyl-o-picoline propyl sulfonate, the upper surface of the cationic nanofiltration membrane and the mass fraction of 5% m-vinyl-o-methyl The distance between the liquid surface of the aqueous solution of pyridine propyl sulfonate is 1.5 mm, irradiated under a 150W ultraviolet lamp for 38 minutes, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 8 cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤11次,除去膜表面残余的间-乙烯基-邻-甲基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 11 times with deionized water to remove residual m-vinyl-o-picoline propylsulfonate on the membrane surface.

实施例2制备得到的两性纳滤膜在0.5MPa下水通量为180L/m2h,对氯化钠的截留率为48.7﹪,对MgCl2的截留率为82.1﹪,对MgSO4的截留率为63.2﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 2 is 180L/m h at 0.5MPa, the rejection rate to sodium chloride is 48.7%, the rejection rate to MgCl is 82.1%, and the rejection rate to MgSO It is 63.2%.

实施例3. Example 3.

步骤(1).将聚醚砜超滤膜用乙醇洗涤3次,然后用去离子水洗涤9次,去除膜表面杂质; Step (1). The polyethersulfone ultrafiltration membrane is washed 3 times with ethanol, and then washed 9 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚醚砜超滤膜浸泡于质量分数为30﹪二烯丙基二甲基氯化铵的水溶液中,聚醚砜超滤膜的膜上表面与质量分数为30﹪二烯丙基二甲基氯化铵的水溶液液体表面距离为2mm,180W紫外灯下辐照90分钟,聚醚砜超滤膜的膜上表面与紫外灯的距离为10cm,得到阳离子纳滤膜; Step (2). Soak the polyethersulfone ultrafiltration membrane after washing in the aqueous solution of 30% diallyl dimethyl ammonium chloride in mass fraction, the film upper surface and mass fraction of polyethersulfone ultrafiltration membrane are The distance between the liquid surface of the aqueous solution of 30% diallyl dimethyl ammonium chloride is 2 mm, and it is irradiated under a 180W ultraviolet lamp for 90 minutes. The distance between the upper surface of the polyethersulfone ultrafiltration membrane and the ultraviolet lamp is 10 cm, and the cationic nano membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤7次,除去膜表面残余的二烯丙基二甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为10﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的水溶液中,阳离子纳滤膜的膜上表面与质量分数为10﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的水溶液液体表面距离为2mm,180W紫外灯下辐照35min,阳离子纳滤膜的膜上表面与紫外灯的距离为10cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 7 times with deionized water to remove residual diallyl dimethyl ammonium chloride on the membrane surface, and then the cationic nanofiltration membrane after washing is soaked in In an aqueous solution with a mass fraction of 10% acrylamido ethyl dimethyl ammonium propyl sulfonate, the membrane upper surface of the cationic nanofiltration membrane and a mass fraction of 10% acrylamido ethyl dimethyl ammonium propyl sulfonic acid The distance between the liquid surface of the aqueous salt solution is 2 mm, irradiated under a 180W ultraviolet lamp for 35 minutes, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 10 cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤12次,除去膜表面残余的丙烯酰胺基乙基二甲基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 12 times with deionized water to remove residual acrylamido ethyl dimethyl ammonium propyl sulfonate on the membrane surface.

实施例3制备得到的两性纳滤膜在0.5MPa下水通量为100L/m2h,对氯化钠的截留率为65.3﹪,对MgCl2的截留率为85.9﹪,对MgSO4的截留率为72.7﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 3 is 100L/m h at 0.5MPa, the rejection rate to sodium chloride is 65.3%, the rejection rate to MgCl is 85.9%, and the rejection rate to MgSO It is 72.7%.

实施例4. Example 4.

步骤(1).将聚砜/聚醚酮超滤膜用乙醇洗涤4次,然后用去离子水洗涤5次,去除膜表面杂质; Step (1). The polysulfone/polyetherketone ultrafiltration membrane is washed 4 times with ethanol, and then washed 5 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚酮超滤膜浸泡于质量分数为50﹪甲基丙烯酰氧乙基三甲基氯化铵的水溶液中,聚砜/聚醚酮超滤膜的膜上表面与质量分数为50﹪甲基丙烯酰氧乙基三甲基氯化铵的水溶液液体表面距离为2.5mm,200W紫外灯下辐照80分钟,聚砜/聚醚酮超滤膜的膜上表面与紫外灯的距离为12cm,得到阳离子纳滤膜; Step (2). Soak the washed polysulfone/polyetherketone ultrafiltration membrane in an aqueous solution with a mass fraction of 50% methacryloyloxyethyltrimethylammonium chloride, polysulfone/polyetherketone ultrafiltration The distance between the upper surface of the membrane and the liquid surface of an aqueous solution with a mass fraction of 50% methacryloyloxyethyltrimethylammonium chloride is 2.5mm, irradiated by a 200W ultraviolet lamp for 80 minutes, polysulfone/polyetherketone ultrafiltration The distance between the membrane upper surface of the membrane and the ultraviolet lamp is 12cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤8次,除去膜表面残余的甲基丙烯酰氧乙基三甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡质量分数为20﹪ 2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐的水溶液中,阳离子纳滤膜的膜上表面与质量分数为20﹪ 2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐的水溶液液体表面距离为2mm,200W紫外灯下辐照32min,阳离子纳滤膜的膜上表面与紫外灯的距离为12cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 8 times with deionized water to remove residual methacryloyloxyethyltrimethylammonium chloride on the membrane surface, and then the washed cationic nanofiltration In an aqueous solution where the membrane is soaked with a mass fraction of 20% 2-methacrylamide ethyl diethylammonium propyl sulfonate, the membrane upper surface of the cationic nanofiltration membrane and the mass fraction of 20% 2-methacrylamide ethyl The distance between the liquid surface of the aqueous solution of diethylammonium propyl sulfonate is 2mm, irradiated under a 200W ultraviolet lamp for 32min, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 12cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤13次,除去膜表面残余的2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 13 times with deionized water to remove residual 2-methacrylamide ethyl diethyl ammonium propyl sulfonate on the membrane surface.

