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CN106178696A - 用于大气中多形态汞采集的纳米纤维材料及制备方法 - Google Patents

用于大气中多形态汞采集的纳米纤维材料及制备方法 Download PDF

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CN106178696A
CN106178696A CN201610523782.6A CN201610523782A CN106178696A CN 106178696 A CN106178696 A CN 106178696A CN 201610523782 A CN201610523782 A CN 201610523782A CN 106178696 A CN106178696 A CN 106178696A
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康学军
柳雄威
黄晶晶
卫兰兰
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Southeast University
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Abstract

本发明是一种用于大气中多形态汞采集的纳米纤维材料及制备方法，该纳米纤维材料为一步成型的表面负载巯基的多功能高分子纳米纤维。制备方法为：将高分子聚合物溶解在溶剂中，搅拌配成纺丝液；再用溶剂溶解含巯基的试剂制成溶液后添加入所述的纺丝液；选取4‑甲氧基‑2,6‑叔丁基苯酚BHA、4‑甲基‑2,6‑二叔丁基苯酚BHT、叔丁基氢醌TBHQ和没食子酸丙酯PG、亚硫酸盐中的一种加入纺丝液中起到抗氧化稳定作用；加入醋酸盐、柠檬酸盐、碳酸盐、氢氧化物或铵盐调节介质酸碱度；利用静电纺丝技术，以透气性薄膜材料为衬底材料接收纳米纤维，裁剪后制滤膜；再以致密不透气薄膜材料为衬底材料接收纳米纤维，用纳米纤维连同衬底制层叠式柱。

