CN114573354B - 一种低温制备陶瓷膜的方法 - Google Patents

一种低温制备陶瓷膜的方法 Download PDF

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CN114573354B
CN114573354B CN202210203940.5A CN202210203940A CN114573354B CN 114573354 B CN114573354 B CN 114573354B CN 202210203940 A CN202210203940 A CN 202210203940A CN 114573354 B CN114573354 B CN 114573354B
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ceramic membrane
ceramic
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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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Abstract

一种低温制备陶瓷膜的方法，它涉及一种低温制备陶瓷膜的方法。本发明的目的是要解决现有陶瓷膜的烧结温度过高，添加低温粘结剂的量大，膜的渗透性能差和对有机物的去除效果不佳的问题。方法：一、制备高分散性低温纳米粘结剂；二、低温烧结，得到陶瓷膜。本发明仿生涂覆形式，增加低温纳米粘结剂分散性；然后与陶瓷粉体与致孔剂共混，制得陶瓷膜共混料；将所述共混料经过烧结后可以成型；使用该种方法制备的陶瓷膜可以明显降低烧结温度、增加孔隙率与抗折强度，提升膜的渗透性与耐污染性。本发明可获得一种低温制备陶瓷膜的方法。

Description

一种低温制备陶瓷膜的方法
技术领域
本发明涉及一种低温制备陶瓷膜的方法。
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，陶瓷膜烧结温度过高，一般超过1000℃。已有报道中虽然有报道低温粘结剂进行烧结，但是低温粘结剂往往存在分散问题，导致低温粘结剂添加量较大，膜孔隙率有待提升，膜的渗透性仍有很大提升空间。此外，粘结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。
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，制备低温烧结陶瓷膜。
发明内容
本发明的目的是要解决现有陶瓷膜的烧结温度过高，添加低温粘结剂的量大，膜的渗透性能差和对有机物的去除效果不佳的问题，而提供一种低温制备陶瓷膜的方法。
一种低温制备陶瓷膜的方法，具体是按以下步骤完成的：
一、制备高分散性低温纳米粘结剂：
①、制备混合液：
将多巴胺、聚乙烯亚胺和pH＝8.5的Tris-HCl缓冲溶液混合，得到混合溶液；
②、将低温纳米粘结剂加入到混合溶液中，搅拌，真空干燥，得到高分散性低温纳米粘结剂；
步骤一②中所述的低温纳米粘结剂为钾长石、氧化锌、氧化钙、氧化镁、碳酸钡、滑石和硼砂中的一种或两种以上的组合；
二、低温烧结：将陶瓷粉体、高分散性低温纳米粘结剂、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；对泥料进行低温烧结，得到陶瓷膜。
相对于现有技术，本发明的优势在于：
一、低温粘结剂近年来陶瓷纳滤膜制备过程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，用量较大，所制备的膜通量相对较小，孔隙率较低(<50％)，抗折强度差(<50MPa),为规模化制备性能稳定陶瓷膜一个重要难点；但是，本发明仿生涂覆形式，增加低温纳米粘结剂分散性；然后与陶瓷粉体与致孔剂共混，制得陶瓷膜共混料；将所述共混料经过烧结后可以成型；使用该种方法制备的陶瓷膜可以明显降低烧结温度、增加孔隙率与抗折强度，提升膜的渗透性与耐污染性；