实施例4制备得到的两性纳滤膜在0.5MPa下水通量为72L/m2h,对氯化钠的截留率为78.3﹪,对MgCl2的截留率为89.5﹪,对MgSO4的截留率为82.3﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 4 is 72L/m h at 0.5MPa, the rejection rate to sodium chloride is 78.3%, the rejection rate to MgCl is 89.5%, and the rejection rate to MgSO It is 82.3%.

实施例5. Example 5.

步骤(1).将聚砜/聚醚砜超滤膜用乙醇洗涤5次,然后用去离子水洗涤6次,去除膜表面杂质; Step (1). The polysulfone/polyethersulfone ultrafiltration membrane is washed 5 times with ethanol, and then 6 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚砜超滤膜浸泡于质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的水溶液中,聚砜/聚醚砜超滤膜的膜上表面与质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的水溶液液体表面距离为3mm,250W紫外灯下辐照70分钟,聚砜/聚醚砜超滤膜的膜上表面与紫外灯的距离为15cm,得到阳离子纳滤膜; Step (2). Soak the washed polysulfone/polyethersulfone ultrafiltration membrane in an aqueous solution with a mass fraction of 65% 3-acrylamido-3-methylbutyltrimethylammonium, polysulfone/polyether The distance between the upper surface of the membrane of the sulfone ultrafiltration membrane and the liquid surface of an aqueous solution with a mass fraction of 65% 3-acrylamido-3-methylbutyltrimethylammonium is 3 mm, and the polysulfone/ The distance between the upper surface of the polyethersulfone ultrafiltration membrane and the ultraviolet lamp is 15 cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤9次,除去膜表面残余的3-丙烯酰胺基-3-甲基丁基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为30﹪ 2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐的水溶液中,阳离子纳滤膜的膜上表面与质量分数为30﹪ 2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐的水溶液液体表面距离为3mm,250W紫外灯下辐照28min,阳离子纳滤膜的膜上表面与紫外灯的距离为15cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 9 times with deionized water to remove residual 3-acrylamide-3-methylbutyltrimethylammonium on the surface of the membrane, and then the washed The cationic nanofiltration membrane is immersed in an aqueous solution with a mass fraction of 30% 2-methacryloyloxyethyl dimethyl ammonium propyl sulfonate, and the upper surface of the cationic nanofiltration membrane and the mass fraction are 30% 2-form The distance between the liquid surface of the aqueous solution of acryloyloxyethyl dimethyl ammonium propyl sulfonate is 3mm, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 15cm under the irradiation of 250W ultraviolet lamp for 28min, and the amphoteric nanofiltration membrane is obtained membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤14次,除去膜表面残余的2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 14 times with deionized water to remove residual 2-methacryloyloxyethyldimethylammonium propylsulfonate on the surface of the membrane.

实施例5制备得到的两性纳滤膜在0.5MPa下水通量为65L/m2h,对氯化钠的截留率为80.3﹪,对MgCl2的截留率为91.4﹪,对MgSO4的截留率为87.2﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 5 is 65L/m h at 0.5MPa, the rejection rate to sodium chloride is 80.3%, the rejection rate to MgCl is 91.4 %, and the rejection rate to MgSO It is 87.2%.

实施例6. Example 6.

步骤(1).将聚醚酮/聚醚砜超滤膜用乙醇洗涤6次,然后用去离子水洗涤7次,去除膜表面杂质; Step (1). The polyetherketone/polyethersulfone ultrafiltration membrane is washed 6 times with ethanol, and then washed 7 times with deionized water to remove impurities on the surface of the membrane;

步骤(2).将洗涤后的聚醚酮/聚醚砜超滤膜浸泡于质量分数为1﹪ 4-乙烯基吡啶的甲醇溶液中,聚醚酮/聚醚砜超滤膜的膜上表面与质量分数为1﹪ 4-乙烯基吡啶的甲醇溶液液体表面距离为3.5mm,280W紫外灯下辐照65分钟,超滤膜的膜上表面与紫外灯的距离为20cm,得到阳离子纳滤膜; Step (2). Soak the washed polyetherketone/polyethersulfone ultrafiltration membrane in a methanol solution with a mass fraction of 1% 4-vinylpyridine, and the membrane upper surface of the polyetherketone/polyethersulfone ultrafiltration membrane The distance from the liquid surface of the methanol solution with a mass fraction of 1% 4-vinylpyridine is 3.5mm, irradiated under a 280W ultraviolet lamp for 65 minutes, and the distance between the upper surface of the ultrafiltration membrane and the ultraviolet lamp is 20cm, and a cationic nanofiltration membrane is obtained. ;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤10次,除去膜表面残余的4-乙烯基吡啶,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为1﹪ 2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐的甲醇溶液中,阳离子纳滤膜的膜上表面与质量分数为1﹪ 2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐的甲醇溶液液体表面距离为3.5mm,280W紫外灯下辐照30min,阳离子纳滤膜的膜上表面与紫外灯的距离为20cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 10 times with deionized water to remove residual 4-vinylpyridine on the surface of the membrane, and then the washed cationic nanofiltration membrane is soaked in a 1% mass fraction In the methanol solution of 2-methacryloyloxyethyldiethylammonium propylsulfonate, the membrane upper surface and mass fraction of the cationic nanofiltration membrane are 1% 2-methacryloyloxyethyldiethylammonium The distance between the liquid surface of the methanol solution of propylsulfonate is 3.5mm, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 20cm, and the amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤15次,除去膜表面残余的2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 15 times with deionized water to remove residual 2-methacryloyloxyethyldiethylammonium propylsulfonate on the surface of the membrane.

实施例6制备得到的两性纳滤膜在0.5MPa下水通量为195L/m2h,对氯化钠的截留率为40.3﹪,对MgCl2的截留率为80.9﹪,对MgSO4的截留率为61.2﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 6 is 195L/m h at 0.5MPa, the rejection rate to sodium chloride is 40.3%, the rejection rate to MgCl is 80.9 %, and the rejection rate to MgSO It is 61.2%.

实施例7. Example 7.

