CN114225709A - 固定原位生长银纳米粒子的超双亲油水分离膜的制备方法 - Google Patents
固定原位生长银纳米粒子的超双亲油水分离膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种固定原位生长银纳米粒子的超双亲油水分离膜的制备方法:将聚合物高分子膜基材溶于有机溶剂,然后添加亲水性改性剂、交联剂和引发剂,搅拌溶解,静置脱泡,得到铸膜液;将所得铸膜液在聚合物支撑层上进行刮膜,接着将膜浸入银氨溶液中,再向银氨溶液中加入葡萄糖溶液,在25~60℃下进行相转化2~60min,之后取出清洗,干燥,得到超双亲油水分离膜;本发明制备的超双亲油水分离膜对不同类型的乳液均具有良好的分离性能,同时还具有优异的稳定性与较高的机械强度,在油水分离、污水处理及海洋石油泄漏中均具有广泛的应用价值。
Description
技术领域
本发明属于高分子膜分离技术领域,具体涉及一种原位生长银纳米粒子制备聚合物超双亲油水分离膜的方法。
背景技术
在过去的几十年里,膜技术逐渐成为一种流行的分离技术。在工业过程中使用膜有许多显著的优点,例如,没有相变或化学添加剂,模块化易于扩大,操作简单,相对低能耗等。因此,膜技术已被广泛应用于水处理、气体净化、食品加工、医药工业、环保等领域。膜是膜分离技术的关键,直接影响工艺效率和实际应用价值。目前,几乎所有工业用膜都是由无机材料和/或有机聚合物制成的,后者在现有膜市场上占主导地位。有机聚合物的例子包括聚砜(PSF)、聚醚砜(PES)、聚丙烯腈(PAN)、聚酰胺、聚酰亚胺、聚偏氟乙烯(PVDF)和聚四氟乙烯(PTFE)。聚合物膜由于其优异的热稳定性、良好的耐化学性和成膜性能,已广泛应用于科研和工业生产。
聚合物膜在水处理中的污染和膜接触器的润湿性是制约其应用的两个主要问题。污染和湿润会降低膜的效率,降低膜的性能,从而增加运行成本,甚至导致膜失效。对聚合物膜进行适当的亲水性改性,可以有效地提高膜的耐污性或润湿性。通过有机-无机杂化的方式,将无机纳米粒子与聚合物相结合,是改善膜抗污染能力的有效手段。常用的无机纳米粒子包括氧化锌(ZnO)、二氧化钛(TiO2)、二氧化硅(SiO2)、碳纳米管(CNT)以及氧化石墨烯等。但是在成膜的过程中,无机纳米粒子与聚合物膜的相容性较差,容易在膜材料结构中团聚,导致分离膜的抗污染性不稳定。
本发明通过原位生长直接在表面固定银纳米颗粒,得到的聚合物超双亲油水分离膜具有高强度、高通量的特点,且在油水分离过程中通量稳定,分离性能优异,在油水分离、污水处理及海洋石油泄漏中均具有广泛的应用价值。
发明内容
本发明的目的是公开一种通过原位生长直接在表面固定银纳米颗粒制备聚合物超双亲油水分离膜的方法,解决膜在分离过程中产生严重的膜污染现象,导致通量下降的问题。作为聚合物膜的凝固浴,采用在相转化的过程中原位生长银纳米粒子从而将银纳米粒子很好的固定在膜孔道与表面上,得到一种多孔超双亲油水分离聚合物膜,可以用于实现高效的油水分离。
本发明的技术方案如下:
一种固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,所述制备方法为:
将聚合物高分子膜基材溶于有机溶剂,然后添加亲水性改性剂、交联剂和引发剂,搅拌溶解,静置脱泡,得到铸膜液;将所得铸膜液在聚合物支撑层上进行刮膜,接着将膜浸入银氨溶液中,再向银氨溶液中加入葡萄糖溶液,在25~60℃下进行相转化2~60min,之后取出清洗,干燥(20~80℃),得到超双亲油水分离膜;
所述聚合物高分子膜基材为聚偏氟乙烯、聚砜、聚醚砜或聚丙烯腈;
所述有机溶剂为磷酸三乙酯(TEP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)中的一种或两种以上任意比例的混合溶剂;
所述亲水性改性剂为乙二醇二甲基丙烯酸酯、甲基丙烯酸二甲氨乙酯、聚乙烯醇、聚乙烯吡咯烷酮或聚乙二醇;
