CN108452685A - 一种高性能复合正渗透膜及其制备方法 - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Abstract
本发明涉及一种高性能复合正渗透膜及其制备方法。主要解决了现有的正渗透膜不能同时具备高水通量和高盐截留率的问题。所述高性能复合正渗透膜包括无纺布支撑层、醋酸纤维素多孔底层、聚芳香酰胺致密分离层,所述醋酸纤维素多孔层位于无纺布支撑层、聚芳香酰胺致密分离层之间;所述聚芳香酰胺致密分离层由多于一个功能团的芳香胺和多于一个功能团的芳香酰氯通过界面聚合生成。本发明的高性能复合正渗透膜在维持聚酰胺层的高盐截流的条件下,结合了相转化法制备的含有大量亲水基团的醋酸纤维素多孔底层,保证了高水通量和高盐截留率。
Description
技术领域
本发明涉及膜分离技术领域,具体涉及一种高性能复合正渗透膜及其制备方法。
背景技术
FO(Forward Osmosis)技术是一种化学位差或者渗透压引导的渗透驱动膜过程,具有低能耗、低污染、高回收等特点,急救水袋、航空航天、食品浓缩、制药、绿色能源、植物保护箱、海水淡化、硬水软化、工业废水等领域有着现实或潜在的应用前景。然而,由于缺乏高效的FO膜材料,极大地制约FO技术的发展。目前用于FO过程的膜材料都具有非对称结构,由薄的选择分离层和多孔支撑层组成,在FO过程中都存在外浓差极化和内浓差极化,尤其是内浓差极化,导致FO膜实际水通量远远小于理论水通量。通常情况下,外浓差极化发生在膜与溶液的界面处,可以通过增加流速等流体力学得以缓解;内浓差极化发生是FO过程所特有的现象,在FO过程中根据膜的取向,溶质在膜多孔支撑层内积累或稀释,形成浓缩和稀释的内浓差极化,极大的降低了膜两侧的有效渗透压差。内浓差极化发生在多孔支撑层内,难以通过改变外界条件而缓解。由于内浓差极化的产生,降低膜通量的同时溶质也逆向扩散到原液中,也降低了膜两侧的渗透压,进一步降低了膜通量,研究表明内浓差极化与膜多孔支撑层结构(孔隙率、孔弯曲度、膜厚度)以及膜材料本身的物理化学性质(亲疏水性、选择性)有很大的关系。支撑层厚度越小,孔隙率越高,孔弯曲度越小,亲水性越好,则膜结构参数则越小,内浓差极化越小。
现有的构建有机正渗透膜分离层的主要方法包含相转化法和界面聚合法:相转化法制备的醋酸纤维素基的正渗透膜,虽然有较高的通量,但是其盐阻隔性能太差;基于界面聚合制备的具有聚芳香酰胺分离层的正渗透膜,虽然有高的盐阻隔性能,但是由于使用了聚砜,聚偏氟乙烯等疏水的底层,其通量很低,不能满足实际应用的需求。
发明内容
为了克服背景技术的不足,本发明提供一种高性能复合正渗透膜及其制备方法,主要解决了现有的正渗透膜不能同时具备高水通量和高盐截留率的问题,本发明的高性能复合正渗透膜在维持聚酰胺层的高盐截流的条件下,结合了相转化法制备的含有大量亲水基团的醋酸纤维素多孔底层,保证了高水通量和高盐截留率,同时还具有高机械强度,耐溶剂性,抗污染性,可以用于急救水袋、航空航天、食品浓缩、制药、绿色能源、植物保护箱、海水淡化、硬水软化、工业废水等领域。
本发明所采用的技术方案是:一种高性能复合正渗透膜,包括无纺布支撑层、醋酸纤维素多孔底层、聚芳香酰胺致密分离层,所述醋酸纤维素多孔层位于无纺布支撑层、聚芳香酰胺致密分离层之间;所述醋酸纤维素多孔底层为醋酸纤维素、二醋酸纤维素、三醋酸纤维素中任意一种或两种质量比为1:1~1:4的混合物;所述无纺布支撑层为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;所述聚芳香酰胺致密分离层由多于一个功能团的芳香胺和多于一个功能团的芳香酰氯通过界面聚合生成;所述多于一个功能团的芳香胺为间苯二胺、邻苯二胺、二乙烯三胺、三乙烯四胺、哌嗪或其衍生物中任意一种或两种质量比为1:1~1:4的混合物;所述多于一个功能团的芳香酰氯为均苯三甲酰氯、间苯二甲酰氯、对苯二甲酰氯、多元磺酰氯中的一种或任意两种质量比为1:1~1:4的混合物。