步骤(1).将聚砜/聚醚酮/聚醚砜超滤膜用乙醇洗涤7次,然后用去离子水洗涤11次,去除膜表面杂质; Step (1). The polysulfone/polyetherketone/polyethersulfone ultrafiltration membrane is washed 7 times with ethanol, and then washed 11 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚酮/聚醚砜超滤膜浸泡于质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的甲醇溶液中,聚砜/聚醚酮/聚醚砜超滤膜的膜上表面与质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的甲醇溶液液体表面距离为4mm,300W紫外灯下辐照60分钟,聚砜/聚醚酮/聚醚砜超滤膜的膜上表面与紫外灯的距离为18cm,得到阳离子纳滤膜; Step (2). Soak the washed polysulfone/polyether ketone/polyethersulfone ultrafiltration membrane in the methanol solution of 5% 3-methacrylamidopropyltrimethylammonium in mass fraction, polysulfone/polyether ketone The distance between the upper surface of the polyetherketone/polyethersulfone ultrafiltration membrane and the liquid surface of the methanol solution with a mass fraction of 5% 3-methacrylamidopropyltrimethylammonium is 4mm, and it is irradiated under a 300W ultraviolet lamp for 60 minutes , the distance between the upper surface of the polysulfone/polyetherketone/polyethersulfone ultrafiltration membrane and the ultraviolet lamp is 18cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤5次,除去膜表面残余的3-甲基丙烯酰胺基丙基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为5﹪ 2-乙烯基吡啶丙基磺酸盐的甲醇溶液中,阳离子纳滤膜的膜上表面与质量分数为5﹪ 2-乙烯基吡啶丙基磺酸盐的甲醇溶液液体表面距离为4.5mm,300W紫外灯下辐照25min,阳离子纳滤膜的膜上表面与紫外灯的距离为18cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 5 times with deionized water to remove residual 3-methacrylamidopropyltrimethylammonium on the membrane surface, and then the washed cationic nanofiltration The membrane is immersed in a methanol solution with a mass fraction of 5% 2-vinylpyridine propyl sulfonate. The liquid surface distance is 4.5mm, irradiated under a 300W ultraviolet lamp for 25min, and the distance between the membrane upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 18cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤16次,除去膜表面残余的2-乙烯基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 16 times with deionized water to remove residual 2-vinylpyridinepropylsulfonate on the membrane surface.

实施例7制备得到的两性纳滤膜在0.5MPa下水通量为140L/m2h,对氯化钠的截留率为50.4﹪,对MgCl2的截留率为83.2﹪,对MgSO4的截留率为65.3﹪。 The water flux of the amphoteric nanofiltration membrane prepared in embodiment 7 is 140L/m h at 0.5MPa, the rejection rate to sodium chloride is 50.4%, the rejection rate to MgCl is 83.2 %, and the rejection rate to MgSO It is 65.3%.

实施例8. Example 8.

步骤(1).将聚砜超滤膜用乙醇洗涤8次,然后用去离子水洗涤12次,去除膜表面杂质; Step (1). The polysulfone ultrafiltration membrane is washed 8 times with ethanol, and then washed 12 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜超滤膜浸泡于质量分数为20﹪二烯丙基二甲基氯化铵的甲醇溶液中,聚砜超滤膜的膜上表面与质量分数为20﹪二烯丙基二甲基氯化铵的甲醇溶液液体表面距离为5mm,350W紫外灯下辐照50分钟,聚砜超滤膜的膜上表面与紫外灯的距离为22cm,得到阳离子纳滤膜; Step (2). Soak the polysulfone ultrafiltration membrane after washing in the methanol solution of 20% diallyl dimethyl ammonium chloride in mass fraction, the film upper surface and mass fraction of polysulfone ultrafiltration membrane are 20% ﹪Diallyldimethylammonium chloride methanol solution liquid surface distance is 5mm, irradiated under 350W ultraviolet lamp for 50 minutes, the distance between the membrane upper surface of the polysulfone ultrafiltration membrane and the ultraviolet lamp is 22cm, to obtain cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤6次,除去膜表面残余的二烯丙基二甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为8﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的甲醇溶液中,阳离子纳滤膜的膜上表面与质量分数为8﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的甲醇溶液液体表面距离为5mm,350W紫外灯下辐照22min,阳离子纳滤膜的膜上表面与紫外灯的距离为22cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 6 times with deionized water to remove residual diallyl dimethyl ammonium chloride on the membrane surface, and then the cationic nanofiltration membrane after washing is soaked in In the methanol solution with a mass fraction of 8% m-vinyl-o-picoline propyl sulfonate, the membrane upper surface of the cationic nanofiltration membrane and the mass fraction of 8% m-vinyl-o-picoline propyl The methanol solution liquid surface distance of base sulfonate is 5mm, 22min is irradiated under the 350W ultraviolet lamp, the film upper surface of cationic nanofiltration membrane and the distance of ultraviolet lamp are 22cm, obtain amphoteric nanofiltration membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤17次,除去膜表面残余的间-乙烯基-邻-甲基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 17 times with deionized water to remove residual m-vinyl-o-picoline propylsulfonate on the membrane surface.

实施例8制备得到的两性纳滤膜在0.5MPa下水通量为85L/m2h,对氯化钠的截留率为67.3﹪,对MgCl2的截留率为86.4﹪,对MgSO4的截留率为74.5﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 8 is 85L/m h at 0.5MPa, the rejection rate to sodium chloride is 67.3%, the rejection rate to MgCl is 86.4 %, and the rejection rate to MgSO It is 74.5%.

实施例9. Example 9.

