CN114478024A - 一种荷负电耐污染陶瓷膜的制备方法 - Google Patents

一种荷负电耐污染陶瓷膜的制备方法 Download PDF

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CN114478024A
CN114478024A CN202210202865.0A CN202210202865A CN114478024A CN 114478024 A CN114478024 A CN 114478024A CN 202210202865 A CN202210202865 A CN 202210202865A CN 114478024 A CN114478024 A CN 114478024A
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马军
张瑛洁
李江岑
程喜全
王凯
徐宇涵
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Shandong Zhong'ou Membrane Technology Research Co ltd
Harbin Institute of Technology Weihai
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Harbin Institute of Technology Weihai
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Abstract

一种荷负电耐污染陶瓷膜的制备方法，它涉及陶瓷膜制备技术领域，本发明要解决陶瓷膜制备中荷负电添加剂分散性差，陶瓷膜性能不佳的问题。所述方法：超高分散性电纳米添加剂的制备；陶瓷粉料共混及陶瓷膜烧结。本发明的荷负电耐污染陶瓷膜在饮用水净化及污水处理中展现出优异性能。本发明的陶瓷膜呈现明显电负性与臭氧催化性能，展现出优异耐污染性能；电负性纳米添加剂在陶瓷骨料中分散均匀不团聚；陶瓷膜材料透水性优异；对浊度去除率达99.9％以上，藻类去除率达100％；溶解性有机碳(DOC)去除率为85％以上；总有机碳去除率为85％以上；CODMn去除率为85％以上，耐污染性能优异，通量恢复率可达95％以上，清洗周期长。