所述交联剂为N,N-亚甲基双丙烯酰胺;
所述引发剂为2,2-偶氮二异丁腈或偶氮二异丁酸二甲酯;
所述聚合物高分子膜基材溶于有机溶剂的条件为:在60~85℃下搅拌3~5h;所得溶液的浓度为10~20%;所得溶液与亲水性改性剂、交联剂、引发剂的质量比为100:6~14:0.02~0.1:0.02~0.08;
所述添加亲水性改性剂、交联剂和引发剂的具体操作方法为:先添加亲水性改性剂和交联剂,在氮气氛围、60~85℃下搅拌20min后,再加入引发剂,在氮气氛围、60~85℃下搅拌反应8~12h;
所述聚合物支撑层为:由聚酯、聚烯烃、尼龙等聚合物中的一种或多种组成的纤维无纺布或纺织材料;
所述刮膜的条件为:环境温度25±1℃,湿度38±2%,刮膜厚度300μm;
所述银氨溶液的配制方法为:将硝酸银溶解于水中,配制成质量分数为0.5~2%的硝酸银溶液,向硝酸银溶液中滴加氨水(25~28wt%)至澄清,即得;
所述葡萄糖溶液由葡萄糖、聚乙烯吡咯烷酮(致孔剂)溶解于水中而得,其中葡萄糖的质量分数为0.5~4%,聚乙烯吡咯烷酮的质量分数为0.03~0.05%;
所述银氨溶液和葡萄糖溶液的体积比为1:1~5。
本发明制备的超双亲油水分离膜包含:聚合物支撑层、在聚合物支撑层上的多孔聚合物分离层、在多孔聚合物分离层上的银纳米颗粒组成的表面微纳米粗糙结构;
其中,聚合物支撑层的厚度为30~300μm,多孔聚合物分离层的表征分离孔径大小约为0.01~10μm,银纳米粒子的大小为20nm~2μm,银纳米粒子的含量为0.01~5%;
膜在空气中的水接触角<10°,油(正己烷)接触角<10°。
本发明制备的超双亲油水分离膜可应用于油水分离。
本发明的有益效果在于:
本发明通过原位生长和相转化结合直接在表面固定银纳米颗粒的方法,构思新颖,操作简单。由于使用被葡萄糖溶液还原的银氨溶液作为凝固浴直接原位生长银纳米粒子,很容易解决了粒子团聚的问题。同时在相转化的过程中,由于纳米粒子的存在改变了膜表面的形貌与结构,使得膜具有多孔疏松结构,从而进一步提高膜的亲水性。
本发明制备的超双亲油水分离膜对不同类型的乳液均具有良好的分离性能,同时还具有优异的稳定性与较高的机械强度,在油水分离、污水处理及海洋石油泄漏中均具有广泛的应用价值。
附图说明
图1:空白聚偏氟乙烯超滤膜的SEM图;膜表面结构较为光滑,存在致密的孔结构,孔径在1~5μm。
图2:固定银纳米粒子的聚偏氟乙烯膜的SEM图;膜表面形貌为多孔网络状的结构,孔径在3~7μm还覆盖了大量的银纳米粒子,银纳米粒子大小为0.3~0.5μm。
图3:空白聚偏氟乙烯膜的水接触角图片,在空气中水接触角为102°。
图4:固定银纳米粒子的聚偏氟乙烯膜的水接触角图片,在空气中膜在1.4s内被完全润湿。
图5:固定银纳米粒子的聚偏氟乙烯膜的油(正己烷)接触角图片,在空气中膜在0.86s内被完全润湿。
图6:固定银纳米粒子的聚偏氟乙烯膜水下油(泵油)接触角图片,在水下泵油的接触角为155.7°。
图7:固定银纳米粒子的聚偏氟乙烯膜油(泵油)下水接触角图片,在泵油下水的接触角为156.9°。
图8:(a)是不同种类水包油型乳液在0.09MPa压力下的分离效率和通量图,膜对水包正己烷、水包石油醚、水包石蜡、水包甲苯型乳液的分离效率都在99%以上;(b)是不同种类油包水型乳液在0.09MPa压力下的分离效率和通量图,膜对正己烷包水、石油醚包水、石蜡包水、甲苯包水型乳液的分离效率都在99%左右。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
实施例1
(1)将6g聚偏氟乙烯粉末溶于44g N-甲基吡咯烷酮中,在80℃下搅拌3h待其完全溶解;
(2)加入4g亲水物质甲基丙烯酸二甲氨乙酯和0.04g N,N-亚甲基双丙烯酰胺,20min后将0.02g引发剂2,2-偶氮二异丁腈添加进入上述混合液中,在氮气气氛保护下于80℃下搅拌10h,得到均一、透明的铸膜液;