步骤(1).将聚醚酮超滤膜用乙醇洗涤9次,然后用去离子水洗涤14次,去除膜表面杂质; Step (1). The polyetherketone ultrafiltration membrane is washed 9 times with ethanol, and then washed 14 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚醚酮超滤膜浸泡于质量分数为50﹪甲基丙烯酰氧乙基三甲基氯化铵的甲醇溶液中,聚醚酮超滤膜的膜上表面与质量分数为50﹪甲基丙烯酰氧乙基三甲基氯化铵的甲醇溶液液体表面距离为2.5mm,380W紫外灯下辐照40分钟,聚醚酮超滤膜的膜上表面与紫外灯的距离为25cm,得到阳离子纳滤膜; Step (2). Soak the polyetherketone ultrafiltration membrane after washing in the methanol solution of 50% methacryloyloxyethyltrimethylammonium chloride by mass fraction, the membrane upper surface of the polyetherketone ultrafiltration membrane The distance from the liquid surface of the methanol solution with a mass fraction of 50% methacryloyloxyethyltrimethylammonium chloride is 2.5mm, and irradiated under a 380W ultraviolet lamp for 40 minutes, the upper surface of the polyetherketone ultrafiltration membrane and the ultraviolet The distance between the lamps is 25cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤7次,除去膜表面残余的甲基丙烯酰氧乙基三甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为20﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的甲醇溶液中,阳离子纳滤膜的膜上表面与质量分数为20﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的甲醇溶液液体表面距离为2.5mm,380W紫外灯下辐照20min,阳离子纳滤膜的膜上表面与紫外灯的距离为25cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 7 times with deionized water to remove residual methacryloyloxyethyltrimethylammonium chloride on the membrane surface, and then the washed cationic nanofiltration The membrane is immersed in a methanol solution with a mass fraction of 20% acrylamido ethyl dimethyl ammonium propyl sulfonate. The distance between the liquid surface of the methanol solution of propylsulfonate is 2.5mm, and the irradiated under a 380W ultraviolet lamp for 20min, the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 25cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤18次,除去膜表面残余的丙烯酰胺基乙基二甲基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 18 times with deionized water to remove residual acrylamido ethyl dimethyl ammonium propyl sulfonate on the membrane surface.

实施9制备得到的两性纳滤膜在0.5MPa下水通量为62L/m2h,对氯化钠的截留率为81.2﹪,对MgCl2的截留率为92.5﹪,对MgSO4的截留率为89.4﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Implementation 9 is 62L/m 2 h at 0.5MPa, the rejection rate to sodium chloride is 81.2%, the rejection rate to MgCl is 92.5%, and the rejection rate to MgSO is 89.4%.

实施例10. Example 10.

步骤(1).将聚醚砜超滤膜用乙醇洗涤10次,然后用去离子水洗涤15次,去除膜表面杂质; Step (1). The polyethersulfone ultrafiltration membrane is washed 10 times with ethanol, and then washed 15 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚醚砜超滤膜浸泡于质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的甲醇溶液中,聚醚砜超滤膜的膜上表面与质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的甲醇溶液液体表面距离为3.5mm,400W紫外灯下辐照30分钟,聚醚砜超滤膜的膜上表面与紫外灯的距离为30cm,得到阳离子纳滤膜; Step (2). Soak the polyethersulfone ultrafiltration membrane after washing in the methanol solution of 65% 3-acrylamido-3-methylbutyltrimethylammonium in mass fraction, the polyethersulfone ultrafiltration membrane The distance between the upper surface of the membrane and the liquid surface of methanol solution with a mass fraction of 65% of 3-acrylamido-3-methylbutyltrimethylammonium is 3.5mm, irradiated under 400W ultraviolet lamp for 30 minutes, polyethersulfone ultrafiltration membrane The distance between the upper surface of the membrane and the ultraviolet lamp is 30cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤8次,除去膜表面残余的3-丙烯酰胺基-3-甲基丁基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为30﹪ 2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐的甲醇溶液中,阳离子纳滤膜的膜上表面与质量分数为30﹪ 2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐的甲醇溶液液体表面距离为3.5mm,400W紫外灯下辐照18min,阳离子纳滤膜的膜上表面与紫外灯的距离为30cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 8 times with deionized water to remove residual 3-acrylamido-3-methylbutyltrimethylammonium on the surface of the membrane, and then the washed The cationic nanofiltration membrane is soaked in a methanol solution with a mass fraction of 30% 2-methacrylamide ethyl diethylammonium propyl sulfonate, the upper surface of the cationic nanofiltration membrane and the mass fraction of 30% 2-form The distance between the liquid surface of the methanol solution of methacrylamide ethyl diethylammonium propyl sulfonate is 3.5 mm, irradiated under a 400W ultraviolet lamp for 18 minutes, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 30 cm, and the amphoteric Nanofiltration;

步骤(4).将得到的两性纳滤膜用去离子水洗涤19次,除去膜表面残余的2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 19 times with deionized water to remove residual 2-methacrylamide ethyl diethyl ammonium propyl sulfonate on the membrane surface.

实施例10制备得到的两性纳滤膜在0.5MPa下水通量为55L/m2h,对氯化钠的截留率为85﹪,对MgCl2的截留率为97﹪,对MgSO4的截留率为93﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 10 is 55L/m h at 0.5MPa, the rejection rate to sodium chloride is 85%, the rejection rate to MgCl is 97%, and the rejection rate to MgSO is 93%.

实施例11. Example 11.

步骤(1).将聚砜/聚醚酮超滤膜用乙醇洗涤5次,然后用去离子水洗涤16次,去除膜表面杂质; Step (1). The polysulfone/polyetherketone ultrafiltration membrane is washed 5 times with ethanol, and then washed 16 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚酮超滤膜浸泡于质量分数为1﹪ 4-乙烯基吡啶的乙醇溶液中,聚砜/聚醚酮超滤膜的膜上表面与质量分数为1﹪ 4-乙烯基吡啶的乙醇溶液液体表面距离为4.5mm,450W紫外灯下辐照100分钟,聚砜/聚醚酮超滤膜的膜上表面与紫外灯的距离为32cm,得到阳离子纳滤膜; Step (2). Soak the polysulfone/polyetherketone ultrafiltration membrane after washing in the ethanol solution of 1% 4-vinylpyridine with a mass fraction, the membrane upper surface and mass of the polysulfone/polyetherketone ultrafiltration membrane The distance between the liquid surface of the ethanol solution with a fraction of 1% of 4-vinylpyridine is 4.5mm, irradiated under a 450W ultraviolet lamp for 100 minutes, and the distance between the upper surface of the polysulfone/polyetherketone ultrafiltration membrane and the ultraviolet lamp is 32cm, and the obtained Cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤5~10次,除去膜表面残余的4-乙烯基吡啶,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为1﹪ 2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐的乙醇溶液中,阳离子纳滤膜的膜上表面与质量分数为1﹪ 2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐的乙醇溶液液体表面距离为4.5mm,450W紫外灯下辐照10min,阳离子纳滤膜的膜上表面与紫外灯的距离为32cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 5 to 10 times with deionized water to remove residual 4-vinylpyridine on the surface of the membrane, and then the washed cationic nanofiltration membrane is soaked in a mass fraction of In the ethanol solution of 1% 2-methacryloyloxyethyl dimethyl ammonium propyl sulfonate, the membrane upper surface and mass fraction of the cationic nanofiltration membrane are 1% 2-methacryloyloxyethyl dimethyl The liquid surface distance of the ethanol solution of ammonium propyl sulfonate is 4.5mm, irradiated under 450W ultraviolet lamp for 10min, and the distance between the membrane upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 32cm, and the amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤20次,除去膜表面残余的2-甲基丙烯酰氧乙基二甲基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 20 times with deionized water to remove residual 2-methacryloyloxyethyldimethylammonium propylsulfonate on the surface of the membrane.

