WO2021248896A1 - Preparation method for titania ceramic ultrafiltration membrane - Google Patents

Preparation method for titania ceramic ultrafiltration membrane Download PDF

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WO2021248896A1
WO2021248896A1 PCT/CN2020/142010 CN2020142010W WO2021248896A1 WO 2021248896 A1 WO2021248896 A1 WO 2021248896A1 CN 2020142010 W CN2020142010 W CN 2020142010W WO 2021248896 A1 WO2021248896 A1 WO 2021248896A1
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titanium oxide
preparation
sol
ultrafiltration membrane
titania
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PCT/CN2020/142010
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French (fr)
Chinese (zh)
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陈云强
洪昱斌
方富林
蓝伟光
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三达膜科技（厦门）有限公司
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    • B01D67/0039—Inorganic membrane manufacture
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Definitions

  • the invention belongs to the technical field of membrane separation, and specifically relates to a preparation method of a titanium oxide ceramic ultrafiltration membrane.
  • Membrane separation is mainly divided into microfiltration, ultrafiltration, nanofiltration and reverse osmosis.
  • the application field of membrane separation technology has penetrated into all aspects of people's life and production, such as chemical industry, environmental protection, electronics, textile, medicine, food, etc.
  • Organic membranes are not resistant to high temperatures, poorly resistant to chemical corrosion, easy to pollute, swelling and shrinking in solvents, etc., so that organic membranes are restricted in some separation processes that require special conditions.
  • Inorganic membrane has the characteristics of good chemical stability, high mechanical strength, high temperature resistance, anti-microbial corrosion and long service life, so that it can be used in some harsh conditions.
  • methods for preparing nanoparticles mainly include chemical precipitation, sol-gel, hydrothermal, and microemulsion methods.
  • the sol-gel method is the most important method for preparing the titanium dioxide ceramic ultrafiltration membrane by the liquid phase method.
  • the hydrothermal preparation of titanium dioxide can avoid the problem of hard agglomeration that may be caused by high temperature treatment in wet chemistry.
  • the prepared titanium dioxide has a good crystal structure and a high specific surface area.
  • the hydrothermal preparation requires relatively high equipment, high temperature and high pressure are required. It can be prepared under the conditions.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a titanium oxide ceramic ultrafiltration membrane.
  • a preparation method of titanium oxide ceramic ultrafiltration membrane includes the following steps:
  • the emulsifier is composed of cyclohexane, n-hexanol and OP-10 (condensation of alkylphenol and ethylene oxide).
  • step (2) The material obtained in step (2) is subjected to shearing or ultrasonic treatment to obtain a transparent titanium oxide nano-solution;
  • the molar ratio of the cyclohexane, n-hexanol and OP-10 is 7-9:2:1.
  • the added amount of the emulsifier is 1-5% by weight of the titanium oxide sol.
  • the organic titanium salt is n-butyl titanate or isopropanol titanate, and its molar ratio to water is preferably 1:10-50.
  • the first dispersant is sodium citrate or sodium polyacrylate
  • the second dispersant is polyethylene glycol
  • the added amount of the first dispersant is preferably that of titanium oxide sol. 0.1-1wt%
  • the added amount of the second dispersant is preferably 0.1-1wt% of the titanium oxide nano solution.
  • the plasticizer is polyvinyl alcohol, and its addition amount is preferably 1-5 wt% of the titanium oxide nano solution.
  • the binder is hydroxyethyl cellulose, and its addition amount is preferably 0.1-5 wt% of the titanium oxide nano solution.
  • the defoaming agent is a silicone defoaming agent, and its addition amount is preferably 0.01-0.1 wt% of the titanium oxide nano solution.
  • the drying temperature is 80-120°C, and the time is 2-5h.
  • the calcination temperature is 350-500° C., and the time is 2-5 h. .
  • the sol-gel method is combined with the microemulsion medium hydrothermal method to prepare titanium oxide nano sol, additives are added to the titania sol to make a coating liquid, which is dipped and coated on the porous alumina ceramic membrane, and then dried and calcined Obtain the titanium oxide ultrafiltration membrane layer.
  • the titania nano sol is prepared under a shorter time and a lower temperature hydrothermal reaction.
  • the coating solution is prepared, dried, dried, and calcined. It is possible to prepare defect-free, high-quality titanium oxide ultrafiltration membranes without multiple coatings.
  • Figure 1 is a scanning electron micrograph of the contrast film prepared in Comparative Example 1 of the present invention.
  • Figure 2 is a scanning electron micrograph of the contrast film prepared in Comparative Example 2 of the present invention.
  • Fig. 3 is a scanning electron microscope photograph of the titanium oxide ceramic ultrafiltration membrane prepared in Examples 1 to 3 of the present invention.
  • step (3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
  • the above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
  • the above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
  • the comparative film prepared in this comparative example is shown in Fig. 1, the film layer is cracked, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 0%.
  • step (3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
  • the above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
  • the above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
  • the comparative film prepared in this comparative example is shown in Fig. 2, the film layer is cracked, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 15%.
  • step (3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
  • the above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
  • the above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
  • the titanium oxide ceramic ultrafiltration membrane prepared in this example is shown in FIG. 3, the membrane layer is complete, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 94%.
  • step (3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
  • the above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
  • the above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
  • the titanium oxide ceramic ultrafiltration membrane prepared in this embodiment is shown in FIG. 3, and the membrane layer is complete, and the rejection rate for 2 g/L dextran (molecular weight 20,000) is 95%.
  • step (3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
  • the above-mentioned drying is: heating up to 120°C at a rate of 1°C/min, holding and drying for 5 hours;
  • the above-mentioned calcination is: heating up to 450°C at a rate of 5°C/min, heat preservation and calcination for 5 hours.
  • the titanium oxide ceramic ultrafiltration membrane prepared in this embodiment is shown in FIG. 3, and the membrane layer is complete, and the rejection rate for 2 g/L dextran (molecular weight 20,000) is 90%.
  • the invention discloses a preparation method of a titanium oxide ceramic ultrafiltration membrane.
  • a sol-gel method is combined with a microemulsion medium hydrothermal method to prepare a titanium oxide nano sol, an additive is added to the titania sol to prepare a coating liquid, which is dipped and coated on a porous alumina ceramic membrane, and is dried and calcined to obtain oxidation Titanium ultrafiltration membrane layer.
  • a specific emulsifier is added to the titanium oxide sol, and the titanium oxide nanosol is prepared under a hydrothermal reaction in a shorter time and at a lower temperature. Titanium ultrafiltration membrane has industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A preparation method for a titania ceramic ultrafiltration membrane. A sol-gel process is combined with hydrothermal processing of a microemulsion medium to prepare a titania nanosol. An additive is introduced into a titania sol to form a membrane coating solution, which is dip-coated onto a porous alumina ceramic membrane; said membrane is then dried and calcined such that a titania ultrafiltration membrane layer may be obtained. In the invention, a specific emulsifier is added to a titania sol; a titania nanosol is prepared by means of a low-temperature hydrothermal reaction having a short reaction time; a membrane coating solution is formulated, and drying and calcining are carried out, thus producing a titania ultrafiltration membrane.

