CN112726195A - 一种荷正电微纳米纤维改性膜及其制备方法和应用 - Google Patents
一种荷正电微纳米纤维改性膜及其制备方法和应用 Download PDFInfo
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- CN112726195A CN112726195A CN202011548097.1A CN202011548097A CN112726195A CN 112726195 A CN112726195 A CN 112726195A CN 202011548097 A CN202011548097 A CN 202011548097A CN 112726195 A CN112726195 A CN 112726195A
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- modified membrane
- positively charged
- metal oxide
- membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000002121 nanofiber Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 24
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- 230000008569 process Effects 0.000 claims abstract description 17
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
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- 238000001035 drying Methods 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001523 electrospinning Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
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- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ZPRWYEFEBXYEEJ-UHFFFAOYSA-K aluminum formaldehyde triacetate Chemical compound C(C)(=O)[O-].[Al+3].C=O.C(C)(=O)[O-].C(C)(=O)[O-] ZPRWYEFEBXYEEJ-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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Abstract
本发明提供了一种荷正电微纳米纤维改性膜及其制备方法和应用，所述制备方法包括：将金属氧化物与高聚物混合配制成纺丝液，纺丝液通过静电纺丝过程制备出纤维改性膜后，将金属氧化物溶胶涂覆在纤维改性膜表面，得到所述荷正电微纳米纤维改性膜；本发明提供的荷正电微纳米纤维改性膜的制备方法，无需添加其它任何助剂和粘附剂，相比于现有的荷电纤维，操作过程简单方便，制备得到的荷正电微纳米纤维改性膜，比表面积大，通过掺杂金属氧化物与静电纺丝技术结合，提升了吸附能力，控制通量在合理的范围，跨膜压差低，相比于现有的荷电纤维膜，具有更好的性能，可以广泛应用于水处理中。
Description
技术领域
本发明属于膜分离领域，涉及一种荷正电微纳米纤维改性膜及其制备方法和应用。
背景技术
目前市场上水处理领域，污染物的去除技术主要是采用纯粹的物理孔径拦截，如微滤膜、超滤膜、反渗透膜等膜的拦截。这些产品为了达到良好的去除性能，不可避免的存在通量低、压阻高等相应的缺陷。而荷电膜是一种携带正电荷的过滤材料，以孔径截留为基础，附加静电吸附功能，不仅可以去除水中的大分子杂质，还可以去除水中的细菌、病毒、胶体以及部分重金属和有机物等污染物，是一种多功能的滤材。与此同时，荷电膜水通量大，跨膜压降小，可应用于工业反渗透水处理前置，家用水壶滤芯，复合超滤滤芯等方面。
金属氧化物纳米颗粒具有比表面积大，表面活性中心多，催化效率高，电学性质好等优点，广泛应用在催化剂、光电器件、气体传感器、功能复合材料等各个领域。
CN111701466A公开了一种复合材料，采用荷负电纤维，特种带电粘结材料，粘结剂以及多尺度微纳米荷正电金属氧化物相结合的方式，制备了一种带正电的复合材料，能够通过电荷吸附去除水中带负电的污染物且去除效率高。