实施例11制备得到的两性纳滤膜在0.5MPa下水通量为193L/m2h,对氯化钠的截留率为41.3﹪,对MgCl2的截留率为81.7﹪,对MgSO4的截留率为61.5﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 11 is 193 L/m h at 0.5 MPa, the rejection rate to sodium chloride is 41.3%, the rejection rate to MgCl is 81.7 %, and the rejection rate to MgSO It is 61.5%.

实施例12. Example 12.

步骤(1).将聚砜/聚醚砜超滤膜用乙醇洗涤7次,然后用去离子水洗涤18次,去除膜表面杂质; Step (1). The polysulfone/polyethersulfone ultrafiltration membrane is washed 7 times with ethanol, and then washed 18 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚砜超滤膜浸泡于质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的乙醇溶液中,聚砜/聚醚砜超滤膜的膜上表面与质量分数为5﹪ 3-甲基丙烯酰胺基丙基三甲基铵的乙醇溶液液体表面距离为4mm,500W紫外灯下辐照10分钟,聚砜/聚醚砜超滤膜的膜上表面与紫外灯的距离为35cm,得到阳离子纳滤膜; Step (2). Soak the washed polysulfone/polyethersulfone ultrafiltration membrane in an ethanol solution with a mass fraction of 5% 3-methacrylamidopropyltrimethylammonium, polysulfone/polyethersulfone ultrafiltration The distance between the upper surface of the filter membrane and the liquid surface of the ethanol solution with a mass fraction of 5% 3-methacrylamidopropyltrimethylammonium is 4mm, and the polysulfone/polyethersulfone ultra- The distance between the membrane upper surface of the filter membrane and the ultraviolet lamp is 35cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤9次,除去膜表面残余的3-甲基丙烯酰胺基丙基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为5﹪ 2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐的乙醇溶液中,阳离子纳滤膜的膜上表面与质量分数为5﹪ 2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐的乙醇溶液液体表面距离为4mm,500W紫外灯下辐照15min,阳离子纳滤膜的膜上表面与紫外灯的距离为35cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 9 times with deionized water to remove residual 3-methacrylamidopropyltrimethylammonium on the membrane surface, and then the washed cationic nanofiltration The membrane is immersed in an ethanol solution with a mass fraction of 5% 2-methacryloyloxyethyldiethylammonium propyl sulfonate, and the upper surface of the cationic nanofiltration membrane and the mass fraction of 2-methacrylic acid The distance between the liquid surface of the ethanol solution of acyloxyethyl diethylammonium propyl sulfonate is 4mm, irradiated under a 500W ultraviolet lamp for 15min, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 35cm, and the amphoteric nanofiltration is obtained. membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤20次,除去膜表面残余的2-甲基丙烯酰氧乙基二乙基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 20 times with deionized water to remove residual 2-methacryloyloxyethyldiethylammonium propylsulfonate on the surface of the membrane.

实施例12制备得到的两性纳滤膜在0.5MPa下水通量为120L/m2h,对氯化钠的截留率为55.3﹪,对MgCl2的截留率为84.5﹪,对MgSO4的截留率为67.2﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 12 is 120L/m h at 0.5MPa, the rejection rate to sodium chloride is 55.3%, the rejection rate to MgCl is 84.5 %, and the rejection rate to MgSO It is 67.2%.

实施例13. Example 13.

步骤(1).将聚醚酮/聚醚砜超滤膜用乙醇洗涤9次,然后用去离子水洗涤20次,去除膜表面杂质; Step (1). The polyetherketone/polyethersulfone ultrafiltration membrane is washed 9 times with ethanol, and then washed 20 times with deionized water to remove impurities on the surface of the membrane;

步骤(2).将洗涤后的超滤膜浸泡于质量分数为40﹪二烯丙基二甲基氯化铵的乙醇溶液中,超滤膜的膜上表面与质量分数为40﹪二烯丙基二甲基氯化铵的乙醇溶液液体表面距离为5mm,550W紫外灯下辐照3分钟,超滤膜的膜上表面与紫外灯的距离为38cm,得到阳离子纳滤膜; Step (2). Soak the ultrafiltration membrane after washing in the ethanol solution of 40% diallyl dimethyl ammonium chloride in mass fraction, the film upper surface and mass fraction of ultrafiltration membrane are 40% diallyl The ethanol solution liquid surface distance of dimethyl ammonium chloride is 5mm, irradiates 3 minutes under the 550W ultraviolet lamp, and the film upper surface of ultrafiltration membrane and the distance of ultraviolet lamp are 38cm, obtain cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤10次,除去膜表面残余的二烯丙基二甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为15﹪ 2-乙烯基吡啶丙基磺酸盐的乙醇溶液中,阳离子纳滤膜的膜上表面与质量分数为15﹪ 2-乙烯基吡啶丙基磺酸盐的乙醇溶液液体表面距离为5mm,550W紫外灯下辐照5min,阳离子纳滤膜的膜上表面与紫外灯的距离为38cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 10 times with deionized water to remove residual diallyl dimethyl ammonium chloride on the membrane surface, and then the cationic nanofiltration membrane after washing is soaked in In an ethanol solution with a mass fraction of 15% of 2-vinylpyridine propyl sulfonate, the distance between the upper surface of the cationic nanofiltration membrane and the liquid surface of an ethanol solution with a mass fraction of 15% of 2-vinyl pyridine propyl sulfonate 5mm, irradiated for 5min under a 550W ultraviolet lamp, and the distance between the membrane upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 38cm to obtain an amphoteric nanofiltration membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤15次,除去膜表面残余的2-乙烯基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 15 times with deionized water to remove residual 2-vinylpyridinepropylsulfonate on the surface of the membrane.

