CN113800938B - 一种氧化钛陶瓷超滤膜的制备方法 - Google Patents

一种氧化钛陶瓷超滤膜的制备方法 Download PDF

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CN113800938B
CN113800938B CN202010539827.5A CN202010539827A CN113800938B CN 113800938 B CN113800938 B CN 113800938B CN 202010539827 A CN202010539827 A CN 202010539827A CN 113800938 B CN113800938 B CN 113800938B
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titanium oxide
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ultrafiltration membrane
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CN113800938A (zh
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陈云强
洪昱斌
方富林
蓝伟光
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Suntar Membrane Technology Xiamen Co Ltd
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Abstract

本发明公开了一种氧化钛陶瓷超滤膜的制备方法。本发明将溶胶‑凝胶法结合微乳介质水热法制备氧化钛纳米溶胶，在氧化钛溶胶中加入添加剂制成涂膜液，浸涂在多孔氧化铝陶瓷膜上，经过干燥、煅烧得到氧化钛超滤膜层。本发明通过在氧化钛溶胶中加入特定乳化剂，在较短的时间和较低的温度的水热反应下制备出氧化钛纳米溶胶，通过配制涂膜液，经过干燥烘干和煅烧制备了氧化钛超滤膜。

Description

一种氧化钛陶瓷超滤膜的制备方法
技术领域
本发明属于膜分离技术领域，具体涉及一种氧化钛陶瓷超滤膜的制备方法。
背景技术
膜分离主要分为微滤、超滤、纳滤和反渗透。膜分离技术的应用领域已经深入到人们生活和生产的各个方面，例如化工、环保、电子、纺织、医药、食品等。有机膜由于不耐高温、耐化学腐蚀差、易污染，在溶剂中溶胀收缩等，使有机膜在一些需要特殊条件的分离过程中受到限制。无机膜具有化学稳定性好、机械强度高、耐高温、抗微生物腐蚀和使用寿命长等，特点，使其能够应用在一些条件苛刻的领域。
现有技术中，纳米粒子制备方法主要有化学沉淀法、溶胶-凝胶法、水热法和微乳液法等。其中溶胶-凝胶法是液相法制备二氧化钛陶瓷超滤膜最主要的方法。但是通过溶胶- 凝胶法获得的二氧化钛纳米溶液制备陶瓷超滤膜时，由于煅烧过程中收缩严重，需要多次涂膜，且制备的溶胶稳定性对涂膜效果影响较大，在一定程度下限制溶胶-凝胶法的扩大生产。水热法制备二氧化钛可以避免湿化学需高温处理可能产生的硬团聚的问题，所制备的二氧化钛晶型结构好，比表面积较高，但是，由于水热法制备对设备要求比较高，需要高温高压条件下才能制备。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种氧化钛陶瓷超滤膜的制备方法。
本发明的技术方案如下：
一种氧化钛陶瓷超滤膜的制备方法，包括如下步骤：
(1)用包括有机钛盐和第一分散剂在内的原料通过溶胶凝胶法制备氧化钛溶胶；
(2)在上述氧化钛溶胶中加入乳化剂，于100-150℃进行水热反应1-3h，该乳化剂由环己烷、正己醇和OP-10(烷基酚与环氧乙烷的缩合物)组成；
(3)将步骤(2)所得的物料进行剪切或超声处理，获得透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入第二分散剂、增塑剂、粘结剂和消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液涂覆于支撑体上，依次经干燥、煅烧和自然冷却，获得氧化钛陶瓷超滤膜。
在本发明的一个优选实施方案中，所述环己烷、正己醇和OP-10的摩尔比为7-9∶2∶1。
进一步优选的，所述乳化剂的加入量为所述氧化钛溶胶的1-5wt％。