(3)将上述制备的铸膜液静置12h脱泡后,在25℃下刮膜,膜厚为300μm,刮膜在PET无纺布(购自杭州水处理中心)上进行;将1g硝酸银溶解于120ml水中,向硝酸银溶液中滴加氨水至澄清,即为银氨溶液;将膜放入上述银氨溶液中。将1g葡萄糖和0.04g聚乙烯吡咯烷酮溶解于120ml水中,溶解完倒入放入膜的银氨溶液中,25℃下相转化1h。
(4)最后将平板膜置于纯水中清洗,取出在40℃下干燥,得到超双亲油水分离的聚偏氟乙烯膜。
实施例2
(1)将6g聚偏氟乙烯粉末溶于44g N-甲基吡咯烷酮中,在70℃下搅拌3h待其完全溶解;
(2)加入5g亲水物质甲基丙烯酸二甲氨乙酯和0.04g N,N-亚甲基双丙烯酰胺,20min后将0.03g引发剂2,2-偶氮二异丁腈添加进入上述混合液中,在氮气气氛保护下于70℃下搅拌10h,得到均一、透明的铸膜液;
(3)将上述制备的铸膜液静置12h脱泡后,在25℃下刮膜,膜厚为300μm,刮膜在PET无纺布上进行;将1.2g硝酸银溶解于120ml水中,向硝酸银溶液中滴加氨水至澄清,即为银氨溶液;将膜放入上述银氨溶液中。将2.4g葡萄糖和0.048g聚乙烯吡咯烷酮溶解于120ml水中,溶解完倒入放入膜的银氨溶液中,水浴加热40℃下相转化30min。
(4)最后将平板膜置于纯水中清洗,取出在40℃下干燥,得到超双亲油水分离的聚偏氟乙烯膜。
实施例3
(1)将7g聚偏氟乙烯粉末溶于43g N-甲基吡咯烷酮中,在80℃下搅拌4h待其完全溶解;
(2)加入4g亲水物质甲基丙烯酸二甲氨乙酯和0.04g N,N-亚甲基双丙烯酰胺,20min后将0.02g引发剂2,2-偶氮二异丁腈添加进入上述混合液中,在氮气气氛保护下于80℃下搅拌10h,得到均一、透明的铸膜液;
(3)将上述制备的铸膜液静置12h脱泡后,在25℃下刮膜,膜厚为300μm,刮膜在PET无纺布上进行;将1.2g硝酸银溶解于120ml水中,向硝酸银溶液中滴加氨水至澄清,即为银氨溶液;将膜放入上述银氨溶液中。将2.4g葡萄糖和0.048g聚乙烯吡咯烷酮溶解于120ml水中,溶解完倒入放入膜的银氨溶液中,水浴加热40℃下相转化40min。
(4)最后将平板膜置于纯水中清洗,取出在40℃下干燥,得到超双亲油水分离的聚偏氟乙烯膜。
实施例3改性的聚偏氟乙烯膜的水接触角如图4所示在1.4s内变为0°,油接触角如图5所示在0.86s内变为零度,同时膜的水下油(泵油)接触角为155.7°与油(泵油)下水接触角156.9°,分别如图6、图7所示,膜表面形貌为多孔网络状的结构,具体如图2所示。
实施例4
(1)将7g聚偏氟乙烯粉末溶于43g N-甲基吡咯烷酮中,在85℃下搅拌3h待其完全溶解;
(2)加入5g亲水物质甲基丙烯酸二甲氨乙酯和0.04g N,N-亚甲基双丙烯酰胺,20min后将0.02g引发剂2,2-偶氮二异丁腈添加进入上述混合液中,在氮气气氛保护下于85℃下搅拌10h,得到均一、透明的铸膜液;
(3)将上述制备的铸膜液静置12h脱泡后,在25℃下刮膜,膜厚为300μm,刮膜在PET无纺布上进行;将1.2g硝酸银溶解于120ml水中,向硝酸银溶液中滴加氨水至澄清,即为银氨溶液;将2.4g葡萄糖和0.04g聚乙烯吡咯烷酮溶解于120ml水中,溶解完倒入上述银氨溶液中,将膜放入上述溶液中,在60℃下相转化15min。
(4)最后将平板膜置于纯水中清洗,取出在30℃下干燥,得到超双亲油水分离的聚偏氟乙烯膜。
实施例5
(1)将6g聚丙烯腈粉末溶于44g N-甲基吡咯烷酮中,搅拌4h待其完全溶解;
(2)加入4g亲水物质甲基丙烯酸二甲氨乙酯和0.02g N,N-亚甲基双丙烯酰胺,20min后将0.02g引发剂2,2-偶氮二异丁腈添加进入上述混合液中,在氮气气氛保护下于75℃下搅拌10h,得到均一、透明的铸膜液;