Description

用于大气中多形态汞采集的纳米纤维材料及制备方法
技术领域
本发明属于大气环境监测技术领域，是一种对大气中痕量多形态汞进行采样捕集的纳米纤维材料制备和使用方法。
背景技术
汞是一种具有生物富集性的高毒性重金属，它存在于空气、水和土壤中。汞有多种存在形式,包括元素汞、无机汞和有机汞。汞及其化合物是重要的环境污染物,煤燃烧是大气汞污染的一个主要来源,对其研究己成为当今环境研究的前沿问题。汞也是唯一主要以气态形式存在于大气的重金属污染物。大气环境是汞迁移转化的重要场所，大气环境中的汞依据物理化学形态主要分为：气态单质示(Hg0,Gaseous Elemental Mercury,GEM)、活性气态汞(Hg2+,Reactive Gaseous Mercury,RGM)和颗粒态汞(pHg,Particle Mercury，吸附于大气颗粒物中)三种。
目前，对大气中的气态单质汞主要采用镀金石英砂进行吸附，而颗粒态汞则用石英纤维滤膜进行捕集，活性气态汞一般用扩散管法吸收。在实际应用中，难以将三者统一结合，且吸附效率难以提高。
发明内容
技术问题：本发明的目的是提供一种用于大气中多形态汞采集的纳米纤维材料及制备方法，静电纺丝的方法其高分子材料和修饰试剂可以任意选配，因此可以容易的制备含有各种功能特性(如吸附汞作用、巯基稳定和保护作用等)的新材料。制成的材料由于其独特的表面特性，其捕集汞的效率比现有材料显著提高。
技术方案：本发明提出了用新型的功能纳米纤维膜为滤料采集空气中多形态汞。采用巯基修饰电纺纳米纤维的方法制备捕集汞的功能性新材料。根据“软-硬酸碱理论”,巯基能够与具有强极化性的软重金属(Hg,Ag,Au)形成稳定的配合物,与Cd和Zn的作用较弱,而与Ca、Na、Mg等轻金属不发生作用，巯基材料是一种公认的吸附容量大、选择性高、吸附效果好的汞吸附材料。巯基棉就是一种用巯基功能基团修饰棉花制成的可捕集汞的纤维型材料，但是其制备方法需要多种试剂(包括强酸等腐蚀性试剂)在一定条件下较长时间(数天)反应制备。本发明采取静电纺丝的办法一步就可以制备巯基功能基团修饰的纳米纤维型汞捕集材料，制备过程不用强腐蚀性试剂。
本发明的一种用于大气中多形态汞采集的纳米纤维材料为一步成型的表面负载巯基的多功能高分子纳米纤维。
本发明的用于大气中多形态汞采集的纳米纤维材料的制备方法为：将高分子聚合物溶解在溶剂中，搅拌配成纺丝液；再用溶剂溶解含巯基的试剂制成溶液后添加入所述的纺丝液；选取4-甲氧基-2,6-叔丁基苯酚(BHA)、4-甲基-2,6-二叔丁基苯酚(BHT)、叔丁基氢醌(TBHQ)和没食子酸丙酯(PG)、亚硫酸盐中的一种加入纺丝液中起到抗氧化稳定作用；加入醋酸盐、柠檬酸盐、碳酸盐、氢氧化物或铵盐调节介质酸碱度；利用静电纺丝技术，以透气性薄膜材料为衬底材料接收纳米纤维，裁剪后制滤膜；再以致密不透气薄膜材料为衬底材料接收纳米纤维，用纳米纤维连同衬底制层叠式柱。
所述的高分子聚合物为聚苯硫醚、醋酸素、聚苯乙烯、聚已内酰胺、丙烯酸树脂或聚丙烯腈的一种或数种混合。
所述的溶剂为N，N-二甲基甲酰胺、四氢呋喃、乙醇、丙或甲酸。
所述的含巯基的试剂为巯基乙酸及其酯类、巯基聚乙二醇、巯基乙胺盐、巯基乙醇或半胱氨酸及其衍生物的一种或数种混合。
工作原理
疏基化合物于微酸性介质中对汞具有配位能力,可将有机汞与无机汞分别进行吸附及解吸,可用于大气中汞的收集。其作用方程如下:
由于纳米纤维的比表面较大,其捕集汞容量相应地也较大；还由于纳米纤维中有很多孔隙,巯基分子负载于纳米纤维的表面,由于毛细作用，容易与汞作用,产生汞的疏基配位化合物。其收集效应可避免金、银等汞齐法这类收集剂的屏蔽效应与钝化现象，因此捕集汞效果好。此外，与传统的纤维过滤材料相比，静电纺丝无纺纤维膜的组成纤维具有更小的直径(通常小于500mn)，因此在相同压降下，气体在直径较小的纤维周围流动时的扩散、拦截和惯性碰撞频率増加，较细的纳米纤维所形成的无纺纤维膜对细小颗粒物的捕获能力更强，因此可以高效捕获空气颗粒物，特别是细颗粒。而金属元素被细颗粒吸附更多，因此纳米纤维材料对空气颗粒物中金属汞捕集效率也显著提高。
有益效果：
1)混合各种试剂配成溶液，一步法即可制备出高效捕集目标物的材料，制成材料可兼顾稳定、保持功能基团活性，维持吸附作用所需介质环境条件等功能；
2)制成的纳米纤维的比表面积较大，有较多的与目标物相互作用位点，使得新材料对目标物捕集效率大大提高；
3)纳米纤维材料的高孔隙率和表面效应使其兼具气态物质吸附和颗粒物拦截、捕集作用，进而适合于气态、颗粒物汞等多种形态汞的捕集。
附图说明
图1几种滤膜材料采集空气中汞效率比较。
图2两种膜实物图和采集空气中汞效率比较。
具体实施方式
将高分子聚合物(如聚苯硫醚、醋酸素、聚苯乙烯、聚已内酰胺、丙烯酸树脂、聚丙烯腈等一种或数种混合)溶解在一定比例的溶剂(如N，N-二甲基甲酰胺、四氢呋喃、乙醇、丙酮、甲酸等)中，搅拌配成纺丝液。选取适当的溶剂(如N，N-二甲基甲酰胺、四氢呋喃、乙醇、丙酮、甲酸等)溶解适量含巯基的试剂(如巯基乙酸及其酯类、巯基聚乙二醇、巯基乙胺盐、巯基乙醇、半胱氨酸及其衍生物等一种或数种混合)制成溶液后添加入纺丝液。选取4-甲氧基-2,6-叔丁基苯酚(BHA)、4-甲基-2,6-二叔丁基苯酚(BHT)、叔丁基氢醌(TBHQ)和没食子酸丙酯(PG)、亚硫酸盐中的一种或数种适量加入纺丝液中起到抗氧化稳定作用。适量加入醋酸盐、柠檬酸盐、碳酸盐、氢氧化物、铵盐、调节介质酸碱度。利用静电纺丝技术，以适当的面料为接收(透气性衬底接收纳米纤维后制滤膜，致密不透气衬底接收纳米纤维后制柱)，在衬底表面纺制巯基功能性纳米纤维，一步即可成型，连同衬底裁剪后制作成滤膜，或者参照专利号为201410143082.5的方法制成层叠式柱子。将纳米纤维膜安装在尺寸适合的采样夹上，或者将层叠式柱子连接合适的管路系统，可用于环境空气中汞的高效采样。本发明特点是，纳米纤维膜的材质用量比一般的吸附材料少，体积较小，操作方便简单。并且该技术集多形态目标物采集、浓缩于一体，可达到微量、痕量汞的富集浓缩。
大气中金属汞的采集与测定
(1)与商品化石英滤膜比较
把各种材料的膜(巯基功能纳米纤维滤膜以半胱氨酸修饰的聚苯乙烯膜为例)的采样夹安装在采样器上，在采样点平行操作，以5L/min的流量采集空气。
将采样过的滤膜放入聚四氟乙烯烧杯中以硝酸-过氧化氢消解后，并加入1+9的硝酸5ml浸提，转移至容量瓶内，以超纯水定容，摇匀，放置30min后用原子荧光法测定。用同样的方法处理空白对照滤膜，制备空白对照溶液以扣除背景值，测定结果见图1。
巯基修饰后的纳米纤维膜比其它材料膜表现出较高的汞吸附捕集性能，且其随着采集时间的增长，纤维膜的对汞的富集量逐渐增大，而其它两种膜随时间延长，汞富集量增长不明显。
(2)与巯基棉比较
巯基棉因其较高的吸附性能和较为简便的操作被认为是良好的汞吸附材料，但是巯基棉不易于制备和保存，且制备过程较为繁琐，但是目前其仍然作为一种常用的空气中汞的吸附剂。本发明以其为对照，将本发明的材料与之相比较。巯基棉按照行业标准方法制备，将其均匀平铺于和纳米纤维滤膜相同的衬底材料上制成滤膜。把装有各种材料膜(巯基功能纳米纤维滤膜以半胱氨酸修饰膜为例)的采样夹安装在采样器上，在采样点平行操作，以5L/min的流量采集空气。
采样过的巯基棉滤膜按照标准方法，用2mol/L盐酸解吸，定容后用原子荧光法测定。而纳米纤维滤膜则放入聚四氟乙烯烧杯中以硝酸-过氧化氢消解后，并加入1+9的硝酸5ml浸提，转移至容量瓶内，以超纯水定容，摇匀，放置30min后用原子荧光法测定。用同样的方法处理空白对照滤膜，制备空白对照溶液以扣除背景值，测定结果见图2。可以看出，单位质量相比，纳米纤维膜对空气中汞的捕集率显著高于巯基棉数倍。