在本发明的一个优选实施方案中，所述有机钛盐为钛酸正丁酯或钛酸异丙醇酯，其与水的摩尔比优选为1∶10-50。
在本发明的一个优选实施方案中，所述第一分散剂为柠檬酸钠或聚丙烯酸钠，所述第二分散剂为聚乙二醇，第一分散剂的添加量优选为氧化钛溶胶的0.1-1wt％，第二分散剂的添加量优选为氧化钛纳米溶液的0.1-1wt％。
在本发明的一个优选实施方案中，所述增塑剂为聚乙烯醇，其添加量优选为氧化钛纳米溶液的1-5wt％。
在本发明的一个优选实施方案中，所述粘结剂为羟乙基纤维素，其添加量优选为氧化钛纳米溶液的0.1-5wt％。
在本发明的一个优选实施方案中，所述消泡剂为有机硅消泡剂，其添加量优选为氧化钛纳米溶液的0.01-0.1wt％。
在本发明的一个优选实施方案中，所述干燥的温度为80-120℃，时间为2-5h。
在本发明的一个优选实施方案中，所述煅烧的温度为350-500℃，时间为2-5h。
本发明的有益效果是：
1、本发明将溶胶-凝胶法结合微乳介质水热法制备氧化钛纳米溶胶，在氧化钛溶胶中加入添加剂制成涂膜液，浸涂在多孔氧化铝陶瓷膜上，经过干燥、煅烧得到氧化钛超滤膜层。
2、本发明通过在氧化钛溶胶中加入特定乳化剂，在较短的时间和较低的温度的水热反应下制备出氧化钛纳米溶胶，通过配制涂膜液，经过干燥烘干和煅烧，无需多次涂膜就能制备无缺陷、高质量的氧化钛超滤膜。
附图说明
图1为本发明对比例1制得的对比膜的扫描电镜照片。
图2为本发明对比例2制得的对比膜的扫描电镜照片。
图3为本发明实施例1至3制得的氧化钛陶瓷超滤膜的扫描电镜照片。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
对比例1
(1)在钛酸正丁酯和水以1∶10的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt％的柠檬酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
(2)在上述氧化钛溶胶中加入0.5wt％的乳化剂(环己烷、正己醇和OP-10的摩尔比为8∶2∶1)，于100℃进行水热反应3h；
(3)将步骤(2)所得的物料经自然冷却后进行剪切或超声处理，获得半透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入1wt％的聚乙二醇、3wt％的聚乙烯醇和0.3wt％的羟乙基纤维素，充分混匀后加入0.01wt％的有机硅消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液浸涂于平均孔径为0.1um的多孔陶瓷膜支撑体上，依次经干燥、煅烧和自然冷却，获得对比膜；其中，
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。
本对比例制得的对比膜如图1所示，其膜层开裂，对2g/L的葡聚糖(分子量2万) 截留率为0％。
对比例2
(1)在钛酸正丁酯和水以1∶10的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt％的聚丙烯酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
(2)在上述氧化钛溶胶中加入7wt％的乳化剂(环己烷、正己醇和OP-10的摩尔比为8∶2∶1)，于100℃进行水热反应3h；
(3)将步骤(2)所得的物料经自然冷却后进行剪切或超声处理，获得半透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入1wt％的聚乙二醇、3wt％的聚乙烯醇和0.3wt％的羟乙基纤维素，充分混匀后加入0.01wt％的有机硅消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液浸涂于平均孔径为0.1um的多孔陶瓷膜支撑体上，依次经干燥、煅烧和自然冷却，获得对比膜；其中，
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。
本对比例制得的对比膜如图2所示，其膜层开裂，对2g/L的葡聚糖(分子量2万) 截留率为15％。
实施例1
(1)在钛酸正丁酯和水以1∶10的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt％的柠檬酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