该高性能复合正渗透膜的制备方法,包括以下步骤:
步骤(1):将质量百分比为5-17%的醋酸纤维素加入到由二氧六环、丙酮、甲醇和乳酸组成的铸膜液溶剂中,在40-65℃条件下搅拌充分溶解,将溶解好的液体置于频率为20~100千赫兹、温度为10~50℃超声场中超声0.5~3小时,再静置3小时以上使其完全脱泡,即得制备好的铸膜液,备用;
步骤(2):将步骤(1)中制备好的铸膜液涂覆在无纺布上,并采用刮刀均匀的刮在无纺布上形成底膜层,将无纺布上的底膜层在空气中静置5-30秒,然后将底膜层放入凝胶浴中经相转化凝胶成具有多孔结构的底层,所述凝胶浴的成分为去离子水,并将膜置于35-90℃水浴中热处理3-20分钟,清洗之后,在50-100℃烘干,即得醋酸纤维素底膜,保存备用;
步骤(3):将质量百分比为0.5~5﹪的多于一个功能团的芳香胺溶解于纯化水中制得多于一个功能团的芳香胺水溶液;
步骤(4)、将质量百分比为0.05~1﹪的多于一个功能团的芳香酰氯溶解在烷烃溶剂中,配制成多于一个功能团的芳香酰氯有机相溶液;
步骤(5):将多于一个功能团的芳香胺水溶液与步骤(2)制备的醋酸纤维素底膜均匀接触,固定0.5-5min,然后除去多余的多于一个功能团的芳香胺水溶液;
步骤(6):将步骤(4)配制好的多于一个功能团的芳香酰氯有机相溶液与经过步骤(5)处理好后的醋酸纤维素底膜上进行界面聚合0.5~5分钟,除去多余的多于一个功能团的芳香酰氯有机相溶液;然后在50~130℃下热处理2~15分钟,漂洗,烘干得到高性能复合正渗透膜;
所述的铸膜液溶剂,其组分及所占质量分数比例如下:二氧六环40-70份、丙酮12-24份、甲醇5-15份、乳酸2-10份;所述底膜层厚度为0.01-0.2mm;所述烷烃溶剂为正己烷、正庚烷、正辛烷、正十二烷、异十二烷、异十六烷等烷烃类的一种或任意两种质量比为1:1~1:4的混合物。
本发明的有益效果是:由于采取上述技术方案,本发明的高性能复合正渗透膜在维持聚酰胺层的高盐截流的条件下,结合了相转化法制备的含有大量亲水基团的醋酸纤维素多孔底层,保证了高水通量和高盐截留率,同时还具有高机械强度,耐溶剂性,抗污染性,可以用于急救水袋、航空航天、食品浓缩、制药、绿色能源、植物保护箱、海水淡化、硬水软化、工业废水等领域。
具体实施方式
下面对本发明实施例作进一步说明:
实施例1:
步骤(1):将质量百分比为5%的醋酸纤维素加入到质量分数比例为二氧六环70份、丙酮12份、甲醇15份和乳酸2份的混合溶剂中,在65℃条件下搅拌充分溶解,将溶解好的铸膜液置于频率为100千赫兹、温度为50℃超声场中超声0.5小时,再静置3小时以上使其完全脱泡,备用;
步骤(2):将步骤(1)制备好的铸膜液涂覆在无纺布上,无纺布为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;并采用刮刀均匀的刮在无纺布上形成底膜层,底膜层厚度为0.2mm,将无纺布上的底模层在空气中静置5秒,然后将底膜层放入凝胶浴(凝胶浴的成分为去离子水)中经相转化凝胶成具有致密层的膜,并将膜置于35℃水浴中热处理20分钟,清洗之后,在100℃烘干,保存备用;
步骤(3):将质量百分比为5﹪的间苯二胺溶解于纯化水中制得间苯二胺水溶液作为水相;
步骤(4):将质量百分比为1﹪的均苯三甲酰氯溶解在异十二烷中,配制成均苯三甲酰氯异十二烷溶液作为有机相;
步骤(5):将间苯二胺水溶液均匀涂布在步骤(2)制备的醋酸纤维素底膜上,固定5min,然后除去多余的间苯二胺水溶液;
