CN109107395A - 防霾防有害气体空气滤膜、其制备方法及应用 - Google Patents

防霾防有害气体空气滤膜、其制备方法及应用 Download PDF

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Publication number
CN109107395A
CN109107395A CN201710492118.4A CN201710492118A CN109107395A CN 109107395 A CN109107395 A CN 109107395A CN 201710492118 A CN201710492118 A CN 201710492118A CN 109107395 A CN109107395 A CN 109107395A
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China
Prior art keywords
air filter
filter film
pernicious gas
haze
gas air
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CN201710492118.4A
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English (en)
Inventor
赵志刚
王振
丛杉
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Application filed by Suzhou Institute of Nano Tech and Nano Bionics of CAS filed Critical Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority to CN201710492118.4A priority Critical patent/CN109107395A/zh
Priority to PCT/CN2017/097363 priority patent/WO2019000602A1/zh
Priority to US16/482,540 priority patent/US11338249B2/en
Publication of CN109107395A publication Critical patent/CN109107395A/zh
Pending legal-status Critical Current

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Abstract

本发明公开了一种防霾防有害气体空气滤膜、其制备方法及应用。所述空气滤膜包括由纳米纤维制成的、具有二维或三维网络结构的纳米纤维膜。所述纳米纤维膜可以是利用静电纺丝工艺制成的高分子聚合物纳米纤维膜，且其中还可掺杂有能吸附吸收空气中的VOCs、NOx，SOx，NH3等有害气体并产生颜色响应的有机或无机添加剂和/或能通过光催化方式降解这些有害气体的光催化剂等。本发明的防霾防有害气体空气滤膜可以高效的滤除空气中的PM2.5、PM10等颗粒污染物，同时还可高效的识别、清除空气中的多种有害气体，在空气净化领域具有广泛应用前景，例如可以应用于纱窗、口罩、过滤网等空气净化设备。

Description

防霾防有害气体空气滤膜、其制备方法及应用
技术领域
本发明涉及一种空气净化装置，具体涉及一种防霾防有害气体空气滤膜、其制作方法及应用，所述防霾防有害气体空气滤膜的透光性透气率高，且能对有害气体进行颜色响应和降解。
背景技术
目前，由于人类活动带来的空气污染物大量排放，世界上很多城市的空气质量已经严重威胁着人们的身心健康。空气污染物中包括雾霾颗粒，挥发性有机化合物(VOCs)，氨气(NH3)，氮氧化合物(NOx)，硫氧化合物(SOx)。PM颗粒是由小的固体颗粒和液滴组成，传统分类有PM2.5颗粒和PM10颗粒，VOCs气体包括甲醛、乙醛等。这些空气污染物带来的危害已经引起了全世界的关注，过滤是应用最为广泛的净化空气的方法。例如CN201802288U公开了一种防尘纱窗用复合纱窗网，其中通过在复合纱窗中设计活性炭海绵层，可以实现对尘埃和有害气体的过滤吸附，但是它的透光性差，透气性差，且不能对有害气体进行检测和降解。
发明内容
本发明的目的在于提供一种防霾防有害气体空气滤膜、其制备方法及应用，以克服现有技术中的不足。