Description

一种荷负电耐污染陶瓷膜的制备方法
技术领域
本发明涉及陶瓷膜制备技术领域，具体涉及一种荷负电耐污染陶瓷膜的制备方法。
背景技术
随着我国经济快速发展与居民生活质量不断提高，居民对水质要求日益增加。传统絮凝-沉降-过滤工艺难以保障居民饮用水安全。近年来，以膜分离技术与高级氧化技术为代表的水深度处理技术逐渐受到关注。然而，目前高分子膜材料为市场主导，在高级氧化过程中会发生材料老化，导致膜性能产生较大损失，使用寿命下降，运行成本升高。
近年来，以陶瓷为基材的分离膜材料在水深度处理过程中备受关注。一方面，陶瓷膜材料具有优异的耐氧化特性，可以在高浓度高锰酸钾、臭氧条件下使用；另一方面，陶瓷膜材料经过修饰后容易带负电荷，并呈现出优异的催化性能。然而，现有负载技术主要为直接掺杂，导致添加剂容易团聚，且结合性不好，容易发生活性物质流失。此外，添加剂的团聚容易造成陶瓷膜通量下降，存在对有机物的去除效果不佳等缺点。因此，高性能陶瓷膜的制备仍然是一个挑战。荷负电纳米添加剂在改性陶瓷纳滤膜中受到了专家学者们越来越多的关注，但是目前其容易团聚程为规模化制备性能稳定陶瓷膜一个重要难点。
因此，目前非常迫切需要提供了一种能够克服现有技术中所存在的上述技术问题的荷负电的耐污染陶瓷膜。
发明内容
本发明的目的是为了解决陶瓷膜制备中荷负电添加剂分散性差，陶瓷膜性能不佳的问题。而提供一种荷负电耐污染陶瓷膜的制备方法。
本发明的一种荷负电耐污染陶瓷膜的制备方法，所述方法包括如下步骤：
(1)高分散性电纳米添加剂的制备：
将多巴胺与荷负电纳米添加剂混合后，搅拌均匀后，加入胺类物质，再次搅拌均匀后，加入硅烷偶联剂、pH＝8.5的Tris-HCl缓冲溶液和醇溶液，搅拌1～24h后，经过过滤，100℃真空烘干24h后即得到纳米改性超分散纳米添加剂；
(2)陶瓷膜烧结：将陶瓷粉体、步骤(1)纳米改性超分散纳米添加剂、致孔剂、粘结剂和水共混，制得陶瓷膜共混料；对陶瓷膜共混料进行混炼处理并静置，得到混合泥料；将所述泥料进行梯度升温烧结，制得所述陶瓷膜；
其中，制备纳米改性超分散纳米添加剂中，按照重量份数计，多巴胺的添加量为1～3份，荷负电纳米添加剂的添加量为1～3份，胺类的添加量为1～3份，硅烷偶联剂的添加量为1～5份，Tris-HCl缓冲溶液添加量为90～98份，醇溶液的添加量为5～10份；
所述的陶瓷膜烧结中，按照重量份数计，陶瓷粉体的添加量为20～60份，步骤(1)纳米改性超分散纳米添加剂的添加量为10～50份，致孔剂的添加量为10～20份，粘结剂的添加量为5～20份，水的添加量为5～10份。
进一步地，所述的荷负电的纳米添加剂为电气石、改性电气石、氧化石墨烯、氮化硼、Mxene材料中的一种或几种。
进一步地，所述的醇溶液为乙醇或甲醇。
进一步地，所述的醇溶液为体积百分含量为95％的乙醇或甲醇。
进一步地，所述的胺类物质为乙二胺、聚乙烯亚胺、己二胺或聚醚胺。
进一步地，所述的陶瓷膜原料粉末为氧化铝、高岭土、碳化硅、氧化锆或氧化钛。
所述的陶瓷膜原料粉末为氧化铝、高岭土、碳化硅、氧化锆或氧化钛。所述的陶瓷膜原料为纳米级别。
进一步地，所述的致孔剂为羟甲基纤维素、黄糊精、聚乙二醇或甘油。
进一步地，所述的粘结剂为钾长石、二氧化硅、滑石中的一种或两种。
进一步地，所述的硅烷偶联剂为KH560或者KH550
进一步地，步骤(2)中所述的梯度升温烧结为：所述泥料经过工业微波炉干燥后，放入马弗炉焙烧，以4～6℃/min的升温速率升温至350～2000℃进行焙烧，并在该温度下保温7～9h。
进一步地，步骤(2)中所述的梯度升温烧结为：所述泥料经过工业微波炉干燥后，放入马弗炉焙烧，以4～6℃/min的升温速率升温至350～780℃进行焙烧，并在该温度下保温7～9h。
进一步地，步骤(2)中所述的梯度升温烧结为：所述泥料经过工业微波炉干燥后，放入马弗炉焙烧，以4～6℃/min的升温速率升温至350～1000℃进行焙烧，并在该温度下保温7～9h。
进一步地，在加入硅烷偶联剂和pH＝8.5的Tris-HCl缓冲溶液后，边搅拌边加入浓度3～5mmol/L的CuSO4溶液、浓度10～12mmol/L的H2O2溶液和醇溶液，其中，CuSO4溶液、H2O2溶液为等体积加入，CuSO4溶液、H2O2溶液分别均分为两份，其中一份的CuSO4溶液、H2O2溶液与醇溶液加入到反应液中，待加完后，搅拌10～30min后，加入另一份CuSO4溶液、H2O2溶液；搅拌1～24h后，即得到纳米改性超分散纳米添加剂；
按照重量份数计，多巴胺的添加量为1～3份，荷负电纳米添加剂的添加量为1～3份，胺类的添加量为1～3份，硅烷偶联剂的添加量为1～5份，Tris-HCl缓冲溶液添加量为90～98份，醇溶液的添加量为5～10份，CuSO4和H2O2混合溶液的添加量为0.1～0.5份。