Claims (5)

1.一种用于大气中多形态汞采集的纳米纤维材料，其特征在于该纳米纤维材料为一步成型的表面负载巯基的多功能高分子纳米纤维。
2.一种如权利要求1所述的用于大气中多形态汞采集的纳米纤维材料的制备方法，其特征在于：将高分子聚合物溶解在溶剂中，搅拌配成纺丝液；再用溶剂溶解含巯基的试剂制成溶液后添加入所述的纺丝液；选取4-甲氧基-2,6-叔丁基苯酚BHA、4-甲基-2,6-二叔丁基苯酚BHT、叔丁基氢醌TBHQ和没食子酸丙酯PG、亚硫酸盐中的一种加入纺丝液中起到抗氧化稳定作用；加入醋酸盐、柠檬酸盐、碳酸盐、氢氧化物或铵盐调节介质酸碱度；利用静电纺丝技术，以透气性薄膜材料为衬底材料接收纳米纤维，裁剪后制滤膜；再以致密不透气薄膜材料为衬底材料接收纳米纤维，用纳米纤维连同衬底制层叠式柱。
3.如权利要求2所述的用于大气中多形态汞采集的纳米纤维材料的制备方法，其特征在于：所述的高分子聚合物为聚苯硫醚、醋酸素、聚苯乙烯、聚已内酰胺、丙烯酸树脂或聚丙烯腈的一种或数种混合。
4.如权利要求2所述的用于大气中多形态汞采集的纳米纤维材料的制备方法，其特征在于：所述的溶剂为N，N-二甲基甲酰胺、四氢呋喃、乙醇、丙或甲酸。
5.如权利要求2所述的用于大气中多形态汞采集的纳米纤维材料的制备方法，其特征在于：所述的含巯基的试剂为巯基乙酸及其酯类、巯基聚乙二醇、巯基乙胺盐、巯基乙醇或半胱氨酸及其衍生物的一种或数种混合。
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