CN111701339A同样公开了一种复合材料，同样采用荷正电复合材料、多孔荷正电金属氧化物颗粒或纤维、低熔点纤维、吸附材料以及功能性添加剂等相互结合，制备了多尺度荷正电复合滤材。其中荷负电纤维的质量百分比为20wt％～80wt％，特种带电粘结材料的质量百分比为1wt％～10wt％，粘结剂的质量百分比为0.1wt％～2wt％，多尺度微纳米荷正电金属氧化物的质量百分比为20wt％～70wt％。
CN102078771B公开了一种纳米纤维膜，其制备采用以下步骤：①、制备网状陶瓷纤维骨架，②、在步骤①的骨架表面上采用水热法合成棒状或片状纳米颗粒，③、在步骤②的纳米颗粒上采用软模板沉淀法得到针状纳米纤维。
但是目前的方法仍然存在一些缺陷，制备过程复杂，步骤多，需要添加其它助剂、粘附剂等物质。
静电纺丝技术是一种能够直接、连续制备聚合物纳米纤维的方法。当纤维直径从微米缩小至亚微米或纳米时，聚合物纤维与相应的材料相比，会表现出多种惊人的特性。静电纺丝纤维和传统的粗纤维相比，直径小了2-3个数量级，具有超高的比表面积和孔隙率，这赋予了静电纺纤维很多优良的性能。利用静电纺丝纳米纤维制备的水处理膜，具有通量大，吸附性能强的优势。
因此，结合静电纺丝技术，如何开发一种性能更好的荷正电纤维改性膜，对于提升膜的性能具有重要的意义。
发明内容
针对现有技术的不足，本发明的目的在于提供一种荷正电微纳米纤维改性膜及其制备方法和应用，以解决现有的膜需要额外助剂、吸附能力差、压差高的问题，达到提升膜性能的效果。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供了一种荷正电微纳米纤维改性膜的制备方法，所述制备方法包括：将金属氧化物与高聚物混合配制成纺丝液，纺丝液通过静电纺丝过程制备出纤维改性膜后，将金属氧化物溶胶涂覆在纤维改性膜表面，得到所述荷正电微纳米纤维改性膜。
本发明提供的荷正电微纳米纤维改性膜的制备方法，通过静电纺丝技术，将荷正电的微纳米级的金属氧化物颗粒，添加负载到纤维改性膜之间的过程，仅需配制相应的纺丝液，相比于现有的荷电纤维，无需添加其它任何助剂和粘附剂，操作过程简单方便。
优选地，所述金属氧化物包括五氧化二钒、氧化钼、二氧化锰、二氧化钛、氧化铝、勃姆石、氧化锌、氧化铁或氧化铜中的一种或至少两种的组合。本发明金属氧化物包括但不限于上述所列的金属氧化物，还可以是其他可以荷正电的金属氧化物。优选为勃姆石。
在本发明中金属氧化物这种微纳米颗粒，具有比表面积大、表面活性中心多、电学性质好等优点，用于静电纺丝形成的膜中，可有效吸附水体中微小颗粒及胶体。
在本发明中，金属氧化物溶胶指的是金属氧化物在特定分散液中分散形成的均一稳定的胶体。此金属氧化物溶胶中的金属氧化物与纺丝液中的金属氧化物为同一种物质。其中分散液可以是本领域常规的溶剂等。
优选地，所述高聚物包括聚偏氟乙烯、聚丙烯腈、二醋酸纤维素、聚甲基丙烯酸甲酯、聚醚砜、聚苯乙烯、聚氯乙烯、聚丙烯或芳砜纶中的一种或至少两种的组合。
优选地，所述纺丝液的溶剂包括二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、丙酮或氯仿中的任意一种或至少两种的组合。
优选地，所述静电纺丝过程包括接收底布。
优选地，所述接收底布为聚二甲基丙烯酸甲酯(PET)。
优选地，所述纺丝液的浓度为10％-30％，例如可以是10％、15％、20％、25％或30％等。纺丝液的浓度指的是纺丝液中高聚物所占的质量百分含量。
优选地，所述纺丝液中金属氧化物的浓度为0.1％-5％，例如可以是0.1％、0.5％、1％、1.3％、1.5％、2％、2.3％、2.7％、3％、3.5％、3.8％、4％、4.2％、4.6％或5％等。
在本发明中，纺丝液中的金属氧化物浓度对于纺丝过程影响较大，如果浓度过低，金属氧化物含量过少无法提升性能；而如果浓度过高会造成纺丝不稳定，而且超过5％，无法正常静电纺丝。
优选地，所述金属氧化物溶胶的浓度为0.5％-10％，例如可以是0.5％、1％、1.3％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％、9.5％或10％等。金属氧化物溶胶的浓度指的是金属氧化物在分散液中的质量百分比。
优选地，所述静电纺丝过程中，纺丝距离设置为15-25cm。例如可以是15cm、18cm、20cm、22cm、23cm或25cm等。
优选地，纺丝电压为25kV。
优选地，静电纺丝过程中环境温度为25-27℃，例如可以是25℃、26℃、27℃等。
优选地，静电纺丝过程中环境的相对湿度为38％-42％，例如可以是38％、39％、40％、41％或42％等。
优选地，金属氧化物溶胶涂覆在纤维改性膜表面之后，还包括烘干的步骤，得到所述荷正电微纳米纤维改性膜。
在本发明中，烘干的具体过程，指的是纤维改性膜浸没在金属氧化物分散液中，经过涂覆，在一定温度下，金属氧化物溶胶凝胶化沉积在纤维改性膜表面的过程。
优选地，烘干的温度为50-65℃，例如可以是50℃、53℃、55℃、58℃、60℃、62℃、63℃、65℃等，优选为60℃。