步骤(6):将步骤(4)配制好的有机相溶液均匀涂布在步骤(5)处理好的醋酸纤维素底膜上进行界面聚合5分钟,除去多余的溶液;然后在130℃下热处理2分钟,漂洗,烘干得到高性能复合正渗透膜。
本实施例所制备的高性能复合正渗透膜装入膜性能评价装置中,然后以2mol/L的氯化钠水溶液为汲取液,以纯化水为原液,测的膜通量22L/m2.h,盐截留率99.87%。
实施例2:
步骤(1):将质量百分比为8%的二醋酸纤维素加入到质量分数比例为二氧六环60份、丙酮23份、甲醇5份和乳酸5份的混合溶剂中,在40℃条件下搅拌充分溶解,将溶解好的铸膜液置于频率为20千赫兹、温度为10℃超声场中超声1小时,再静置3小时以上使其完全脱泡,备用;
步骤(2):将步骤(1)制备好的铸膜液涂覆在无纺布上,并无纺布为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;采用刮刀均匀的刮在无纺布上形成底膜层,底膜层厚度为0.1mm,将无纺布上的底模层在空气中静置15秒,然后将底膜层放入凝胶浴(凝胶浴的成分为去离子水)中经相转化凝胶成具有致密层的膜,并将膜置于60℃水浴中热处理10分钟,清洗之后,在80℃烘干,保存备用;
步骤(3):将质量百分比为4﹪的间苯二胺溶解于纯化水中制得间苯二胺水溶液作为水相;
步骤(4):将质量百分比为0.7﹪的对苯二甲酰氯溶解在正己烷中,配制成对苯二甲酰氯正己烷溶液作为有机相;
步骤(5):将间苯二胺水溶液均匀涂布在步骤(2)制备的二醋酸纤维素底膜上,固定3min,然后除去多余的间苯二胺水溶液;
步骤(6):将步骤(4)配制好的有机相溶液均匀涂布在步骤(5)处理好的二醋酸纤维素底膜上进行界面聚合3分钟,除去多余的溶液;然后在100℃下热处理5分钟,漂洗,烘干得到高性能复合正渗透膜。
本实施例所制备的高性能复合正渗透膜装入膜性能评价装置中,然后以2mol/L的氯化钠水溶液为汲取液,以纯化水为原液,测的膜通量18L/m2.h,盐截留率99.91%。
实施例3:
步骤(1):将质量百分比为11%的三醋酸纤维素加入到质量分数比例为二氧六环51份、丙酮24份、甲醇8份和乳酸6份的混合溶剂中,在50℃条件下搅拌充分溶解,将溶解好的铸膜液置于频率为40千赫兹、温度为20℃超声场中超声2小时,再静置3小时以上使其完全脱泡,备用;
步骤(2):将步骤(1)制备好的铸膜液涂覆在无纺布上,无纺布为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;并采用刮刀均匀的刮在无纺布上形成底膜层,底膜层厚度为0.01mm,将无纺布上的底模层在空气中静置20秒,然后将底膜层放入凝胶浴(凝胶浴的成分为去离子水)中经相转化凝胶成具有致密层的膜,并将膜置于80℃水浴中热处理6分钟,清洗之后,在60℃烘干,保存备用;
步骤(3):将质量百分比为2﹪的间苯二胺溶解于纯化水中制得间苯二胺水溶液作为水相;
步骤(4):将质量百分比为0.1﹪的均苯三甲酰氯溶解在异十二烷中,配制成均苯三甲酰氯异十二烷溶液作为有机相;
步骤(5):将间苯二胺水溶液均匀涂布在步骤(2)制备的三醋酸纤维素底膜上,固定2min,然后除去多余的间苯二胺水溶液;
步骤(6):将步骤(4)配制好的有机相溶液均匀涂布在步骤(5)处理好的三醋酸纤维素底膜上进行界面聚合2分钟,除去多余的溶液;然后在80℃下热处理9分钟,漂洗,烘干得到高性能复合正渗透膜。
本实施例所制备的高性能复合正渗透膜装入膜性能评价装置中,然后以2mol/L的氯化钠水溶液为汲取液,以纯化水为原液,测的膜通量25L/m2.h,盐截留率99.81%。
实施例4:
步骤(1):将质量百分比为14%的二醋酸纤维素加入到质量分数比例为二氧六环53份、丙酮15份、甲醇10份和乳酸8份的混合溶剂中,在50℃条件下搅拌充分溶解,将溶解好的铸膜液置于频率为60千赫兹、温度为30℃超声场中超声2.5小时,再静置3小时以上使其完全脱泡,备用;
