CN106621845A - 一种抗复合污染型膜材料的制备方法与用途 - Google Patents
一种抗复合污染型膜材料的制备方法与用途 Download PDFInfo
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Abstract
本发明涉及一种抗复合污染型膜材料的制备方法与用途，通过光催化材料的修饰、抑菌物质的负载及成膜步骤制成抗复合污染型膜材料。本发明在膜中加入负载有抗菌物质的光催化材料，使得制成的膜具有同时抑制生物污染和有机污染的能力，使得所制成的膜能够消除复合污染，有效的延长了膜材料的使用寿命。
Description
技术领域
本发明涉及一种膜材料的制备方法，具体涉及一种抗复合污染型膜材料的制备方法与用途。
背景技术
膜技术是利用具有选择透过性的薄膜在外加能量或者化学位差的作用下实现对混合料液中各组分的分离、分级、提纯和富集。膜分离技术由于操作简单、无相变、高效节能、占地面积少等优点在饮用水深度净化、污水处理及资源化领域得到了广泛地应用。然而，膜污染，一直是膜分离技术面临的瓶颈难题。
膜污染不仅会造成膜通量和截留性能的下降，还会增加运行成本，缩短膜的使用寿命，使得膜的净化作用降低。因此，抗污染型膜材料的研制显得十分必要。
对此，现有技术中存在一种抗污染型膜材料，如中国专利文献CN104857858A，其利用生物纳米银的广谱杀菌性，超强的活性及渗透性通过掺杂制备纳米银复合膜对生物污染有很好的抑制作用。
然而，现有的膜污染类型往往并非是单一的生物污染，膜污染一般可分为无机污染、有机污染和生物污染，其中有机污染和生物污染通常同时存在，而CN104857858A公开的膜材料无法消除该种类型的复合污染，因此，研制一种能够抑制复合污染的膜材料成为必要。
发明内容
本发明的目的是克服现有技术中膜材料无法抑制复合污染的缺陷，从而提供一种抗复合污染型膜材料的制备方法。
根据本发明的第一个方面，本发明提供了一种抗复合污染型膜材料的制备方法，包括以下步骤：
步骤一：光催化材料的修饰：将光催化材料粉末与强酸物质混合均匀后，经搅拌、离心，并用去离子水洗涤直至中性，最后在烘箱中干燥，完成后即为修饰后的光催化材料；
步骤二：抑菌物质的负载，将步骤一获得的修饰后的光催化材料与抑菌物质纳米银相互作用；经离心分离、分离后固体采用超纯水洗涤后干燥，再经研磨得到负载抑菌物质的光催化材料；
步骤三：成膜：将步骤二制成的所述负载抑菌物质的光催化材料制成铸膜液并经相转化发成膜以制得所述抗复合污染型膜材料。
进一步的，所述光催化材料为石墨相氮化炭，由以下制备方法制备所得：将三聚氰胺粉末加入带盖的氧化铝坩埚内，在马弗炉中加热至500℃并保持2小时，然后以10℃min-1的速度升温至520℃并保持2小时，自然冷却至室温得黄色块状固体，然后用玛瑙研钵研磨得到淡黄色粉末状石墨相氮化炭。
进一步的，所述步骤一中的所述强酸物质为浓硝酸和浓硫酸以重量比为1:3组成的混合液。
进一步的，所述步骤二中抑菌物质的负载具体步骤为：石墨相氮化炭粉末加入到超纯水中，经超声处理使其充分分散，加入硝酸银水溶液和甲醇，充入氮气20min，最后在磁力搅拌下用125W高压汞灯照射12小时完成光还原过程，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载银固体粉末。
进一步的，所述步骤二中抑菌物质的负载具体步骤为：将乳酸杆菌悬液60mL、2molL-1的NaOH溶液20mL、银氨溶液20mL、0.3g石墨相氮化炭粉末混合均匀；置于30℃摇床中以180rpm振荡培养24h，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载生物纳米银固体粉末。