为实现前述发明目的，本发明采用的技术方案包括：
本发明实施例提供了一种防霾防有害气体空气滤膜，其包括由直径为200～2000nm的纳米纤维制成的、具有二维或三维网络结构的纳米纤维膜，所述纳米纤维膜至少用以滤除空气中粒径不小于设定阈值的颗粒物。
进一步的，所述粒径不小于设定阈值的颗粒物为粒径大于或等于PM10的颗粒物，优选为粒径大于或等于PM2.5的颗粒物。
优选的，当所述空气滤膜的透过率低于90％时，所述空气滤膜对PM2.5颗粒的阻隔效率高于95％。
进一步的，所述纳米纤维的表面是光滑的或具有褶皱结构。或者，更为优选的，所述纳米纤维具有多孔结构，例如表面具有多孔结构或整体具有贯通的三维多孔结构。
进一步的，所述纳米纤维采用高分子聚合物纳米纤维。
在一些优选实施方案中，所述纳米纤维还包含至少用以吸收和/或降解空气中的选定化学物质的有机或无机添加剂。所述选定化学物质可以是挥发性有机化合物(VOCs)，氨气(NH3)，氮氧化合物(NOx)，硫氧化合物(SOx)等或其组合。
进一步优选的，所述有机或无机添加剂选自至少用以吸收空气中的选定化学物质并产生颜色响应的有机或无机添加剂。
进一步优选的，所述有机或无机添加剂选自光催化剂。
进一步的，所述纳米纤维膜可以由静电纺丝工艺制成。
进一步的，所述空气滤膜的透过率为0～95％，优选为0～30％或30％～95％。
本发明实施例还提供了一种制备所述防霾防有害气体空气滤膜的方法，其包括：
提供包含或未包含所述有机或无机添加剂的聚合物溶液，以及
对所述聚合物溶液进行静电方式，制得自支撑的所述纳米纤维膜或与多孔基底结合的所述纳米纤维膜。
本发明实施例还提供了所述防霾防有害气体空气滤膜于空气净化领域的应用。
与现有技术相比，本发明提供的防霾防有害气体空气滤膜可以高效的滤除空气中的PM2.5、PM10等颗粒污染物，同时还可高效的识别、清除空气中的多种有害气体，在空气净化领域具有广泛应用前景。
附图说明
图1是本发明一典型实施方案中一种基于多孔纤维的纳米纤维膜的结构示意图。
图2是本发明实施例1中一种PAN纳米纤维的扫描电镜图。
图3是本发明实施例1中一种PAN纳米纤维膜对于PM2.5、PM10颗粒的移除效率测试图。
图4是本发明实施例2中一种褶皱PAN纳米纤维的扫描电镜图。
图5是本发明实施例3中一种多孔PAN纳米纤维的扫描电镜图。
图6a-图6f是本发明实施例4中多个具有不同透光率的空气滤膜的光学照片。
图7是本发明实施例4中一种空气滤膜在吸附氨气前后的颜色变化图。
具体实施方式
鉴于现有技术中的不足，本案发明人经相关研究和大量实践，得以提出本发明的技术方案，如下将予以详细说明。
本发明实施例的一个方面提供的一种防霾防有害气体空气滤膜包括由直径为200～2000nm的纳米纤维制成的、具有二维或三维网络结构的纳米纤维膜，所述纳米纤维膜至少用以滤除空气中粒径不小于设定阈值的颗粒物。
进一步的，所述粒径不小于设定阈值的颗粒物为粒径大于或等于PM10的颗粒物。
更进一步的，所述粒径不小于设定阈值的颗粒物为粒径大于或等于PM2.5的颗粒物。
进一步的，所述空气滤膜的透过率为0～95％，优选为0～30％或30％～95％，尤其优选在70％～80％以上。
进一步的，当所述空气滤膜的透过率低于90％时，所述空气滤膜对PM2.5颗粒的阻隔效率高于95％。
更为具体的，在所述空气滤膜的透过率为80％，通过风速为4cm/s时，其对于粒径约PM10的颗粒阻隔效率高于99％，而对于粒径约PM2.5的颗粒的阻隔效率也高于99％。
进一步的，所述空气滤膜可以是不透明、半透明或完全透明的。
进一步的，所述空气滤膜可以是不同厚度的，例如其厚度可以为5～5000μm，优选为100～5000μm，也可以优选为5～100μm，尤其优选为15～30μm。
在一些实施方案中，所述纳米纤维的表面是光滑的。
在一些较佳实施方案中，所述纳米纤维的表面具有褶皱结构，即为褶皱纳米纤维，优选的，其中皱褶结构相对于纳米纤维本体的起伏度为0～30％。
在一些更优选的实施方案中，所述纳米纤维具有多孔结构，即为多孔纳米纤维，优选的，所述纳米纤维的表面孔隙覆盖率为0～60％。
当采用前述的皱褶纳米纤维、多孔纳米纤维或者具有相似形貌的纳米纤维(尤其是多孔纳米纤维)时，将有助于高效促进形成的纳米纤维膜吸附捕获空气中的有害气体，比如挥发性有机化合物(VOCs)，NOx，SOx，NH3，等等。
本发明的一典型实施方案中一种基于前述多孔纳米纤维的纳米纤维膜的结构可以如图1所示。