实施例13制备得到的两性纳滤膜在0.5MPa下水通量为77L/m2h,对氯化钠的截留率为72.5﹪,对MgCl2的截留率为88.3﹪,对MgSO4的截留率为80.1﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 13 is 77L/ m2h at 0.5MPa, the rejection rate to sodium chloride is 72.5%, the rejection rate to MgCl is 88.3%, and the rejection rate to MgSO It is 80.1%.

实施例14. Example 14.

步骤(1).将聚砜/聚醚酮/聚醚砜超滤膜用乙醇洗涤8次,然后用去离子水洗涤19次,去除膜表面杂质; Step (1). The polysulfone/polyetherketone/polyethersulfone ultrafiltration membrane is washed 8 times with ethanol, and then washed 19 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜/聚醚酮/聚醚砜超滤膜浸泡于50﹪甲基丙烯酰氧乙基三甲基氯化铵的乙醇溶液中,超滤膜的膜上表面与50﹪甲基丙烯酰氧乙基三甲基氯化铵的乙醇溶液液体表面距离为3.5mm,600W紫外灯下辐照3分钟,聚砜/聚醚酮/聚醚砜超滤膜的膜上表面与紫外灯的距离为40cm,得到阳离子纳滤膜; Step (2). Soak the washed polysulfone/polyether ketone/polyether sulfone ultrafiltration membrane in a 50% ethanol solution of methacryloyloxyethyltrimethylammonium chloride, on the membrane of the ultrafiltration membrane The distance between the surface and the ethanol solution of 50% methacryloyloxyethyltrimethylammonium chloride is 3.5mm, irradiated under 600W ultraviolet lamp for 3 minutes, the ultrafiltration membrane of polysulfone/polyetherketone/polyethersulfone The distance between the upper surface of the membrane and the ultraviolet lamp is 40cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤8次,除去膜表面残余的甲基丙烯酰氧乙基三甲基氯化铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为20﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的乙醇溶液中,阳离子纳滤膜的膜上表面与质量分数为20﹪间-乙烯基-邻-甲基吡啶丙基磺酸盐的乙醇溶液液体表面距离为2mm,600W紫外灯下辐照2min,阳离子纳滤膜的膜上表面与紫外灯的距离为40cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 8 times with deionized water to remove residual methacryloyloxyethyltrimethylammonium chloride on the membrane surface, and then the washed cationic nanofiltration The membrane is soaked in an ethanol solution with a mass fraction of 20% m-vinyl-o-picoline propyl sulfonate. The ethanol solution liquid surface distance of pyridyl propyl group sulfonate is 2mm, irradiates 2min under the 600W ultraviolet lamp, and the film upper surface of cationic nanofiltration membrane and the distance of ultraviolet lamp are 40cm, obtain amphoteric nanofiltration membrane;

步骤(4).将得到的两性纳滤膜用去离子水洗涤18次,除去膜表面残余的间-乙烯基-邻-甲基吡啶丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 18 times with deionized water to remove residual m-vinyl-o-picoline propylsulfonate on the membrane surface.

实施例14制备得到的两性纳滤膜在0.5MPa下水通量为68L/m2h,对氯化钠的截留率为80.1﹪,对MgCl2的截留率为90.8﹪,对MgSO4的截留率为85.7﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 14 is 68 L/m h at 0.5 MPa, the rejection rate to sodium chloride is 80.1%, the rejection rate to MgCl is 90.8%, and the rejection rate to MgSO It is 85.7%.

实施例15. Example 15.

步骤(1).将聚砜超滤膜用乙醇洗涤6次,然后用去离子水洗涤17次,去除膜表面杂质; Step (1). The polysulfone ultrafiltration membrane is washed 6 times with ethanol, and then washed 17 times with deionized water to remove impurities on the membrane surface;

步骤(2).将洗涤后的聚砜超滤膜浸泡于质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的乙醇溶液中,聚砜超滤膜的膜上表面与质量分数为65﹪ 3-丙烯酰胺基-3-甲基丁基三甲基铵的乙醇溶液液体表面距离为5mm,600W紫外灯下辐照5分钟,聚砜超滤膜的膜上表面与紫外灯的距离为30cm,得到阳离子纳滤膜; Step (2). Soak the polysulfone ultrafiltration membrane after washing in the ethanol solution of 65% 3-acrylamido-3-methylbutyltrimethylammonium in mass fraction, on the membrane of polysulfone ultrafiltration membrane The distance between the surface and the liquid surface of the ethanol solution with a mass fraction of 65% of 3-acrylamido-3-methylbutyltrimethylammonium is 5 mm, and the upper surface of the polysulfone ultrafiltration membrane is irradiated for 5 minutes under a 600W ultraviolet lamp. The distance from the ultraviolet lamp is 30cm to obtain a cationic nanofiltration membrane;

步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤8次,除去膜表面残余的3-丙烯酰胺基-3-甲基丁基三甲基铵,然后将洗涤后的阳离子纳滤膜浸泡于质量分数为30﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的乙醇溶液中,阳离子纳滤膜的膜上表面与质量分数为30﹪丙烯酰胺基乙基二甲基铵丙基磺酸盐的乙醇溶液液体表面距离为5mm,600W紫外灯下辐照30min,阳离子纳滤膜的膜上表面与紫外灯的距离为30cm,得到两性纳滤膜; Step (3). The cationic nanofiltration membrane obtained after ultraviolet radiation is washed 8 times with deionized water to remove residual 3-acrylamido-3-methylbutyltrimethylammonium on the surface of the membrane, and then the washed The cationic nanofiltration membrane is soaked in an ethanol solution with a mass fraction of 30% acrylamido ethyl dimethyl ammonium propyl sulfonate, the upper surface of the cationic nanofiltration membrane and the mass fraction of 30% acrylamido ethyl di The liquid surface distance of the ethanol solution of methylammonium propyl sulfonate is 5 mm, irradiated under a 600W ultraviolet lamp for 30 minutes, and the distance between the upper surface of the cationic nanofiltration membrane and the ultraviolet lamp is 30 cm, and an amphoteric nanofiltration membrane is obtained;

步骤(4).将得到的两性纳滤膜用去离子水洗涤15次,除去膜表面残余的丙烯酰胺基乙基二甲基铵丙基磺酸盐。 Step (4). The obtained amphoteric nanofiltration membrane was washed 15 times with deionized water to remove residual acrylamido ethyl dimethyl ammonium propyl sulfonate on the membrane surface.