二、本发明通过多巴胺涂覆改性了低温纳米粘结剂，大幅度提升了低温粘结剂的分散性能，高温下，多巴胺涂层能够分解，不影响膜性能，降低了低温粘结剂使用量，增加了孔隙率(60％以上)与抗折强度(80MPa以上)，渗透性能优异，水通量可达6000Lm-2h-1bar-1以上，浊度去除率为99.9％以上，藻类去除率可达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；通量恢复率达95％以上，清洗周期达1d以上。
本发明可获得一种低温制备陶瓷膜的方法。
附图说明
图1为实施例1制备的陶瓷膜的示差扫描-热失重曲线；
图2为实施例1制备的陶瓷膜的微观形貌图；
图3为实施例2制备的陶瓷膜的微观形貌图；
图4为对比例2制备的陶瓷膜的微观形貌图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行更加清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
具体实施方式一：本实施方式一种低温制备陶瓷膜的方法，具体是按以下步骤完成的：
一、制备高分散性低温纳米粘结剂：
①、制备混合液：
将多巴胺、聚乙烯亚胺和pH＝8.5的Tris-HCl缓冲溶液混合，得到混合溶液；
②、将低温纳米粘结剂加入到混合溶液中，搅拌，真空干燥，得到高分散性低温纳米粘结剂；
步骤一②中所述的低温纳米粘结剂为钾长石、氧化锌、氧化钙、氧化镁、碳酸钡、滑石和硼砂中的一种或两种以上的组合；
二、低温烧结：将陶瓷粉体、高分散性低温纳米粘结剂、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；对泥料进行低温烧结，得到陶瓷膜。
具体实施方式二：本实施方式与具体实施方式一不同点是：步骤一①中所述的混合溶液中多巴胺的质量分数1％～5％，聚乙烯亚胺的质量分数为1％～5％，pH＝8.5的Tris-HCl缓冲溶液的质量分数90％～98％。其它步骤与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二之一不同点是：步骤一②中所述的低温纳米粘结剂与混合溶液中多巴胺的质量比为20:1。其它步骤与具体实施方式一或二相同。
具体实施方式四：本实施方式与具体实施方式一至三之一不同点是：步骤一②中所述的搅拌时间为1h～24h，所述的真空干燥的温度为100℃，真空干燥的时间为10h～20h。其它步骤与具体实施方式一至三相同。
具体实施方式五：本实施方式与具体实施方式一至四之一不同点是：步骤二中所述的陶瓷粉体为氧化铝、高岭土、氧化锆或氧化钛。其它步骤与具体实施方式一至四相同。
具体实施方式六：本实施方式与具体实施方式一至五之一不同点是：步骤二中所述的致孔剂为羟甲基纤维素、黄糊精、聚乙二醇或甘油。其它步骤与具体实施方式一至五相同。
具体实施方式七：本实施方式与具体实施方式一至六之一不同点是：步骤二中所述的陶瓷膜共混料中陶瓷粉体的质量分数为40％～80％，高分散性低温纳米粘结剂的质量分数为5％～15％，致孔剂的质量分数为10％～20％，水的质量分数为5％～10％。其它步骤与具体实施方式一至六相同。
具体实施方式八：本实施方式与具体实施方式一至七之一不同点是：步骤二中所述的低温烧结的温度为350℃～800℃，低温烧结的时间为6h～8h。其它步骤与具体实施方式一至七相同。
具体实施方式九：本实施方式与具体实施方式一至八之一不同点是：对步骤二得到的陶瓷膜进行改性，得到抗蛋白污染的陶瓷膜；所述的改性具体是按以下步骤完成的：
将陶瓷膜浸入到多巴胺、δ-葡萄糖酸内酯、三乙胺和去离子水的混合溶液中，再升温至90℃～95℃加热回流，将陶瓷膜取出，干燥，得到抗蛋白污染的陶瓷膜。其它步骤与具体实施方式一至八相同。
具体实施方式十：本实施方式与具体实施方式一至九之一不同点是：所述的多巴胺与δ-葡萄糖酸内酯的摩尔比为1:1；δ-葡萄糖酸内酯的质量与三乙胺的体积比为(0.5g～1.5g):1mL；δ-葡萄糖酸内酯的质量与去离子水的体积比为(0.5g～1.5g):(20mL～25mL)；所述的加热回流的时间为10h～12h。其它步骤与具体实施方式一至九相同。