(2)在上述氧化钛溶胶中加入1wt％的乳化剂(环己烷、正己醇和OP-10的摩尔比为8∶2∶1)，于100℃进行水热反应3h；
(3)将步骤(2)所得的物料经自然冷却后进行剪切或超声处理，获得半透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入1wt％的聚乙二醇、3wt％的聚乙烯醇和0.3wt％的羟乙基纤维素，充分混匀后加入0.01wt％的有机硅消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液浸涂于平均孔径为0.1um的多孔陶瓷膜支撑体上，依次经干燥、煅烧和自然冷却，获得氧化钛陶瓷超滤膜；其中，
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。
本实施例制得的氧化钛陶瓷超滤膜如图3所示，其膜层完整，对2g/L的葡聚糖(分子量2万)截留率为94％。
实施例2
(1)在钛酸正丁酯和水以1∶10的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt％的柠檬酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
(2)在上述氧化钛溶胶中加入3wt％的乳化剂(环己烷、正己醇和OP-10的摩尔比为8∶2∶1)，于100℃进行水热反应3h；
(3)将步骤(2)所得的物料经自然冷却后进行剪切或超声处理，获得半透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入1wt％的聚乙二醇、3wt％的聚乙烯醇和0.3wt％的羟乙基纤维素，充分混匀后加入0.01wt％的有机硅消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液浸涂于平均孔径为0.1um的多孔陶瓷膜支撑体上，依次经干燥、煅烧和自然冷却，获得氧化钛陶瓷超滤膜；其中，
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。
本实施例制得的氧化钛陶瓷超滤膜如图3所示，其膜层完整，对2g/L的葡聚糖(分子量2万)截留率为95％。
实施例3
(1)在钛酸正丁酯和水以1∶50的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt％的聚丙烯酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
(2)在上述氧化钛溶胶中加入3wt％的乳化剂(环己烷、正己醇和OP-10的摩尔比为8∶2∶1)，于150℃进行水热反应1h；
(3)将步骤(2)所得的物料经自然冷却后进行剪切或超声处理，获得半透明的氧化钛纳米溶液；
(4)在上述氧化钛纳米溶液中加入1wt％的聚乙二醇、5wt％的聚乙烯醇和1wt％的羟乙基纤维素，充分混匀后加入0.1wt％的有机硅消泡剂，充分搅拌，获得涂膜液；
(5)将上述涂膜液浸涂于平均孔径为0.1um的多孔陶瓷膜支撑体上，依次经干燥、煅烧和自然冷却，获得氧化钛陶瓷超滤膜；其中，
上述干燥为：以1℃/min的速率升温至120℃，保温干燥5h；
上述煅烧为：以5℃/min的速率升温至450℃，保温煅烧5h。
本实施例制得的氧化钛陶瓷超滤膜如图3所示，其膜层完整，对2g/L的葡聚糖(分子量2万)截留率为90％。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (1)

1.一种氧化钛陶瓷超滤膜的制备方法，其特征在于：包括如下步骤：
（1）在钛酸正丁酯和水以1:10-50的摩尔比混合进行溶胶凝胶反应，再加入酸进行解胶，解胶后的物料的pH为3，然后加入1wt%的柠檬酸钠或聚丙烯酸钠，混合均匀后，获得分散良好的氧化钛溶胶；
（2）在上述氧化钛溶胶中加入乳化剂，于100-150℃进行水热反应1-3h，该乳化剂由环己烷、正己醇和OP-10以8:2:1的摩尔比组成，乳化剂的加入量为所述氧化钛溶胶的1-3wt%；
（3）将步骤（2）所得的物料进行剪切或超声处理，获得透明的氧化钛纳米溶液；
（4）在上述氧化钛纳米溶液中加入聚乙二醇、聚乙烯醇、羟乙基纤维素和有机硅消泡剂，充分搅拌，获得涂膜液；
（5）将上述涂膜液涂覆于支撑体上，依次经干燥、煅烧和自然冷却，获得氧化钛陶瓷超滤膜；干燥的温度为80-120℃，时间为2-5h；煅烧的温度为350-500℃，时间为2-5h。
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