实施例15制备得到的两性纳滤膜在0.5MPa下水通量为57L/m2h,对氯化钠的截留率为83.2﹪,对MgCl2的截留率为94.3﹪,对MgSO4的截留率为91.7﹪。 The water flux of the amphoteric nanofiltration membrane prepared in Example 15 is 57 L/m h at 0.5 MPa, the rejection rate to sodium chloride is 83.2%, the rejection rate to MgCl is 94.3%, and the rejection rate to MgSO It is 91.7%.

上述实施例1~15所用的紫外灯的波长为290~400nm的高压汞灯,在10~30℃下反应,空气中进行;膜上表面到紫外灯的距离和紫外灯的功率是用来控制辐射强度的。 The wavelength of the used ultraviolet lamp of above-mentioned embodiment 1~15 is the high-pressure mercury lamp of 290~400nm, reacts at 10~30 ℃, carries out in the air; radiation intensity.

本发明所制备两性纳滤膜的过滤性能是在膜评价仪中进行评价的。测试温度为常温,压强为0.5MPa。两性纳滤膜的过滤性能分别在该条件的水通量表示(单位:L/m2h)渗透性;用对1g/L NaCl水溶液、1g/L MgSO4水溶液和1g/L MgCl2水溶液的截留率来表示其选择性。 The filtration performance of the amphoteric nanofiltration membrane prepared in the present invention is evaluated in a membrane evaluation instrument. The test temperature is normal temperature and the pressure is 0.5MPa. The filtration performance of the amphoteric nanofiltration membrane is represented by the water flux (unit: L/m 2 h) permeability under the conditions; The rejection rate is used to represent its selectivity.

Claims (8)

