CN117085659A - 一种含气凝胶的聚合物吸附膜及其制备方法 - Google Patents
一种含气凝胶的聚合物吸附膜及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种含气凝胶的高聚物吸附膜及其制备方法,将高聚物粉末和具有吸附功能的气凝胶共混后经相转化成膜,通过气凝胶独特的纳米颗粒骨架,具有高通透性多分枝孔和纳米骨架组成的三维空间纳米网络结构,从而达到对溶液中铀的吸附作用,制备出的杂化超滤膜成本低、重复性能好、制备过程简单、表面结构稳定并能够减少吸附材料的质量损失。
Description
技术领域
本发明属于膜吸附领域,具体涉及一种含气凝胶的聚合物吸附膜及其制备方法。
背景技术
世界能源需求持续增加,是人类面临的最大环境挑战。由于传统化石燃料的短缺,核能在满足能源需求方面起着至关重要的作用。虽然核能是一种无碳能源,没有温室气体排放,但相当数量的放射性核素,如铀(235,238U),具有半衰期长、迁移率高等特点,这些放射性核素会对地表水以及地下水造成严重的污染,并对人类健康产生巨大的危害。
吸附法是常用的水处理技术之一,具有操作简单、适应性强等优点。吸附法主要是依靠具有较大比表面积和吸附容量的材料将污染物从水中分离去除,从而达到净水之目的。优质的吸附材料具有吸附能力强、成本低、易回收等特点,且吸附材料在空气净化、污水处理、化工提纯、医药过滤、海水淡化等领域有着广泛的应用。但一些先进的功能性纳米材料,如粘土矿物、沸石、碳材料和金属有机框架(MOFs),因其吸附动力学慢、吸附容量低,限制了其实际应用,此外如MOF、COF等材料,它们实际用量大,并且价格昂贵,故成本较高,不利于实际应用。
气凝胶由纳米颗粒骨架构成,具有高通透性多分枝孔和纳米骨架组成的三维空间纳米网络结构,气凝胶孔洞率最高可达99%,而且这些孔洞的尺度仅为几十纳米,形成了巨大的比表面积,非常有利于对气体的吸附,是具有广阔应用前景的一类吸附剂材料。近年来随着溶胶-凝胶技术,特别是常压干燥技术的发展,避免了昂贵繁琐的超临界干燥过程,气凝胶的制备成本大幅下降,使得大规模生产和应用气凝胶成为可能。通过对某些气凝胶的疏水改性,使其应用在有机气体或溶液离子的吸附领域,吸附效率及吸附容量为等同质量活性的10倍以上,且吸附循环性良好。然而气凝胶这种新材料密度仅为3.55千克每立方米,仅为空气密度的2.75倍,因而分散在水中体积庞大,不利于回收重复利用,如何降低材料损失,防止吸附特性降低,将吸附材料固定在聚合物中是一个重要的目标,可以使这些材料应用于大规模应用。
膜吸附在吸附领域应用较为广泛,膜吸附主要靠改性基团或者添加粒子来对溶液中某种离子进行选择性吸附,成膜后吸附有效面积较大,并且能够防止功能性粒子的质量损失,易于重复回收利用。目前制备超滤膜的材料主要包括聚偏氟乙烯、聚砜、聚醚砜、聚丙烯腈等材料,这些材料具有良好的机械性能、热稳定性和成膜性,在膜吸附领域应用广泛。
发明内容
为了解决上述吸附成本高,吸附材料质量易损失等问题,本发明提供了一种含气凝胶的聚合物吸附膜及其制备方法,将气凝胶与高聚物共混,再通过相转化法成膜,以达到共混膜对铀的吸附作用。采用具有吸附功能的气凝胶与高聚物成膜提取铀,大大减少了吸附材料质量损失。此外制备的共混膜操作简单,力学性能优异、抗污性能强、成本极低、吸附平衡时间短,能够长期稳定运行。
为此,本发明的技术方案如下:
1)气凝胶的制备:将基体原料与水混合,用酸将混合物体系pH调节至凝胶环境,使其凝胶化,形成水凝胶,通过冲洗,自然沥干,减少水凝胶中的盐分,然后用表面活性剂配制的水溶液清洗自然沥干,将水凝胶送入常压干燥炉,通过直接加热干燥得到气凝胶。
2)杂化膜的制备:将一定比例的气凝胶和高聚物粉末加到80~86wt%溶剂中,超声分散,得到分散均匀的溶液,水浴加热并机械搅拌反应6~15h,其中水浴温度为45~80℃,机械搅拌速率为100~400r/min,反应完成后真空脱泡,用自动涂膜机涂制平板膜,随后浸泡在去离子水中。