(3)将上述制备的铸膜液静置12h脱泡后,在25℃下刮膜,膜厚为300μm,刮膜在PET无纺布上进行;将1.2g硝酸银溶解于120ml水中,向硝酸银溶液中滴加氨水至澄清,即为银氨溶液;将2.4g葡萄糖和0.04g聚乙烯吡咯烷酮溶解于120ml水中,溶解完倒入上述银氨溶液中,将膜放入上述溶液中,水浴加热60℃下相转化20min。
(4)最后将平板膜置于纯水中清洗,取出在60℃下干燥,得到超双亲油水分离的聚丙烯腈膜。
表1固定银纳米粒子的聚合物膜的银纳米粒子的大小、水接触角、油接触角、分离效率和通量
对比例1空白聚偏氟乙烯膜的制备方法
将7g聚偏氟乙烯粉末溶于43g N-甲基吡咯烷酮中,在80℃搅拌4h,静置12h除泡。刮膜要求同实施例3,将初始膜直接浸入纯水的凝固浴中进行相转化,然后干燥保存。
对比例1制备的初始聚偏氟乙烯膜的接触角稳定在102°,如图3所示;膜表面结构较为光滑,存在致密的孔结构,具体如图1所示。
Claims (10)
1.一种固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述制备方法为:
将聚合物高分子膜基材溶于有机溶剂,然后添加亲水性改性剂、交联剂和引发剂,搅拌溶解,静置脱泡,得到铸膜液;将所得铸膜液在聚合物支撑层上进行刮膜,接着将膜浸入银氨溶液中,再向银氨溶液中加入葡萄糖溶液,在25~60℃下进行相转化2~60min,之后取出清洗,干燥,得到超双亲油水分离膜;
所述聚合物高分子膜基材为聚偏氟乙烯、聚砜、聚醚砜或聚丙烯腈;
所述有机溶剂为磷酸三乙酯、N,N-二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上任意比例的混合溶剂;
所述亲水性改性剂为乙二醇二甲基丙烯酸酯、甲基丙烯酸二甲氨乙酯、聚乙烯醇、聚乙烯吡咯烷酮或聚乙二醇;
所述交联剂为N,N-亚甲基双丙烯酰胺;
所述引发剂为2,2-偶氮二异丁腈或偶氮二异丁酸二甲酯;
所述葡萄糖溶液由葡萄糖、聚乙烯吡咯烷酮溶解于水中而得。
2.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述聚合物高分子膜基材溶于有机溶剂的条件为:在60~85℃下搅拌3~5h;所得溶液的浓度为10~20%;所得溶液与亲水性改性剂、交联剂、引发剂的质量比为100:6~14:0.02~0.1:0.02~0.08。
3.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述添加亲水性改性剂、交联剂和引发剂的操作方法为:先添加亲水性改性剂和交联剂,在氮气氛围、60~85℃下搅拌20min后,再加入引发剂,在氮气氛围、60~85℃下搅拌反应8~12h。
4.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述聚合物支撑层为:由聚酯、聚烯烃、尼龙中的一种或多种组成的纤维无纺布或纺织材料。
5.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述刮膜的条件为:环境温度25±1℃,湿度38±2%,刮膜厚度300μm。
6.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述银氨溶液的配制方法为:将硝酸银溶解于水中,配制成质量分数为0.5~2%的硝酸银溶液,向硝酸银溶液中滴加氨水至澄清,即得。
7.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述葡萄糖溶液中,葡萄糖的质量分数为0.5~4%,聚乙烯吡咯烷酮的质量分数为0.03~0.05%。
8.如权利要求1所述固定原位生长银纳米粒子的超双亲油水分离膜的制备方法,其特征在于,所述银氨溶液和葡萄糖溶液的体积比为1:1~5。
9.如权利要求1~8任一项所述制备方法制得的超双亲油水分离膜。
10.如权利要求9所述超双亲油水分离膜在油水分离中的应用。
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