优选地，烘干的时间为10-30min，例如可以是10min、12min、15min、16min、18min、20min、22min、25min、29min或30min等，优选为20min。
第二方面，本发明提供了一种第一方面所述的制备方法制备得到的荷正电微纳米纤维改性膜。
本发明提供的荷正电微纳米纤维改性膜，比表面积大，具有合理的通量，有利于吸附过程的进行，吸附能力强，相比于现有的荷电纤维膜，具有更好的性能。
第三方面，本发明提供了一种荷正电微纳米纤维改性膜在制备水处理滤芯和工业反渗透水处理中的应用。
与现有技术相比，本发明的有益效果为：
本发明提供的荷正电微纳米纤维改性膜的制备方法，无需添加其它任何助剂和粘附剂，相比于现有的荷电纤维，操作过程简单方便。
本发明提供的荷正电微纳米纤维改性膜，比表面积大，通过掺杂金属氧化物与静电纺丝技术结合，提升了吸附能力，并且具有合理的通量，跨膜压差低，相比于现有的荷电纤维膜，具有更好的性能，可以广泛应用于水处理中。
具体实施方式
为更好地说明本发明，便于理解技术方案，下面对本发明进一步详细说明。
实施例1
配制浓度为25％的聚丙烯腈与DMAc的混合溶液，其中添加0.5％荷正电勃姆石，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度25℃，湿度40％，获得掺杂勃姆石颗粒的聚丙烯腈纳米纤维改性膜，将纳米纤维改性膜浸没在2％的微纳米勃姆石溶胶中，时间为1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min获得表面荷正电的纳米纤维改性膜。
实施例2
配制浓度为20％的聚偏氟乙烯与DMF溶液，其中添加1％荷正电二氧化钛，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度26℃，湿度41％，获得掺杂二氧化钛颗粒的聚偏氟乙烯纳米纤维改性膜，将此纳米纤维改性膜浸没在1％的微纳米二氧化钛溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min获得表面荷正电的纳米纤维改性膜。
实施例3
配制浓度为10％的聚苯乙烯与DMSO溶液，其中添加2％荷正电二氧化锰，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度27℃，湿度39％，获得掺杂二氧化锰颗粒的聚苯乙烯纳米纤维改性膜，将此纳米纤维改性膜浸没在3％的微纳米二氧化锰溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min获得表面荷正电的纳米纤维改性膜。
实施例4
配制浓度为30％的聚醚砜与丙酮溶液，其中添加1.5％荷正电氧化铜，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度26℃，湿度42％，获得掺杂氧化铜颗粒的聚醚砜纳米纤维改性膜，将此纳米纤维改性膜浸没在5％的微纳米氧化铜溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min获得表面荷正电的纳米纤维改性膜。
实施例5
配制浓度为25％的二醋酸纤维素与DMF溶液，其中添加3％荷正电氧化钼，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度25℃，湿度38％，获得掺杂氧化钼颗粒的二醋酸纤维素纳米纤维膜，将此纳米纤维改性膜浸没在10％的微纳米氧化钼溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min，获得表面荷正电的纳米纤维改性膜。
实施例6
配制浓度为25％的聚甲基丙烯酸甲酯与DMAc溶液，其中添加5％荷正电氧化铜，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度27℃，湿度42％，获得掺杂氧化铜颗粒的聚甲基丙烯酸甲酯纳米纤维改性膜，将此纳米纤维改性膜膜浸没在0.5％的微纳米氧化铜溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min，获得表面荷正电的纳米纤维改性膜。
实施例7
配制浓度为25％的聚苯乙烯与氯仿溶液，其中添加0.1％荷正电氧化锌，以PET为接收基材，进行静电纺丝，纺丝距离20cm，纺丝电压25kV，纺丝温度27℃，湿度38％，获得掺杂氧化锌颗粒的聚苯乙纳米纤维改性膜，将此纳米纤维改性膜浸没在0.5％的微纳米氧化锌溶胶中1min，进行膜表面涂覆，然后在60℃烘箱下烘烤20min，获得表面荷正电的纳米纤维改性膜。
实施例8
本实施例与实施例1的区别仅在于，本实施例中聚丙烯腈与DMAc的混合溶液的浓度为40％
实施例9
本实施例与实施例1的区别仅在于，本实施例中荷正电勃姆石的浓度为7％。本实施例无法正常进行静电纺丝。
实施例10
本实施例与实施例1的区别仅在于，本实施例中微纳米勃姆石溶胶的浓度6.5％。本实施例无法正常进行静电纺丝。
对比例1