3)海水提铀试验:吸附实验使用不同初始浓度的铀溶液进行试验;pH由HNO3和NaOH调节;在脱附实验中,用1mol/L的HCl溶液进行解吸附;吸附和脱附过程均采用ICP等离子光谱仪测试溶液中铀浓度变化,吸附实验装置采用实验室常用水通量测试装置。
进一步,步骤1)中所述的气凝胶为二氧化硅气凝胶、氧化铝气凝胶。
进一步,步骤1)中所述的酸为醋酸、硅酸、盐酸中的其中一种。
进一步,步骤1)中所述的表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、二辛基琥珀酸磺酸钠中的其中一种。
进一步,步骤2)中所述气凝胶在高聚物粉末中的占比为质量百分比20%至75%。
进一步,步骤2)中所述的高聚物粉末为聚丙烯腈(PAN)、聚醚砜(PES)、聚偏氟乙烯(PVDF)中的其中一种。
进一步,步骤2)中所述溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)或N-甲基吡咯烷酮(NMP)中的其中一种。
与现有技术相比,本发明具有如下优点:
1)所用的气凝胶在溶剂中的溶解性较好,相对于一般粒子,可较大量添加至杂化膜内,并且杂化膜的成膜性能好。
2)首次将气凝胶运用到溶液中离子的吸附,并且将气凝胶材料固定在膜内,解决了粒子在吸附过程中的质量损失,不易重复利用的问题。
3)本发明制备的杂化超滤膜通量较高、表面结构稳定、吸附平衡时间短,能够长期稳定运行,所使用的气凝胶绿色环保、价格低廉,可大量实际应用。
附图说明
图1为实施例2得到的二氧化硅气凝胶的扫描电镜图
图2为实施例3得到的含二氧化硅气凝胶的聚丙烯腈杂化膜吸附前后的照片
具体实施方式
下面结合附图和实施例对本发明做进一步的说明。
实施例1~2
1)氧化铝气凝胶的制备:将铝源与水混合,用醋酸将混合物体系pH调节至凝胶环境,使其凝胶化,形成水凝胶,通过冲洗,自然沥干,减少水凝胶中的盐分,然后用十六烷基三甲基溴化铵配制的水溶液清洗自然沥干,将水凝胶送入常压干燥炉,通过直接加热干燥得到氧化铝气凝胶。
2)二氧化硅气凝胶的制备:将硅源与水混合,用醋酸将混合物体系pH调节至凝胶环境,使其凝胶化,形成水凝胶,通过冲洗,自然沥干,减少水凝胶中的盐分,然后用十六烷基三甲基溴化铵配制的水溶液清洗自然沥干,将水凝胶送入常压干燥炉,通过直接加热干燥得到二氧化硅气凝胶。
3)气凝胶的准备:称量如表1所示制得的两种气凝胶各50mg,分别置于烧杯中,待步骤4)所配制的铀溶液加入,开始测量吸附时间和吸附容量。
4)海水提铀试验:吸附实验使用不同初始浓度的铀溶液进行试验;pH由HNO3和NaOH调节;在脱附实验中,用1mol/L的HCl溶液进行解吸附;吸附和脱附过程均采用ICP等离子光谱仪测试溶液中铀浓度变化,吸附实验装置采用实验室常用水通量测试装置。
对实施列2得到的二氧化硅气凝胶进行扫面电镜的表征,如图1所示二氧化硅气凝胶呈现出具有蜂窝状多孔网络骨架,它由许多不规则的球形颗粒堆积连接而成,骨架间存在大量孔洞,有利于物质的吸附。
表1实施例1~2具体实施方案
由实施例1~2可知,二氧化硅气凝胶的吸附量为167.9mg/g,吸附平衡时间为240min,综合性能优于氧化铝气凝胶。
实施例3~6
其制备过程基本相同,不同仅在于:改变步骤2)中的气凝胶添加比例。
1)二氧化硅气凝胶的制备:将硅源与水混合,用醋酸将混合物体系pH调节至凝胶环境,使其凝胶化,形成水凝胶,通过冲洗,自然沥干,减少水凝胶中的盐分,然后用十六烷基三甲基溴化铵配制的水溶液清洗自然沥干,将水凝胶送入常压干燥炉,通过直接加热干燥得到二氧化硅气凝胶。
2)杂化膜的制备:将二氧化硅气凝胶和聚丙烯腈粉末(PAN)按表2所示比例加到84wt%DMAc溶剂中,超声分散,得到分散均匀的溶液,水浴加热并机械搅拌反应15h,其中水浴温度为60℃,机械搅拌速率为200r/min,反应完成后真空脱泡,用自动涂膜机涂制平板膜,随后浸泡在去离子水中。
3)海水提铀试验:吸附实验使用不同初始浓度的铀溶液进行试验;pH由HNO3和NaOH调节;在脱附实验中,用1mol/L的HCl溶液进行解吸附;吸附和脱附过程均采用ICP等离子光谱仪测试溶液中铀浓度变化,吸附实验装置采用实验室常用水通量测试装置。