本发明通过多巴胺涂覆改性了荷负电纳米添加剂，使得荷负电纳米添加剂表面包覆有聚多巴胺，利用聚多巴胺带有的相同电荷形成的排斥力，大幅度提升了纳米添加剂的分散性能，高温下，多巴胺涂层能够分解，不影响膜的电荷性能，同时所制备荷负电纳米添加剂呈现出明显的臭氧催化性能与稳定性，长时间使用也没有颗粒浸出；渗透性能优异。
本发明以仿生涂覆形式，增加荷负电无机纳米添加剂分散性；然后与陶瓷膜原料粉末、致孔剂与粘结剂共混，制得陶瓷膜共混料；将所述共混料经过烧结后可以成型并有效去除荷负电纳米添加剂的有机涂层。使用该种方法之制备陶瓷膜可以明显增加荷负电纳米添加剂比例，提升电负性与耐污染性，同时赋予陶瓷膜优异催化性能。
本发明加入醇类物质，尤其是甲醇、乙醇等短链的醇类，能够显著增强多巴胺在荷负电纳米添加剂的润湿性，利于多巴胺涂敷在荷负电纳米添加剂表面。硫酸铜与过氧化氢的氧化物质的加入，能够加快多巴胺涂敷在荷负电纳米添加剂表面，并且发现，改变醇类物质与硫酸铜与过氧化氢的加入方式，将硫酸铜与过氧化氢分阶段加入，并不会过度影响醇类物质的润湿作用。胺类物质增加多巴胺上的电荷数量。
所制备的陶瓷膜性能如下：(i)独特荷负电性能及超优异纳米分散性；(ii)渗透性能优异，水通量可达5000Lm-2h-1bar-1以上；(iii)浊度去除率为99.9％以上，藻类去除率可达100％；(iv)溶解性有机碳(DOC)去除率为85％以上；(v)总有机碳去除率为85％以上；(vi)CODMn去除率为85％以上；(vii)通量恢复率达95％以上，清洗周期达1d以上。
附图说明
图1为实施例1中所制备陶瓷膜的表面形貌图；
图2为对比例2中所制备陶瓷膜的表面形貌图；
图3为实施例1中所制备陶瓷膜的示差扫描-热失重图。
具体实施方式
下文将通过实施例的形式对本发明进行进一步的说明，但是本发明请求保护的范围不限于这些实施例。
实施例1
本实施例中制备荷负电耐污染陶瓷膜包括如下步骤：
(1)超高分散性电纳米添加剂的制备：所选用纳米添加剂为2g的电气石，2g的多巴胺，胺类物质为2g的乙二胺，硅烷偶联剂为1g的KH560，97mL的pH＝8.5的Tris-HCl缓冲溶液，然后加入6mL的体积百分含量为95％的乙醇，0.5mL的浓度为5mmol/L的CuSO4溶液，0.5mL的浓度10mmol/L的H2O2溶液，搅拌15min后，加入0.5mL的浓度为5mmol/L的CuSO4溶液，0.5mL的浓度10mmol/L的H2O2溶液，经过搅拌24h后，即可得到纳米改性超分散纳米添加剂；
(2)陶瓷膜共混料的制备：选用40g的Al2O3作为陶瓷基体；35g的电气石纳米添加剂；10g的致孔剂选择黄糊精；10g的粘结剂选择钾长石与滑石；5mL的水，经过高速混料机强力搅拌共混；
(3)陶瓷膜的烧结：经过工业微波炉干燥后，放入马弗炉焙烧，以5℃/min的升温速率升温至780℃进行焙烧，并在该温度下保温8小时，制得陶瓷膜。
经检测，所制备陶瓷膜Zeta点位为-80mV，纯水通量可达6240Lm-2h-1bar-1，对浊度去除率达99.93％，在臭氧浓度为2.5mg/L时对溶解性有机碳(DOC)去除率为88.3％，总有机碳去除率89.8％，CODMn去除率90.2％，通量恢复率为95.4％，清洗周期为3天。如有检测标准方法请说明或者介绍出处例如国家标准。
实施例2
采用与实施例1基本相同的方法进行，不同之处在于，采用陶瓷粉料为TiO2，代替氧化铝粉末。
对比例1
采用与实施例1基本相同的方式进行，不同之处在于，采用等质量的硅藻土作为纳米添加剂。
对比例2
采用与实施例1基本相同的方式进行，不同之处在于，采用等质量电气石作为纳米添加剂，但是未经多巴胺涂覆。
对比例3
采用与实施例1基本相同的方式进行，不同之处在于，未加入醇类物质。
对比例4
采用与实施例1基本相同的方式进行，不同之处在于，CuSO4溶液、H2O2溶液并未采用分两份加入，即：加入6mL的体积百分含量为95％的乙醇，1mL的浓度为5mmol/L的CuSO4溶液，1mL的浓度10mmol/L的H2O2溶液，经过搅拌24h后，即可得到纳米改性超分散纳米添加剂。
表1.各实施例和对比例中制得的陶瓷膜的性能
Figure BDA0003528065450000051
从上表的结果可以看出，各实施例中制得的陶瓷膜的负离子纳米添加剂分散性能优异，不发生团聚，透水性优异，对污染物去除效率高，耐污染性能优异，通过表面电位来看，实施例1和2通过加入多巴胺后电位增加，在加入胺类物质、醇类物质后电位能够得到显著的提高。在臭氧用量条件下，催化效率较各对比例中制得的陶瓷膜的催化效率提升20％以上，并且能够有效缓解膜污染。
通过图1和图2的比较，可以得出多巴胺引入使荷负电纳米粒子分散更为均匀，而且经过胺类物质、醇类物质的处理后，使得实施例1制备出的陶瓷膜的各物质分散性更加均匀。图3为制备陶瓷膜在780℃烧结后的示差扫描-热失重图。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的主旨。