进一步的，所述纳米纤维可采用高分子聚合物纳米纤维。优选的，所述纳米纤维的材质可以包括聚乙烯醇缩丁醛(PVB)，或者聚丙烯晴(PAN)，或者聚乙烯吡咯烷酮(PVP)，或者聚氧化乙烯(PEO)，或者聚甲基丙烯酸甲酯(PMMA)，或者聚酰胺(PA)，等等。在一些优选实施方案中，所述纳米纤维还可包含至少用以吸收和/或降解空气中的选定化学物质的有机或无机添加剂。其中，所述选定化学物质包括挥发性有机化合物(VOCs)、氮氧化合物(NOx)、硫氧化合物(SOx)、氨气(NH3)中的一种或多种，且不限于此。进一步的，所述有机或无机添加剂可以选自至少用以吸收空气中的选定化学物质并产生颜色响应的有机或无机添加剂。优选的，所述有机或无机添加剂于纳米纤维膜中的添加量足以使纳米纤维膜在吸收选定化学物质时产生的颜色响应肉眼可辨识。
在一些更为具体的实施方案中，所述选定化学物质为挥发性有机化合物，而相应的有机或无机添加剂为VOC显色试剂，例如所述VOC显色试剂可以包括沸石粉或对氨基苯硫酚等。如此，当这些显色试剂吸附VOCs后，其可以对VOCs产生颜色响应，使得空气滤膜的颜色相应发生改变，不仅可以去除空气中的此类有害物质，而且可以向用户发出直观的警示，令其了解空气中有害物质的种类等。
在一些更为具体的实施方案中，所述选定化学物质为氨气，而相应的有机或无机添加剂为氨气显色试剂；优选的，所述氨气显色试剂包括普鲁士蓝，当其吸附氨气后，使得空气滤膜的颜色发生改变。
在一些更为具体的实施方案中，所述选定化学物质为氮氧化合物，而相应的有机或无机添加剂为氮氧化合物显色试剂；优选的，所述氮氧化合物显色试剂包括氨基苯磺酰胺或二氨基荧光素，当其吸附氮氧化合物后，空气滤膜的颜色发生改变。
在一些更为具体的实施方案中，所述选定化学物质为硫氧化合物，而相应的有机或无机添加剂为硫氧化合物显色试剂；优选的，所述硫氧化合物显色试剂包括石蕊，当其吸附硫氧化合物后，使得空气滤膜的颜色发生改变。
进一步的，所述有机或无机添加剂也可以选自光催化剂，例如TiO2、ZnO、W18O49或WO3等等，使得所述空气滤膜在滤除空气中颗粒污染物的同时，还可进一步降解其中的有害气体，如VOCs气体(如甲醛、乙醛)，等等。
当然，在一些实施方案中，所述纳米纤维可以同时包含前述的各类显色试剂和光催化剂等，以达成联合清除空气中有害气体的效果。
进一步的，所述的纳米纤维膜可以是自支撑的且不依附于基底，或者也可以是与基底结合的。这些基底优选采用多孔基底，例如可以选用不锈钢丝网、玻璃纤维网、尼龙网、铝合金丝网等等。优选的，这些基底所含孔洞的孔径为200～20目。
在一些实施方案中，所述纳米纤维膜可以由静电纺丝工艺制成。
本发明实施例的另一个方面提供的一种制备所述防霾防有害气体空气滤膜的方法，其包括：
提供包含或未包含所述有机或无机添加剂的聚合物溶液，以及
对所述聚合物溶液进行静电方式，制得自支撑的所述纳米纤维膜或与多孔基底结合的所述纳米纤维膜。
进一步的，所述聚合物溶液可以是按照业界已知的任何方式，通过将高分子聚合物溶于溶剂中形成。优选的，还可在聚合物溶液中均匀分散或溶入前述的一种或多种有机或无机添加剂。
进一步的，前述静电纺丝工艺可以依照业界已知的方式，利用各类合适的静电纺丝设备实现。
总之，本发明的防霾防有害气体空气滤膜是基于纳米纤维膜而形成，其不仅对于空气中的PM2.5、PM10等颗粒污染物有很高的阻隔效率，而且还能通过颜色响应等方式识别空气中的挥发性有机化合物(VOC)，NOx，SOx，NH3等有害气体，并结合吸附、光催化降解等方式高效清除此类有害气体。
本发明实施例的另一个方面还提供了所述防霾防有害气体空气滤膜于空气净化领域的应用。例如，可以应用所述空气滤膜制备空气净化产品，如纱窗、口罩或过滤网等，但不限于此。
以下通过若干实施例并结合附图进一步详细说明本发明的技术方案。然而，所选的实施例仅用于说明本发明，而不限制本发明的范围。
实施例1：本实施例涉及的一种防霾防有害气体空气滤膜包含聚丙烯晴(PAN)纳米纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为8wt％的PAN溶液，PAN的重均分子量为150000，溶剂为二甲基甲酰胺，电压25kV，基底用不锈钢丝网承接。请参阅图2是组成该纳米纤维膜的PAN纳米纤维的SEM图。该空气滤膜可以高效阻碍PM2.5，PM10颗粒的通过。图3是本实施例中不同透过率的纳米纤维空气滤膜在微风下对PM2.5和PM10颗粒的阻隔效率结果图。