图2为实施例3得到的含二氧化硅的聚丙烯腈杂化膜吸附前后的照片,吸附后杂化膜颜色变黄,可从表观上判断溶液中铀离子被成功吸附。
表2实施例3~6具体实施方案
由实施例3~6可知,当二氧化硅气凝胶在聚丙烯腈中的占比为30%时,拉伸强度适中为1.31MPa,通量较高为340L/m2·h·bar,吸附容量为133.6mg/g。
对比例1
1)超滤膜的制备:将聚丙烯腈(PAN)粉末加到84wt%DMAc溶剂中,超声分散,水浴加热并机械搅拌反应15h,其中水浴温度为60℃,机械搅拌速率为200r/min,反应完成后真空脱泡,用自动涂膜机涂制平板膜,随后浸泡在去离子水中。
2)海水提铀试验:吸附实验使用不同初始浓度的铀溶液进行试验;pH由HNO3和NaOH调节;在脱附实验中,用1mol/L的HCl溶液进行解吸附;吸附和脱附过程均采用ICP等离子光谱仪测试溶液中铀浓度变化,吸附实验装置采用实验室常用水通量测试装置。
对实施例4,对比例1进行拉伸强度、纯水通量,吸附容量的测试,对实施例2进行吸附容量的测试,数据如表3。
表3实施例2、4、对比例1具体实施方案
实施例4相对于纯PAN膜,加入气凝胶后的杂化膜纯水通量增大,但增大并不显著,可能是纳米级气凝胶部分填充了膜的孔洞,且拉伸强度略微下降;实例4相对于气凝胶粒子,吸附容量降低,可能由于成膜后有效吸附材料减少。综上所述,实施例4的综合性能较好。
尽管上面结合附图、附表对本发明进行了描述,但是本发明并不受上述方式的限制,只要采用了本发明的方法构思和技术方案进行的各种改进,均在本发明的保护范围内。
Claims (7)
1.一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于包括如下步骤:
1)气凝胶的制备:将基体原料与水混合,用酸将混合物体系pH调节至凝胶环境,使其凝胶化,形成水凝胶,通过冲洗,自然沥干,减少水凝胶中的盐分,然后用表面活性剂配制的水溶液清洗自然沥干,将水凝胶送入常压干燥炉,通过直接加热干燥得到气凝胶。
2)杂化膜的制备:将一定比例的气凝胶和高聚物粉末加到80~86wt%溶剂中,超声分散,得到分散均匀的溶液,水浴加热并机械搅拌反应6~15h,其中水浴温度为45~80℃,机械搅拌速率为100~400r/min,反应完成后真空脱泡,用自动涂膜机涂制平板膜,随后浸泡在去离子水中。
3)海水提铀试验:吸附实验使用不同初始浓度的铀溶液进行试验;pH由HNO3和NaOH调节;在脱附实验中,用1mol/L的HCl溶液进行解吸附;吸附和脱附过程均采用ICP等离子光谱仪测试溶液中铀浓度变化,吸附实验装置采用实验室常用水通量测试装置。
2.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤1)中所述的气凝胶为二氧化硅气凝胶、氧化铝气凝胶。
3.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤1)中所述的酸为醋酸、硅酸、盐酸中的其中一种。
4.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤1)中所述的表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、二辛基琥珀酸磺酸钠中的其中一种。
5.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤2)中所述的气凝胶在高聚物粉末中的占比为质量百分比20%至75%。
6.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤2)中所述的高聚物粉末为聚丙烯腈(PAN)、聚醚砜(PES)、聚偏氟乙烯(PVDF)中的其中一种。
7.根据权利要求1所述的一种含气凝胶的聚合物吸附膜及其制备方法,其特征在于:步骤2)中所述的溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)或N-甲基吡咯烷酮(NMP)中的其中一种。
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