Claims (10)

1.一种荷负电耐污染陶瓷膜的制备方法，其特征在于，所述方法包括如下步骤：
(1)高分散性电纳米添加剂的制备：
将多巴胺与荷负电纳米添加剂混合后，搅拌均匀后，加入胺类物质，再次搅拌均匀后，加入硅烷偶联剂、pH＝8.5的Tris-HCl缓冲溶液和醇溶液，搅拌1～24h后，经过过滤，100℃真空烘干24h后即得到纳米改性超分散纳米添加剂；
(2)陶瓷膜烧结：将陶瓷粉体、步骤(1)纳米改性超分散纳米添加剂、致孔剂、粘结剂和水共混，制得陶瓷膜共混料；对陶瓷膜共混料进行混炼处理并静置，得到混合泥料；将所述泥料进行梯度升温烧结，制得所述陶瓷膜；
其中，制备纳米改性超分散纳米添加剂中，按照重量份数计，多巴胺的添加量为1～3份，荷负电纳米添加剂的添加量为1～3份，胺类的添加量为1～3份，硅烷偶联剂的添加量为1～5份，Tris-HCl缓冲溶液添加量为90～98份，醇溶液的添加量为5～10份；
所述的陶瓷膜烧结中，按照重量份数计，陶瓷粉体的添加量为20～60份，步骤(1)纳米改性超分散纳米添加剂的添加量为10～50份，致孔剂的添加量为10～20份，粘结剂的添加量为5～20份，水的添加量为5～10份。
2.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的荷负电的纳米添加剂为电气石、改性电气石、氧化石墨烯、氮化硼、Mxene材料中的一种或几种。
3.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的醇溶液为乙醇或甲醇。
4.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的胺类物质为乙二胺、聚乙烯亚胺、己二胺或聚醚胺。
5.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的陶瓷膜原料粉末为氧化铝、高岭土、碳化硅、氧化锆或氧化钛。
6.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的致孔剂为羟甲基纤维素、黄糊精、聚乙二醇或甘油。
7.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于所述的粘结剂为钾长石、二氧化硅、滑石中的一种或两种。
8.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于步骤(2)中所述的梯度升温烧结为：所述泥料经过工业微波炉干燥后，放入马弗炉焙烧，以4～6℃/min的升温速率升温至350～2000℃进行焙烧，并在该温度下保温7～9h。
9.根据权利要求1或8所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于步骤(2)中所述的梯度升温烧结为：所述泥料经过工业微波炉干燥后，放入马弗炉焙烧，以4～6℃/min的升温速率升温至350～780℃进行焙烧，并在该温度下保温7～9h。
10.根据权利要求1所述的一种荷负电耐污染陶瓷膜的制备方法，其特征在于在加入硅烷偶联剂和pH＝8.5的Tris-HCl缓冲溶液后，边搅拌边加入浓度3～5mmol/L的CuSO4溶液、浓度10～12mmol/L的H2O2溶液和醇溶液，其中，CuSO4溶液、H2O2溶液为等体积加入，CuSO4溶液、H2O2溶液分别均分为两份，其中一份的CuSO4溶液、H2O2溶液与醇溶液加入到反应液中，待加完后，搅拌10～30min后，加入另一份CuSO4溶液、H2O2溶液；搅拌1～24h后，即得到纳米改性超分散纳米添加剂；
按照重量份数计，多巴胺的添加量为1～3份，荷负电纳米添加剂的添加量为1～3份，胺类的添加量为1～3份，硅烷偶联剂的添加量为1～5份，Tris-HCl缓冲溶液添加量为90～98份，醇溶液的添加量为5～10份，CuSO4和H2O2混合溶液的添加量为0.1～0.5份。
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