采用以下实施例验证本发明的有益效果：
实施例1：一种低温制备陶瓷膜的方法，具体是按以下步骤完成的：
一、制备高分散性低温纳米粘结剂：
①、制备混合液：
将多巴胺、聚乙烯亚胺和pH＝8.5的Tris-HCl缓冲溶液混合，得到混合溶液；
步骤一①中所述的混合溶液中多巴胺的质量分数2％，聚乙烯亚胺的质量分数为2％，pH＝8.5的Tris-HCl缓冲溶液的质量分数96％；
②、将低温纳米粘结剂加入到混合溶液中，搅拌24h，再在真空100℃下干燥24h，得到高分散性低温纳米粘结剂；
步骤一②中所述的低温纳米粘结剂与混合溶液中多巴胺的质量比为1:1；
步骤一②中所述的低温纳米粘结剂为钾长石和硼砂的混合物，其中钾长石和硼砂的质量比为1:1；
二、低温烧结：将陶瓷粉体、高分散性低温纳米粘结剂、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；将泥料以5℃/min的升温速率升温至720℃，在720℃下焙烧8h，得到陶瓷膜；
步骤二中所述的陶瓷粉体为氧化铝；
步骤二中所述的致孔剂为黄糊精；
步骤二中所述的陶瓷膜共混料中陶瓷粉体的质量分数为70％，高分散性低温纳米粘结剂的质量分数为10％，致孔剂的质量分数为15％，水的质量分数为5％。
实施例1制备的陶瓷膜的纯水通量可达6927Lm-2h-1bar-1，对浊度去除率达99.97％，藻类去除率100％，孔隙率达65％，抗折强度达85MPa，通量恢复率达97％。
实施例2：本实施例与实施例1的不同点是：步骤二中所述的陶瓷粉体为二氧化钛；步骤二中将泥料以5℃/min的升温速率升温至590℃，在590℃下焙烧8h，得到陶瓷膜。其它步骤及参数与实施例1均不同。
对比例1：一种采用硅藻土作为纳米粘结剂制备陶瓷膜的方法，具体是按以下步骤完成的：
将陶瓷粉体、硅藻土、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；将泥料以5℃/min的升温速率升温至1200℃，在1200℃下焙烧8h，得到陶瓷膜；
步骤二中所述的陶瓷粉体为氧化铝；
步骤二中所述的致孔剂为黄糊精；
步骤二中所述的陶瓷膜共混料中陶瓷粉体的质量分数为70％，硅藻土的质量分数为10％，致孔剂的质量分数为15％，水的质量分数为5％。
对比例2：一种采用未改性的硼砂及钾长石为纳米粘结剂制备陶瓷膜的方法，具体是按以下步骤完成的：
将陶瓷粉体、低温纳米粘结剂、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；将泥料以5℃/min的升温速率升温至820℃，在820℃下焙烧8h，得到陶瓷膜；
所述的低温纳米粘结剂为钾长石和硼砂的混合物，其中钾长石和硼砂的质量比为1:1；
所述的陶瓷粉体为氧化铝；
所述的致孔剂为黄糊精；
所述的陶瓷膜共混料中陶瓷粉体的质量分数为70％，低温纳米粘结剂的质量分数为10％，致孔剂的质量分数为15％，水的质量分数为5％。
图2为实施例1制备的陶瓷膜的微观形貌图；
图3为实施例2制备的陶瓷膜的微观形貌图；
图4为对比例2制备的陶瓷膜的微观形貌图。
从图2～图4可知，实施例1和实施例2制备的陶瓷膜分散均匀，对比例2制备的陶瓷膜明显团聚结构，分散不均匀。
将实施例1、实施例2、对比例1和对比例2制备的陶瓷膜的性能列于表1；
表1
Figure BDA0003528395580000051
Figure BDA0003528395580000061
从表1的结果可以看出，各实施例中制得的陶瓷膜可实现低温烧结，低温粘结剂分散性能优异，不发生团聚，所制备陶瓷膜孔隙率高、抗折强度高，透水性优异，对污染物去除效率高，耐污染性能优异；而对比例1和对比例2制备的陶瓷膜的烧结温度高，纯水通量低、空隙率小、强度低和需要清洗的时间短。
实施例3：对实施例1步骤二得到的陶瓷膜进行改性，得到抗蛋白污染的陶瓷膜；所述的改性具体是按以下步骤完成的：
将陶瓷膜浸入到多巴胺、δ-葡萄糖酸内酯、三乙胺和去离子水的混合溶液中，再升温至90℃～95℃加热回流，将陶瓷膜取出，干燥，得到抗蛋白污染的陶瓷膜；