1.一种大通量两性纳滤膜的制备方法,其特征在于该方法包括以下步骤:1. a preparation method of large flux amphoteric nanofiltration membrane, is characterized in that the method may further comprise the steps: 步骤(1).将超滤膜用乙醇洗涤1~10次,然后用去离子水洗涤5~20次,去除膜表面杂质;Step (1). Wash the ultrafiltration membrane with ethanol for 1 to 10 times, and then wash it with deionized water for 5 to 20 times to remove impurities on the surface of the membrane; 步骤(2).将洗涤后的超滤膜浸泡于烯烃类阳离子单体溶液中,超滤膜的膜上表面与烯烃类阳离子单体溶液的液体表面距离为1~5mm,100~600W紫外灯下辐照3~120分钟,超滤膜的膜上表面与紫外灯的距离为5~40cm,得到阳离子纳滤膜;Step (2). Soak the washed ultrafiltration membrane in the olefinic cationic monomer solution, the distance between the upper surface of the ultrafiltration membrane and the liquid surface of the olefinic cationic monomer solution is 1-5mm, 100-600W ultraviolet lamp Under irradiation for 3 to 120 minutes, the distance between the upper surface of the ultrafiltration membrane and the ultraviolet lamp is 5 to 40 cm, and a cationic nanofiltration membrane is obtained; 所述的烯烃类阳离子单体溶液为质量分数为1~65﹪烯烃类阳离子单体的水溶液或甲醇溶液或乙醇溶液;The olefinic cationic monomer solution is an aqueous solution or a methanol solution or an ethanol solution with a mass fraction of 1 to 65% of the olefinic cationic monomer; 所述的烯烃类阳离子单体为含有叔胺基的烯烃;The olefinic cationic monomer is an olefin containing a tertiary amino group; 步骤(3).将紫外辐射后得到的阳离子纳滤膜用去离子水洗涤5~10次,除去膜表面残余的烯烃类阳离子单体,然后将洗涤后的阳离子纳滤膜浸泡于两性烯烃类单体溶液中,阳离子纳滤膜的膜上表面与两性烯烃类单体溶液的液体表面距离为1~5mm,100~600W紫外灯下辐照2~40min,阳离子纳滤膜的膜上表面与紫外灯的距离为5~40cm,得到两性纳滤膜;Step (3). Wash the cationic nanofiltration membrane obtained after ultraviolet radiation with deionized water for 5 to 10 times to remove residual olefin cationic monomers on the surface of the membrane, and then soak the washed cationic nanofiltration membrane in amphoteric olefins In the monomer solution, the distance between the upper surface of the cationic nanofiltration membrane and the liquid surface of the amphoteric olefin monomer solution is 1 to 5 mm, and the upper surface of the cationic nanofiltration membrane and the liquid surface of the amphoteric olefin monomer solution are irradiated for 2 to 40 minutes under a 100-600W ultraviolet lamp. The distance of the ultraviolet lamp is 5-40cm, and the amphoteric nanofiltration membrane is obtained; 所述的两性烯烃类单体溶液为质量分数为1~30﹪两性烯烃类单体的水溶液或甲醇溶液或乙醇溶液;The amphoteric olefin monomer solution is an aqueous solution or methanol solution or ethanol solution with a mass fraction of 1 to 30% amphoteric olefin monomer; 所述的两性烯烃类单体为丙烯酰胺基乙基二甲基铵丙基磺酸盐或2-甲基丙烯酰胺乙基二乙基铵丙基磺酸盐;The amphoteric olefinic monomer is acrylamido ethyl dimethyl ammonium propyl sulfonate or 2-methacrylamide ethyl diethyl ammonium propyl sulfonate; 步骤(4).将得到的两性纳滤膜用去离子水洗涤10~20次,除去膜表面残余的两性烯烃类离子单体。Step (4). Washing the obtained amphoteric nanofiltration membrane with deionized water for 10 to 20 times to remove residual amphoteric olefin ionic monomers on the surface of the membrane. 2.如权利要求1所述的一种大通量两性纳滤膜的制备方法,其特征在于步骤(1)中所述的超滤膜的材质为聚砜、聚醚酮、聚醚砜的一种或多种。2. the preparation method of a kind of large flux amphoteric nanofiltration membrane as claimed in claim 1 is characterized in that the material of the ultrafiltration membrane described in step (1) is polysulfone, polyetherketone, polyethersulfone one or more. 3.如权利要求1所述的一种大通量两性纳滤膜的制备方法,其特征在于步骤(2)中所述的紫外灯是波长为290~400nm的高压汞灯,在10~30℃下空气中进行反应。3. the preparation method of a kind of large-flux amphoteric nanofiltration membrane as claimed in claim 1 is characterized in that the ultraviolet lamp described in step (2) is the high-pressure mercury lamp that wavelength is 290~400nm, at 10~30 The reaction was carried out in air at ℃. 4.如权利要求1所述的一种大通量两性纳滤膜的制备方法,其特征在于步骤(1)中超滤膜用乙醇洗涤4~7次,然后用去离子水洗涤10~15次。4. the preparation method of a kind of large-flux amphoteric nanofiltration membrane as claimed in claim 1 is characterized in that in step (1), ultrafiltration membrane is washed 4~7 times with ethanol, then washes 10~15 with deionized water. Second-rate. 5.如权利要求1所述的一种大通量两性纳滤膜的制备方法,其特征在于步骤(2)中紫外灯的功率为300~500W,紫外辐照时间为5~30min,超滤膜的膜上表面与紫外灯的距离为10~30cm。5. the preparation method of a kind of large-flux amphoteric nanofiltration membrane as claimed in claim 1 is characterized in that the power of ultraviolet lamp is 300~500W in the step (2), and the ultraviolet irradiation time is 5~30min, ultrafiltration The distance between the upper surface of the film and the ultraviolet lamp is 10-30 cm. 6.如权利要求1所述的一种大通量两性纳滤膜的制备方法,其特征在于步骤(3)中紫外灯的功率为300~500W,紫外辐照时间为10~30min,阳离子纳滤膜的膜上表面与紫外灯的距离为10~30cm。6. the preparation method of a kind of large-flux amphoteric nanofiltration membrane as claimed in claim 1 is characterized in that the power of the ultraviolet lamp is 300~500W in the step (3), and the ultraviolet irradiation time is 10~30min, and cationic nanofiltration The distance between the upper surface of the filter membrane and the ultraviolet lamp is 10-30 cm. 7.如权利要求3所述的一种大通量两性纳滤膜的制备方法,其特征在于烯烃类阳离子单体溶液中烯烃类阳离子单体的质量含量为5~50﹪。7. The preparation method of a large-flux amphoteric nanofiltration membrane as claimed in claim 3, characterized in that the mass content of the olefin cationic monomer in the solution of the olefin cationic monomer is 5-50%. 8.如权利要求5所述的一种大通量两性纳滤膜的制备方法,其特征在于两性烯烃类单体溶液中两性烯烃类单体的质量含量为5~20﹪。8 . The method for preparing a large-flux amphoteric nanofiltration membrane according to claim 5 , wherein the mass content of the amphoteric olefinic monomer in the amphoteric olefinic monomer solution is 5-20%.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412922A (en) * 1980-07-02 1983-11-01 Abcor, Inc. Positive-charged ultrafiltration membrane for the separation of cathodic/electrodeposition-paint compositions
JPS62266103A (en) * 1986-05-14 1987-11-18 Toray Ind Inc Composite semipermeable membrane
US4849106A (en) * 1983-06-06 1989-07-18 Koch Membrane Systems, Inc. Positive-charged ultrafiltration membrane for the separation of cathodic electrodeposition paint compositions
CN1124175A (en) * 1995-10-27 1996-06-12 复旦大学 Hydrophilic pervaporation separation membrane and preparation method thereof
EP0884096A1 (en) * 1997-06-10 1998-12-16 Crosswinds, Inc. Semipermeable encapsulated membranes with improved acid and base stability process for their manufacture and their use
CN1858090A (en) * 2006-05-11 2006-11-08 复旦大学 Method for hydrophilic modifying of poly-vinylidene fluoride film
CN101934204A (en) * 2010-09-17 2011-01-05 南京林业大学 A kind of amphoteric charged nanofiltration membrane and preparation method thereof
CN101934205A (en) * 2010-09-17 2011-01-05 南京林业大学 A kind of preparation method of amphoteric charged nanofiltration membrane
CN102836648A (en) * 2012-08-29 2012-12-26 南京林业大学 Method for preparing zwitter ion-containing positively-charged nanofiltration membrane

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412922A (en) * 1980-07-02 1983-11-01 Abcor, Inc. Positive-charged ultrafiltration membrane for the separation of cathodic/electrodeposition-paint compositions
US4849106A (en) * 1983-06-06 1989-07-18 Koch Membrane Systems, Inc. Positive-charged ultrafiltration membrane for the separation of cathodic electrodeposition paint compositions
JPS62266103A (en) * 1986-05-14 1987-11-18 Toray Ind Inc Composite semipermeable membrane
CN1124175A (en) * 1995-10-27 1996-06-12 复旦大学 Hydrophilic pervaporation separation membrane and preparation method thereof
EP0884096A1 (en) * 1997-06-10 1998-12-16 Crosswinds, Inc. Semipermeable encapsulated membranes with improved acid and base stability process for their manufacture and their use
CN1858090A (en) * 2006-05-11 2006-11-08 复旦大学 Method for hydrophilic modifying of poly-vinylidene fluoride film
CN101934204A (en) * 2010-09-17 2011-01-05 南京林业大学 A kind of amphoteric charged nanofiltration membrane and preparation method thereof
CN101934205A (en) * 2010-09-17 2011-01-05 南京林业大学 A kind of preparation method of amphoteric charged nanofiltration membrane
CN102836648A (en) * 2012-08-29 2012-12-26 南京林业大学 Method for preparing zwitter ion-containing positively-charged nanofiltration membrane

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