CN113230906A - 一种自制粉煤灰疏水陶瓷复合膜的制备方法 - Google Patents
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Abstract
本发明公开了一种自制粉煤灰疏水陶瓷复合膜的制备方法,包括以下步骤:(1)分别用乙醇、丙酮和去离子水将自制粉煤灰陶瓷膜进行超声清洗、干燥;(2)取无水乙醇和乙酸乙酯混合,然后加入1H,1H,2H,2H‑全氟癸基三乙氧基硅烷,混合均匀后静置;(3)将步骤(1)得到的粉煤灰陶瓷膜浸泡到步骤(2)的接枝溶液中,静置后取出;(4)将步骤(3)中得到的粉煤灰陶瓷膜在干燥箱中干燥;(5)将步骤(4)得到的粉煤灰陶瓷膜用乙醇和去离子水清洗、干燥,得到疏水粉煤灰复合陶瓷膜。本发明的粉煤灰疏水陶瓷膜为复合材料,有机氟硅烷聚合物与无机粉煤灰陶瓷膜层之间以共价键的方式结合,膜层稳定不易脱落,适合用于海水淡化或废水处理的膜蒸馏过程。
Description
技术领域
本发明属于膜技术领域,具体涉及一种自制粉煤灰疏水陶瓷复合膜的制备方法,可用于海水淡化、废水处理等膜蒸馏过程应用研究中。
背景技术
目前全球正面临着严重的水资源短缺问题,这对全球经济以及工业的快速发展产生了严重的影响。作为最大的发展中国家,我国尤其是西北部地区也面临着水资源严重短缺的形势。因此,关于水资源的回收利用以及淡水的制备成为研究的热点。常用的脱盐技术有反渗透、热蒸发等,但是这些方法都需要在较大的压差或较高的温度下进行,耗能很高,水回收成本较高。相比于传统的脱盐技术,膜蒸馏技术作为一种新兴的除盐工艺,操作过程简单,分离过程几乎在常压下进行;所需温度较低,只需要维持膜两侧适当温差即可进行分离过程,因此可以充分利用太阳能、地热能以及工厂中的废热等廉价能源,耗能较低,在脱盐技术中表现出明显的优势。用于膜蒸馏的膜材料必须满足疏水性才能保证分离过程具有良好的截盐率。
近年来,用于膜蒸馏过程的多为一些具有低表面能的有机高分子聚合物制备的疏水膜,如:聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、聚丙烯(PP)等,表现出良好的分离性能,但是由于有机物膜本身机械强度较低,对高温敏感易发生热溶胀,同时对强酸或强碱耐受性能差,所以限制了其工业化应用。与有机膜相比,陶瓷膜具有优异的机械强度,耐酸碱性,可以在极端条件下应用。但是陶瓷膜由于表面羟基的存在而表现出亲水性,故必须对其表面进行憎水处理才可以用于膜蒸馏过程。
本发明使用自制的粉煤灰陶瓷膜,对其表面进行疏水改性处理,得到了粉煤灰疏水陶瓷复合膜,表现出良好的疏水性。
发明内容
本发明提供一种粉煤灰疏水陶瓷复合膜的制备方法。
粉煤灰疏水陶瓷复合膜的制备方法,包括以下步骤:
(1)将自制的粉煤灰陶瓷膜分别用85vol.%乙醇、丙酮和去离子水超声清洗15min,取出后在干燥箱中烘干;
(2)分别取10mL无水乙醇和乙酸乙酯混合,然后将1g1H,1H,2H,2H-全氟癸基三乙氧基硅烷加入乙醇和乙酸乙酯的混合溶液中,得到0.1mol/L的1H,1H,2H,2H-全氟癸基三乙氧基硅烷的乙醇和乙酸乙酯混合溶液,室温下静置12h;
(3)将经步骤(1)预处理过的粉煤灰陶瓷膜浸泡到步骤(2)制备的1H,1H,2H,2H-全氟癸基三乙氧基硅烷的乙醇和乙酸乙酯混合溶液中,在30℃下静置24h;
(4)将步骤(3)中得到的粉煤灰陶瓷膜取出放在干燥箱中,在110℃下固化2h;
(5)将步骤(4)的粉煤灰陶瓷膜用乙醇和去离子水清洗,之后置于干燥箱中,在60℃下干燥6h,得到疏水粉煤灰复合陶瓷膜。
本发明的有益效果为:
(1)采用自制粉煤灰陶瓷膜为基体,制作原料廉价易得,疏水陶瓷膜的制备成本减少,进而降低膜蒸馏运行成本,相较于市场中氧化铝陶瓷膜等更具竞争力;
(2)可以回收利用电厂废弃物粉煤灰,提高了废弃物回收再利用效率,有利于可持续发展;
(3)本发明制备的疏水陶瓷膜通量较高,解决了膜蒸馏通量不高的问题,同时具有良好的截盐率,除盐效果良好,适用于海水淡化以及电厂废水处理等恶劣环境。
附图说明
图1是实例一中所用自制平板粉煤灰陶瓷膜
图2是实例一中改性前后平板粉煤灰陶瓷膜润湿性比较
图3是实例一中改性后平板粉煤灰陶瓷膜静态接触角测量结果。
Claims (8)
1.一种自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:包括以下步骤:
(1)将自制的粉煤灰陶瓷膜分别用为乙醇、丙酮和去离子水超声清洗10-30min,取出后在干燥箱中干燥;
(2)分别取无水乙醇和乙酸乙酯混合,体积比为1:1-4:1,然后将1H,1H,2H,2H-全氟癸基三乙氧基硅烷加入乙醇和乙酸乙酯的混合溶液中,充分搅拌,得到0.05 -0.15mol/L的1H,1H,2H,2H-全氟癸基三乙氧基硅烷的乙醇和乙酸乙酯混合溶液,室温下静置12-24h;
(3)将经步骤(1)预处理过的粉煤灰陶瓷膜浸泡到步骤(2)制备的1H,1H,2H,2H-全氟癸基三乙氧基硅烷的乙醇和乙酸乙酯混合溶液中,在25-35℃下静置24-48h;
(4)将步骤(3)中得到的粉煤灰陶瓷膜取出放在干燥箱中,在80-110℃下固化2-5h;
(5)将步骤(4)的粉煤灰陶瓷膜用乙醇和去离子水清洗,之后置于干燥箱中,在50-80℃下干燥6h,得到疏水粉煤灰复合陶瓷膜。
2.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:所用陶瓷膜包括管状及平板粉煤灰陶瓷膜。
3.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤(1)中乙醇的质量浓度为85%,丙酮质量浓度为97%,超声清洗频率40KHz,功率为400-700W,清洗时间为10-30min;自制粉煤灰陶瓷膜在干燥箱中干燥时间为3-5h,干燥温度为60-80℃。
4.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤2中的氟硅烷溶液包括1H,1H,2H,2H-全氟癸基三乙氧基硅烷以及1H,1H,2H,2H-全氟癸基三氯硅烷。
5.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤(2)中无水乙醇浓度为99.7%,乙酸乙酯浓度为99%,两种溶液混合体积比为1:1-4:1,搅拌时间为15-30min;1H,1H,2H,2H-全氟癸基三乙氧基硅烷的乙醇和乙酸乙酯混合溶液浓度为0.05-0.15mol/L,静置时间为10-15h,静置温度为25-35℃。
6.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤(3)中自制粉煤灰陶瓷膜在溶液中浸泡时间为24-48h,浸泡温度在25-35℃之间。
7.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤(4)中自制粉煤灰陶瓷复合膜固化温度在80-110℃之间,固化时间为2-5h。
8.根据权利要求1所述的自制粉煤灰疏水陶瓷复合膜的制备方法,其特征在于:步骤(5)中陶瓷膜干燥温度为50-80℃,干燥时间为4-8h。
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