步骤(2):将步骤(1)制备好的铸膜液涂覆在无纺布上,无纺布为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;并采用刮刀均匀的刮在无纺布上形成底膜层,底膜层厚度为0.15mm,将无纺布上的底模层在空气中静置25秒,然后将底膜层放入凝胶浴(凝胶浴的成分为去离子水)中经相转化凝胶成具有致密层的膜,并将膜置于90℃水浴中热处理3分钟,清洗之后,在50℃烘干,保存备用;
步骤(3):将质量百分比为1﹪的二乙烯三胺溶解于纯化水中制得二乙烯三胺水溶液作为水相;
步骤(4):将质量百分比为0.1﹪的间苯二甲酰氯溶解在正己烷中,配制成间苯二甲酰氯正己烷溶液作为有机相;
步骤(5):将二乙烯三胺水溶液均匀涂布在二醋酸纤维素底膜上,固定1min,然后除去多余的二乙烯三胺水溶液;
步骤(6):将步骤(4)配制好的有机相溶液均匀涂布在步骤(5)处理好的二醋酸纤维素底膜上进行界面聚合1分钟,除去多余的溶液;然后在60℃下热处理12分钟,漂洗,烘干得到高性能复合正渗透膜。
本实施例所制备的高性能复合正渗透膜装入膜性能评价装置中,然后以2mol/L的氯化钠水溶液为汲取液,以纯化水为原液,测的膜通量21L/m2.h,盐截留率99.83%。
实施例5:
步骤(1):将质量百分比为17%的醋酸纤维素加入到质量分数比例为二氧六环40份、丙酮20份、甲醇13份和乳酸10份的混合溶剂中,在50℃条件下搅拌充分溶解,将溶解好的铸膜液置于频率为80千赫兹、温度为40℃超声场中超声3小时,再静置3小时以上使其完全脱泡,备用;
步骤(2):将步骤(1)制备好的铸膜液涂覆在无纺布上,无纺布为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成;并采用刮刀均匀的刮在无纺布上形成底膜层,底膜层厚度为0.05mm,将无纺布上的底模层在空气中静置30秒,然后将底膜层放入凝胶浴(凝胶浴的成分为去离子水)中经相转化凝胶成具有致密层的膜,并将膜置于50℃水浴中热处理15分钟,清洗之后,在90℃烘干,保存备用;
步骤(3):将质量百分比为0.5﹪的哌嗪溶解于纯化水中制得哌嗪水溶液作为水相;
步骤(4):将质量百分比为0.05﹪的间苯二甲酰氯溶解在正己烷中,配制成间苯二甲酰氯正己烷溶液作为有机相;
步骤(5):将哌嗪水溶液均匀涂布在醋酸纤维素底膜上,固定0.5min,然后除去多余的哌嗪水溶液;
步骤(6):将步骤(4)配制好的有机相溶液均匀涂布在步骤(5)处理好的醋酸纤维素底膜上进行界面聚合0.5分钟,除去多余的溶液;然后在50℃下热处理15分钟,漂洗,烘干得到高性能复合正渗透膜。
本实施例所制备的高性能复合正渗透膜装入膜性能评价装置中,然后以2mol/L的氯化钠水溶液为汲取液,以纯化水为原液,测的膜通量29L/m2.h,盐截留率99.77%。
上述检测结果表明本发明制备的高性能复合正渗透膜具有良好的性能,具有很好推广应用前景和产业化的价值。
实际操作中,醋酸纤维素多孔底层还可以为醋酸纤维素、二醋酸纤维素、三醋酸纤维素中任意一种或两种质量比为1:1~1:4的混合物;多于一个功能团的芳香胺还可以为间苯二胺、邻苯二胺、二乙烯三胺、三乙烯四胺、哌嗪或其衍生物中任意一种或两种质量比为1:1~1:4的混合物;所述多于一个功能团的芳香酰氯为均苯三甲酰氯、间苯二甲酰氯、对苯二甲酰氯、多元磺酰氯中的一种或任意两种质量比为1:1~1:4的混合物;烷烃溶剂还可以为正己烷、正庚烷、正辛烷、正十二烷、异十二烷、异十六烷等烷烃类的一种或任意两种质量比为1:1~1:4的混合物。
本发明的高性能复合正渗透膜在维持聚酰胺层的高盐截流的条件下,结合了相转化法制备的含有大量亲水基团的醋酸纤维素多孔底层,保证了高水通量和高盐截留率,同时还具有高机械强度,耐溶剂性,抗污染性,可以用于急救水袋、航空航天、食品浓缩、制药、绿色能源、植物保护箱、海水淡化、硬水软化、工业废水等领域。