所述的多巴胺与δ-葡萄糖酸内酯的摩尔比为1:1；δ-葡萄糖酸内酯的质量与三乙胺的体积比为1g:1mL；δ-葡萄糖酸内酯的质量与去离子水的体积比为1g:20mL；所述的加热回流的时间为10h～12h。
实施例1制备的陶瓷膜和实施例3制备的抗蛋白污染的陶瓷膜对荧光标记牛血清白蛋白进行吸附，然后在荧光显微镜下观察，荧光标记的牛血清白蛋白发出绿光，荧光的强度就代表着所吸附的蛋白质的量。结果表明：实施例1制备的陶瓷膜出现了一定面积的吸附，而实施例3制备的抗蛋白污染的陶瓷膜几乎看不到荧光存在。表明实施例3制备的抗蛋白污染的陶瓷膜抗蛋白污染效果好。经过试验可知，实施例3制备的抗蛋白污染的陶瓷膜的蛋白吸附率低于0.3mg/m2，通量回复率高，可达92％以上。
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)

1.一种低温制备陶瓷膜的方法，其特征在于一种低温制备陶瓷膜的方法具体是按以下步骤完成的：
一、制备高分散性低温纳米粘结剂：
①、制备混合液：
将多巴胺、聚乙烯亚胺和pH＝8.5的Tris-HCl缓冲溶液混合，得到混合溶液；
②、将低温纳米粘结剂加入到混合溶液中，搅拌，真空干燥，得到高分散性低温纳米粘结剂；
步骤一②中所述的低温纳米粘结剂为钾长石、氧化锌、氧化钙、氧化镁、碳酸钡、滑石和硼砂中的一种或两种以上的组合；
二、低温烧结：将陶瓷粉体、高分散性低温纳米粘结剂、致孔剂和水混合，得到陶瓷膜共混料；对陶瓷膜共混料进行机械搅拌，得到泥料；对泥料进行低温烧结，得到陶瓷膜。
2.根据权利要求1所述的一种低温制备陶瓷膜的方法，其特征在于步骤一①中所述的混合溶液中多巴胺的质量分数1％～5％，聚乙烯亚胺的质量分数为1％～5％，pH＝8.5的Tris-HCl缓冲溶液的质量分数90％～98％。
3.根据权利要求1或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤一②中所述的低温纳米粘结剂与混合溶液中多巴胺的质量比为20:1。
4.根据权利要求1或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤一②中所述的搅拌时间为1h～24h，所述的真空干燥的温度为100℃，真空干燥的时间为10h～20h。
5.根据权利要求1或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤二中所述的陶瓷粉体为氧化铝、高岭土、氧化锆或氧化钛。
6.根据权利要求1或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤二中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或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤二中所述的陶瓷膜共混料中陶瓷粉体的质量分数为40％～80％，高分散性低温纳米粘结剂的质量分数为5％～15％，致孔剂的质量分数为10％～20％，水的质量分数为5％～10％。
8.根据权利要求1或2所述的一种低温制备陶瓷膜的方法，其特征在于步骤二中所述的低温烧结的温度为350℃～800℃，低温烧结的时间为6h～8h。
9.根据权利要求1所述的一种低温制备陶瓷膜的方法，其特征在于对步骤二得到的陶瓷膜进行改性，得到抗蛋白污染的陶瓷膜；所述的改性具体是按以下步骤完成的：
将陶瓷膜浸入到多巴胺、δ-葡萄糖酸内酯、三乙胺和去离子水的混合溶液中，再升温至90℃～95℃加热回流，将陶瓷膜取出，干燥，得到抗蛋白污染的陶瓷膜。
10.根据权利要求9所述的一种低温制备陶瓷膜的方法，其特征在于所述的多巴胺与δ-葡萄糖酸内酯的摩尔比为1:1；δ-葡萄糖酸内酯的质量与三乙胺的体积比为(0.5g～1.5g):1mL；δ-葡萄糖酸内酯的质量与去离子水的体积比为(0.5g～1.5g):(20mL～25mL)；所述的加热回流的时间为10h～12h。
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