实施例2：本实施例涉及的一种防霾防有害气体空气滤膜包含PAN纳米皱褶纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺丝溶液为9wt％PVP/PAN质量比为1/2的混合溶液，溶剂为二甲基甲酰胺，PVP的重均分子量为58000，PAN的重均分子量为150000，电压25kV，基底用不锈钢丝网承接，静电纺丝得到的膜随后在水中蘸洗后取出。请参阅图4是组成该纳米纤维膜的皱褶PAN纳米纤维的SEM图。该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率优于实施例1)，并有较强的有害气体捕获能力，详见下表1。
实施例3：本实施例涉及的一种防霾防有害气体空气滤膜包含PVB多孔纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为6wt％的PVB溶液，PVB的重均分子量为90000-120000，溶剂为THF和DMSO的混合溶剂(体积比例为95/5)，电压25kV。请参阅图5是组成该纳米纤维膜的PVB多孔纤维的SEM图片。该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率优于实施例1)，并有很强的有害气体捕获能力，详见下表2。
实施例4：本实施例涉及的一种防霾防有害气体空气滤膜包含PVB/PB多孔纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为6wt％的PVB溶液(添加有2wt％的PB染料)，溶剂为THF和DMSO的混合溶剂，体积比例为95/5，电压25kV。该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率优于实施例1)，并吸附氨气等有害气体(捕获效率与实施例3相近)，且吸附氨气后颜色发生变化。请参阅图6a-图6e分别示出了本实施例制得的一系列不同透光率的空气滤膜的照片。图7示出了其中一种空气滤膜在吸附氨气前后的颜色改变情况(蓝色→白色)。
实施例5：本实施例涉及的一种防霾防有害气体空气滤膜包含聚氧化乙烯(PEO)纳米纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为10wt％的PEO溶液，PEO的重均分子量为10000，溶剂为水，电压30kV，基底用不锈钢丝网承接，该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率与实施例1相近)。
实施例6：本实施例涉及的一种防霾防有害气体空气滤膜包含聚甲基丙基酸甲酯(PMMA)纳米纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为20wt％的PEO溶液，PMMA的重均分子量为500000，溶剂为乙酸乙酯，电压30kV，基底用不锈钢丝网承接，该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率与实施例1相近)。
实施例7：本实施例涉及的一种防霾防有害气体空气滤膜包含PAN/W18O49纳米纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为8wt％的PAN和1wt％的W18O49纳米线溶液，PAN的重均分子量为150000，溶剂为二甲基甲酰胺，电压25kV，基底用不锈钢丝网承接。该空气滤膜可以高效阻碍PM2.5，PM10颗粒的通过(阻隔效率优于实施例1)，并能够吸附空气中的VOCs气体，且在光照下进行降解。表3是本实施例的一种空气滤膜在光照下对乙醛降解的测试结果。
实施例8：本实施例涉及的一种防霾防有害气体空气滤膜包含PVB/ATP多孔纤维膜，其是利用静电纺丝工艺制成，相应的静电纺丝工艺参数如下：纺织溶液为6wt％的PVB溶液(添加有1wt％的对氨基苯硫酚ATP)，溶剂为THF和DMSO的混合溶剂，体积比例为95/5，电压25kV。该空气滤膜可以高效阻碍PM2.5，PM10的通过(阻隔效率优于实施例1)，并有很强的有害气体捕获能力(与实施例3、4接近)。
表1
材料 乙醛吸附量
PAN光滑纤维 2.73mg/g
PAN褶皱纤维 5.56mg/g
表2
材料 乙醛吸附量
PVB光滑纤维 2.32mg/g
PVB褶皱纤维 4.36mg/g
PVB多孔纤维 7.17mg/g
表3
光照时间 乙醛减少量
0 8.12mg/g
3h 11.43mg/g
6h 14.54mg/g
12h 19.21mg/g