各位技术人员须知:虽然本发明已按照上述具体实施方式做了描述,但是本发明的发明思想并不仅限于此发明,任何运用本发明思想的改装,都将纳入本专利专利权保护范围内。
Claims (10)
1.一种高性能复合正渗透膜,其特征在于:包括无纺布支撑层、醋酸纤维素多孔底层、聚芳香酰胺致密分离层,所述醋酸纤维素多孔层位于无纺布支撑层、聚芳香酰胺致密分离层之间。
2.根据权利要求1所述的高性能复合正渗透膜,其特征在于:所述醋酸纤维素多孔底层为醋酸纤维素、二醋酸纤维素、三醋酸纤维素中任意一种或两种质量比为1:1~1:4的混合物。
3.根据权利要求1所述的高性能复合正渗透膜,其特征在于:所述无纺布支撑层为由聚酯、聚酰胺、聚烯烃或聚醚砜等所制备而成。
4.根据权利要求1所述的高性能复合正渗透膜,其特征在于:所述聚芳香酰胺致密分离层由多于一个功能团的芳香胺和多于一个功能团的芳香酰氯通过界面聚合生成。
5.根据权利要求4所述的高性能复合正渗透膜,其特征在于:所述多于一个功能团的芳香胺为间苯二胺、邻苯二胺、二乙烯三胺、三乙烯四胺、哌嗪或其衍生物中任意一种或两种质量比为1:1~1:4的混合物。
6.根据权利要求4所述的高性能复合正渗透膜,其特征在于:所述多于一个功能团的芳香酰氯为均苯三甲酰氯、间苯二甲酰氯、对苯二甲酰氯、多元磺酰氯中的一种或任意两种质量比为1:1~1:4的混合物。
7.一种如权利要求1所述的高性能复合正渗透膜的制备方法,其特征在于:包括以下步骤:
步骤(1):将质量百分比为5-17%的醋酸纤维素加入到由二氧六环、丙酮、甲醇和乳酸组成的铸膜液溶剂中,在40-65℃条件下搅拌充分溶解,将溶解好的液体置于频率为20~100千赫兹、温度为10~50℃超声场中超声0.5~3小时,再静置3小时以上使其完全脱泡,即得制备好的铸膜液,备用;
步骤(2):将步骤(1)中制备好的铸膜液涂覆在无纺布上,并采用刮刀均匀的刮在无纺布上形成底膜层,将无纺布上的底膜层在空气中静置5-30秒,然后将底膜层放入凝胶浴中经相转化凝胶成具有多孔结构的底层,所述凝胶浴的成分为去离子水,并将膜置于35-90℃水浴中热处理3-20分钟,清洗之后,在50-100℃烘干,即得醋酸纤维素底膜,保存备用;
步骤(3):将质量百分比为0.5~5﹪的多于一个功能团的芳香胺溶解于纯化水中制得多于一个功能团的芳香胺水溶液;
步骤(4):将质量百分比为0.05~1﹪的多于一个功能团的芳香酰氯溶解在烷烃溶剂中,配制成多于一个功能团的芳香酰氯有机相溶液;
步骤(5):将多于一个功能团的芳香胺水溶液与步骤(2)制备的醋酸纤维素底膜均匀接触,固定0.5-5min,然后除去多余的多于一个功能团的芳香胺水溶液;
步骤(6):将步骤(4)配制好的多于一个功能团的芳香酰氯有机相溶液与经过步骤(5)处理好后的醋酸纤维素底膜上进行界面聚合0.5~5分钟,除去多余的多于一个功能团的芳香酰氯有机相溶液;然后在50~130℃下热处理2~15分钟,漂洗,烘干得到高性能复合正渗透膜。
8.根据权利要求7所述的高性能复合正渗透膜的制备方法,其特征在于:所述的铸膜液溶剂,其组分及所占质量分数比例如下:二氧六环40-70份、丙酮12-24份、甲醇5-15份、乳酸2-10份。
9.根据权利要求7所述的高性能复合正渗透膜的制备方法,其特征在于:所述底膜层厚度为0.01-0.2mm。
10.根据权利要求7所述的高性能复合正渗透膜的制备方法,其特征在于:所述烷烃溶剂为正己烷、正庚烷、正辛烷、正十二烷、异十二烷、异十六烷等烷烃类的一种或任意两种质量比为1:1~1:4的混合物。
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