按照CN111701466A中公开的方法，步骤一、按质量百分比50％称取天然纤维，添加水并快速搅拌分散均匀，得到A浆料；步骤二、按质量百分比5％称取聚酰胺聚环氧氯丙烷树脂，添加水并快速搅拌，得到B分散液；步骤三、按质量百分比1％称取聚乙烯醇和质量百分比44％的多尺度微纳米荷正电二氧化钛，添加水并快速搅拌，得到混合C分散液；步骤四、将步骤一得到的A浆料和步骤三得到的B分散液混合均匀；步骤五、将步骤三得到C分散液加入到步骤四得到的混合分散液中，得到混合D溶液，经过高速搅拌(高速为速度大于等于每分钟1000转)，真空抽滤和高温干燥，利用高温脱水活化，溶胶-凝胶，化学交联，静电吸附和/或物理缠结的联合方式，将多尺度微纳米荷正电金属氧化物复合固定于荷负电纤维表面及纤维之间，制备得到多尺度微纳米荷正电复合材料。
对比例2
按照CN102078771B公开的实施例1中方法，制备膜材料。
取99.9％的铝粉和分析纯的盐酸，将盐酸加热至90℃，缓慢加入铝粉，剧烈反应后，放入水浴锅中90℃加热回流10h，至固体全部溶解，得到铝氧溶胶。在铝氧溶胶加入20％(以Al2O3计)甲醛乙酸铝，90℃分散溶解，80℃真空浓缩，至粘度上升至可纺丝程度，进行过滤纺丝成膜。并将得到的素丝膜在80℃条件下干燥12h后进行1000℃烧结，随炉冷却。将得到的纤维膜骨架放入高压釜上层，下层是由10％氨水沉淀2mol/L硝酸铝得到的固体，配制成10％浓度的水溶液，pH＝6，200℃水热24h，取出，纯水洗涤3次，无水乙醇洗涤2次。真空干燥12h，700℃退火1h，得到产品膜。
对比例3
本对比例与实施例1的区别在于，不添加0.5％荷正电勃姆石，制备得到纳米纤维改性膜。
对比例4
本对比例与实施例1的区别在于，静电纺丝后直接获得掺杂勃姆石颗粒的聚丙烯腈纳米纤维改性膜，不进行后续的涂覆烘干步骤。
将上述实施例和对比例制备的改性膜进行性能测试，纯水通量按照HY/T051-1999的标准进行测试，胶体吸附能力(确定水中颗粒物浓度，再将制备的膜分别使同样的水流通过，测试通过膜流出水的颗粒物浓度，计算流出浓度与流出前浓度的比值，即得胶体吸附百分比)结果如下表1所示：
表1
通过以上表1中的数据可知：通过本发明制备方法制备出的微纳米纤维改性膜，具有良好的胶体吸附能力，吸附水中的颗粒物可达到95％以上，同时通量保持在合理的通量值附近，保证了吸附过程的有效进行。而如果没有金属氧化物的添加或者不进行静电纺丝后的涂覆烘干过程，胶体吸附能力下降到仅有80％左右，通量变化较大，无法达到良好的性能。由此可以看出，金属氧化物与静电纺丝技术的结合，协同提升了膜的吸附效果，并且简化工艺，制备过程简单。
本发明通过上述实施例来说明本发明的荷正电微纳米纤维改性膜及其制备方法和应用，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种荷正电微纳米纤维改性膜的制备方法，其特征在于，所述制备方法包括：将金属氧化物与高聚物混合配制成纺丝液，纺丝液通过静电纺丝过程制备出纤维改性膜后，将金属氧化物溶胶涂覆在纤维改性膜表面，得到所述荷正电微纳米纤维改性膜。
2.根据权利要求1所述的制备方法，其特征在于，所述金属氧化物包括五氧化二钒、氧化钼、二氧化锰、二氧化钛、氧化铝、勃姆石、氧化锌、氧化铁或氧化铜中的一种或至少两种的组合；优选为勃姆石。
3.根据权利要求1或2所述的制备方法，其特征在于，所述高聚物包括聚偏氟乙烯、聚丙烯腈、二醋酸纤维素、聚甲基丙烯酸甲酯、聚醚砜、聚苯乙烯、聚氯乙烯、聚丙烯或芳砜纶中的一种或至少两种的组合。
4.根据权利要求1-3中任一项所述的制备方法，其特征在于，所述纺丝液的溶剂包括二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、丙酮或氯仿中的任意一种或至少两种的组合。
5.根据权利要求1-4中任一项所述的制备方法，其特征在于，所述静电纺丝过程包括接收底布；
优选地，所述接收底布为聚二甲基丙烯酸甲酯。
6.根据权利要求1-5中任一项所述的制备方法，其特征在于，所述纺丝液的浓度为10％-30％；
优选地，所述纺丝液中金属氧化物的浓度为0.1％-5％；
优选地，所述金属氧化物溶胶的浓度为0.5％-10％。
7.根据权利要求1-6中任一项所述的制备方法，其特征在于，所述静电纺丝过程中，纺丝距离设置为20cm；
优选地，纺丝电压为25kV；
优选地，静电纺丝过程中环境温度为25-27℃；
优选地，静电纺丝过程中环境的相对湿度为38％-42％。
8.根据权利要求1-7中任一项所述的制备方法，其特征在于，金属氧化物溶胶涂覆在纤维改性膜表面之后，还包括烘干的步骤，得到所述荷正电微纳米纤维改性膜；
优选地，烘干的温度为50-65℃，优选为60℃；
优选地，烘干的时间为10-30min，优选为20min。
9.根据权利要求1-8中任一项所述的制备方法制备得到的荷正电微纳米纤维改性膜。
10.根据权利要求9所述的荷正电微纳米纤维改性膜在制备水处理滤芯和工业反渗透水处理中的应用。
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