以上所述实施例仅用于帮助理解本发明的方法的核心思想，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围内。对这些实施例的多种修改对本领域的专业人员来说显而易见，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其他实施例中实现。因此，本发明专利的保护范围应以所附权利要求为准，不会限制于本文中所示的这些实例，而是要符合与本文所公开的原理和特点相一致的范围。

Claims (15)

1.一种防霾防有害气体空气滤膜，其特征在于包括由直径为200～4000nm的纳米纤维制成的、具有二维或三维网络结构的纳米纤维膜，所述纳米纤维膜至少用以滤除空气中粒径不小于设定阈值的颗粒物。
2.根据权利要求1所述的防霾防有害气体空气滤膜，其特征在于：所述空气滤膜的透过率为0～95％，优选为0～30％或30％～95％；优选的，当所述空气滤膜的透过率低于90％时，所述空气滤膜对PM2.5颗粒的阻隔效率高于95％。
3.根据权利要求1所述的防霾防有害气体空气滤膜，其特征在于：所述粒径不小于设定阈值的颗粒物为粒径大于或等于PM10的颗粒物，优选的，所述粒径不小于设定阈值的颗粒物为粒径大于或等于PM2.5的颗粒物。
4.根据权利要求1所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维的表面是光滑的。
5.根据权利要求1所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维的表面具有褶皱结构；优选的，所述皱褶结构相对于纳米纤维本体的起伏度为0～30％。
6.根据权利要求1所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维具有多孔结构；优选的，所述纳米纤维表面的孔隙覆盖率为0～60％。
7.根据权利要求1-6中任一项所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维采用高分子聚合物纳米纤维；优选的，所述纳米纤维的材质包括聚乙烯醇缩丁醛、聚丙烯晴、聚乙烯吡咯烷酮、聚氧化乙烯、聚甲基丙烯酸甲酯或者聚酰胺。
8.根据权利要求7所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维还包含至少用以吸收和/或降解空气中的选定化学物质的有机或无机添加剂；
优选的，所述选定化学物质包括挥发性有机化合物、氮氧化合物、硫氧化合物、氨气中的任意一种或两种以上的组合。
9.根据权利要求8所述的防霾防有害气体空气滤膜，其特征在于：所述有机或无机添加剂选自至少用以吸收空气中的选定化学物质并产生颜色响应的有机或无机添加剂；
优选的，所述有机或无机添加剂于纳米纤维膜中的添加量足以使纳米纤维膜在吸收选定化学物质时产生的颜色响应肉眼可辨识；
优选的，所述选定化学物质为挥发性有机化合物，而相应的有机或无机添加剂为VOC显色试剂；优选的，所述VOC显色试剂包括沸石粉或对氨基苯硫酚；
优选的，所述选定化学物质为氨气，而相应的有机或无机添加剂为氨气显色试剂；优选的，所述氨气显色试剂包括普鲁士蓝；
优选的，所述选定化学物质为氮氧化合物，而相应的有机或无机添加剂为氮氧化合物显色试剂；优选的，所述氮氧化合物显色试剂包括氨基苯磺酰胺或二氨基荧光素；
优选的，所述选定化学物质为硫氧化合物，而相应的有机或无机添加剂为硫氧化合物显色试剂；优选的，所述硫氧化合物显色试剂包括石蕊。
10.根据权利要求8所述的防霾防有害气体空气滤膜，其特征在于：所述有机或无机添加剂选自光催化剂；优选的，所述光催化剂包括TiO2、ZnO、W18O49或WO3。
11.根据权利要求1-6、8-10中任一项所述的防霾防有害气体空气滤膜，其特征在于还包括与所述纳米纤维膜结合的多孔基底；优选的，所述多孔基底所含孔洞的孔径为200～20目；优选的，所述多孔基底包括不锈钢丝网、玻璃纤维网、尼龙网、铝合金丝网中的任意一种或两种以上的组合。
12.根据权利要求1-6、8-10中任一项所述的防霾防有害气体空气滤膜，其特征在于：所述纳米纤维膜由静电纺丝工艺制成。
13.如权利要求1-12中任一项所述防霾防有害气体空气滤膜的制备方法，其特征在于包括：提供包含或未包含所述有机或无机添加剂的聚合物溶液，以及
对所述聚合物溶液进行静电方式，制得自支撑的所述纳米纤维膜或与多孔基底结合的所述纳米纤维膜。
14.权利要求1-12中任一项所述防霾防有害气体空气滤膜于空气净化领域的应用。
15.根据权利要求14的应用，其特征在于包括：应用所述空气滤膜制备空气净化产品，所述空气净化产品包括纱窗、口罩或过滤网。
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