进一步的，所述步骤三中的铸膜液制备方法为：将负载抑菌物质的光催化材料加入到N，N-二甲基甲酰胺中，超声30min使其分散，随后加入聚醚砜，在30-60℃烘箱中加热搅拌使其溶解，30-60℃烘箱中密闭静置脱泡，形成均质铸膜液。
进一步的，所述步骤三中成膜方法为：将脱泡完全的铸膜液用刮刀在无纺布上刮成一定厚度的薄膜，直接进入凝胶浴中使其相转化成膜。
本发明制备的抗复合污染型膜材料可制备成膜组件用于水处理装置。
本发明相比现有技术的有如下优点：
1.本发明在膜中加入负载有抗菌物质的光催化材料，使得制成的膜具有同时抑制生物污染和有机污染的能力，使得所制成的膜能够消除复合污染，有效的延长了膜材料的使用寿命。
2.本发明采用氮化碳作为光催化材料，使得在可见光下即可实现光催化作用，有效的提高了膜的抗污染能力。
附图说明
图1是本发明具体实施例1中负载纳米银的氮化碳的透射电镜图；
图2是本发明具体实施例1中抗复合污染型膜对大肠杆菌的抑菌效果图；
图3是本发明具体实施例1中抗复合污染型膜对铜绿假单胞菌的抑菌效果图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。
实施例1
一种抗复合污染型膜材料，通过以下方法进行制备：
步骤一：石墨相氮化炭(g-C3N4)的制备及修饰：
将5g三聚氰胺粉末放入带盖的氧化铝坩埚内，在马弗炉中加热至500℃并保持2小时，然后以10℃min-1的速度升温至520℃并保持2小时，自然冷却至室温，黄色块状固体用玛瑙研钵研磨得到淡黄色粉末。
将g-C3N4粉末分散在硝酸和硫酸以1:3组成的混合体系中，浑浊液体在磁力搅拌下过夜，固体粉末经6000rpm离心，用去离子水洗涤直至中性，最后在60℃烘箱中干燥过夜即可得到修饰后的石墨相氮化炭(g-C3N4)。
步骤二：纳米银负载：
0.3g石墨相氮化炭(g-C3N4)粉末加入到100mL超纯水中，经超声处理30min使其充分分散，加入15mL硝酸银水溶液(0.1molL-1)和10mL甲醇，充入氮气20min，最后在磁力搅拌下用125W高压汞灯照射12小时完成光还原过程，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载银(g-C3N4/Ag)固体粉末。
步骤三：铸膜液的配制及相转化法成膜：
将0.714g一定含银量的g-C3N4/Ag固体粉末加入到79.4g的N，N-二甲基甲酰胺(DMF)中，超声30min并搅拌使其分散，随后加入20g聚醚砜，将此混合物于60℃烘箱中加热使其溶解，经磁力搅拌、60℃烘箱中密闭静置脱泡，形成均质铸膜液。
将一定量的铸膜液倒入料槽中，使用0.2mm塞尺控制厚度，用刮刀在聚酯无纺布支撑层上刮制薄膜，立刻浸入25℃纯水凝胶浴中相转化成膜。所制得的膜放入纯水浴中24h以上以完全去除多余的有机溶剂。
在0.1MPa压力下，制备的膜纯水通量为230.5Lm-2h-1，对1000mg/L卵清蛋白的截留率为94.3％，对1000mg/L牛血清蛋白(BSA)的截留率为98.7％，截留分子量(MWCO)为45KDa。对大肠杆菌(图2)和铜绿假单胞菌的抑菌环测试效果明显(图3)。
实施例2
一种抗复合污染型膜材料，通过以下方法进行制备：
步骤一：石墨相氮化炭(g-C3N4)的制备及修饰同实施例1。
步骤二：生物纳米银原位还原负载：
1)乳酸杆菌(LactobacillusfermentumLMG8900)菌悬液的配制：称取2.0g研细的乳酸杆菌干菌粉加入60mL去离子水，搅拌振荡混合均匀备用；
2)银氨溶液的配制：称取15.74g硝酸银，加入去离子水溶解，滴加5％的氨水直到产生的棕褐色沉淀刚好消失，用去离子水定容至100mL；
3)配制2molL-1的氢氧化钠溶液；
4)在250mL的锥形瓶中将乳酸杆菌菌悬液60mL、NaOH溶液20mL、银氨溶液20mL、0.3g石墨相氮化炭(g-C3N4)粉末混合均匀；将混合液置于30℃摇床中以180rpm振荡培养24h，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载生物纳米银(g-C3N4/Bio-Ag0)固体粉末。
乳酸杆菌表面的多糖类基团将Ag+还原为Ag0，由于修饰后的石墨相氮化炭(g-C3N4)表面含有亲水性基团，可以在还原的过程中实现小粒径生物纳米银(Bio-Ag0)的负载。
步骤三：铸膜液的配制及相转化法成膜：
将0.547g一定含银量的g-C3N4/Bio-Ag0固体粉末加入到79.4g的N，N-二甲基甲酰胺(DMF)中，超声30min并搅拌使其分散，随后加入20g聚醚砜，将此混合物于30℃烘箱中加热使其溶解，经磁力搅拌、30℃烘箱中密闭静置脱泡，形成均质铸膜液，然后按照实施例1中方式进行转化成膜等后续步骤。
较低的溶解和静置脱泡温度，可以确保含银量的g-C3N4/Bio-Ag0固体粉末表面生物质成分的稳定，此生物纳米银表面的少量生物质，能够更容易实现与细菌表面的接触粘附，因此其抗菌性能可以更好的发挥。
尽管已经详细描述了本发明的实施方式，但是应该理解的是，在不偏离本发明的精神和范围的情况下，可以对本发明的实施方式做出各种改变、替换和变更。
Claims (8)
1.一种抗复合污染型膜材料的制备方法，其特征在于，包括以下步骤：
步骤一：光催化材料的修饰，将光催化材料粉末与强酸物质混合均匀后，经搅拌、离心，并用去离子水洗涤直至中性，最后在烘箱中干燥，完成后即为修饰后的光催化材料；所述光催化材料为石墨相氮化炭；
步骤二：抑菌物质的负载，将步骤一获得的修饰后的光催化材料与抑菌物质纳米银相互作用；经离心分离、分离后固体采用超纯水洗涤后干燥，再经研磨得到负载抑菌物质的光催化材料；
步骤三：成膜，将步骤二制成的所述负载抑菌物质的光催化材料制成铸膜液并经相转化法成膜以制得所述抗复合污染型膜材料。
2.根据权利要求1所述的制备方法，其特征在于：所述光催化材料石墨相氮化炭由以下制备方法制备所得：将三聚氰胺粉末加入带盖的氧化铝坩埚内，在马弗炉中加热至500℃并保持2小时，然后以10℃min-1的速度升温至520℃并保持2小时，自然冷却至室温得黄色块状固体，然后用玛瑙研钵研磨得到淡黄色粉末状石墨相氮化炭。
3.根据权利要求1所述的制备方法，其特征在于：步骤一中的所述强酸物质为浓硝酸和浓硫酸以重量比为1:3组成的混合液。
4.根据权利要求1所述的制备方法，其特征在于：步骤二中抑菌物质的负载具体步骤为：石墨相氮化炭粉末加入到超纯水中，经超声处理使其充分分散，加入硝酸银水溶液和甲醇，充入氮气20min，最后在磁力搅拌下用125W高压汞灯照射12小时完成光还原过程，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载银固体粉末。
5.根据权利要求1所述的制备方法，其特征在于：步骤二中抑菌物质的负载具体步骤为：将乳酸杆菌悬液60mL、2molL-1的NaOH溶液20mL、银氨溶液20mL、0.3g石墨相氮化炭粉末混合均匀；置于30℃摇床中以180rpm振荡培养24h，固体经离心分离、超纯水洗涤后在60℃烘箱中干燥10小时，经研磨得到石墨相氮化炭载生物纳米银固体粉末。
6.根据权利要求1所述的制备方法，其特征在于：所述步骤三中的铸膜液制备方法为：将负载抑菌物质的光催化材料加入到N，N-二甲基甲酰胺中，超声30min使其分散，随后加入聚醚砜，在30-60℃烘箱中加热搅拌使其溶解，30-60℃烘箱中密闭静置脱泡，形成均质铸膜液。
7.根据权利要求1所述的制备方法，其特征在于：所述成膜方法为：将铸膜液用刮刀在无纺布上刮成一定厚度的薄膜，直接浸入凝胶浴中使其相转化成膜。
8.一种抗复合污染型膜材料的用途，所述抗复合污染型膜材料由权利要求1所述的制备方法制备，其特征在于：所述抗复合污染型膜材料制成的膜组件用于水处理装置。
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