Description

一种氧化钛陶瓷超滤膜的制备方法Method for preparing titanium oxide ceramic ultrafiltration membrane 技术领域Technical field
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。The invention belongs to the technical field of membrane separation, and specifically relates to a preparation method of a titanium oxide ceramic ultrafiltration membrane.
背景技术Background technique
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。Membrane separation is mainly divided into microfiltration, ultrafiltration, nanofiltration and reverse osmosis. The application field of membrane separation technology has penetrated into all aspects of people's life and production, such as chemical industry, environmental protection, electronics, textile, medicine, food, etc. Organic membranes are not resistant to high temperatures, poorly resistant to chemical corrosion, easy to pollute, swelling and shrinking in solvents, etc., so that organic membranes are restricted in some separation processes that require special conditions. Inorganic membrane has the characteristics of good chemical stability, high mechanical strength, high temperature resistance, anti-microbial corrosion and long service life, so that it can be used in some harsh conditions.
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。In the prior art, methods for preparing nanoparticles mainly include chemical precipitation, sol-gel, hydrothermal, and microemulsion methods. Among them, the sol-gel method is the most important method for preparing the titanium dioxide ceramic ultrafiltration membrane by the liquid phase method. However, when the ceramic ultrafiltration membrane is prepared from the titanium dioxide nano solution obtained by the sol-gel method, due to the severe shrinkage during the calcination process, multiple coatings are required, and the stability of the prepared sol has a greater impact on the coating effect. Restrict the expansion of the sol-gel method. The hydrothermal preparation of titanium dioxide can avoid the problem of hard agglomeration that may be caused by high temperature treatment in wet chemistry. The prepared titanium dioxide has a good crystal structure and a high specific surface area. However, because the hydrothermal preparation requires relatively high equipment, high temperature and high pressure are required. It can be prepared under the conditions.
发明内容Summary of the invention
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。The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a titanium oxide ceramic ultrafiltration membrane.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
一种氧化钛陶瓷超滤膜的制备方法，包括如下步骤：A preparation method of titanium oxide ceramic ultrafiltration membrane includes the following steps:
(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；(1) Prepare titanium oxide sol by the sol-gel method with raw materials including organic titanium salt and first dispersant;
(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；(2) Add an emulsifier to the above-mentioned titanium oxide sol, and conduct a hydrothermal reaction at 100-150°C for 1-3h. The emulsifier is composed of cyclohexane, n-hexanol and OP-10 (condensation of alkylphenol and ethylene oxide).物) Composition;
(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；(3) The material obtained in step (2) is subjected to shearing or ultrasonic treatment to obtain a transparent titanium oxide nano-solution;
(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；(4) Add the second dispersant, plasticizer, binder and defoamer to the above-mentioned titanium oxide nano solution, and stir it fully to obtain a coating liquid;
(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。(5) Coating the above-mentioned coating liquid on the support, successively drying, calcining and natural cooling to obtain a titanium oxide ceramic ultrafiltration membrane.
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。In a preferred embodiment of the present invention, the molar ratio of the cyclohexane, n-hexanol and OP-10 is 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％。Further preferably, the added amount of the emulsifier is 1-5% by weight of the titanium oxide sol.
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。In a preferred embodiment of the present invention, the organic titanium salt is n-butyl titanate or isopropanol titanate, and its molar ratio to water is preferably 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％。In a preferred embodiment of the present invention, the first dispersant is sodium citrate or sodium polyacrylate, the second dispersant is polyethylene glycol, and the added amount of the first dispersant is preferably that of titanium oxide sol. 0.1-1wt%, and the added amount of the second dispersant is preferably 0.1-1wt% of the titanium oxide nano solution.
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％。In a preferred embodiment of the present invention, the plasticizer is polyvinyl alcohol, and its addition amount is preferably 1-5 wt% of the titanium oxide nano solution.
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％。In a preferred embodiment of the present invention, the binder is hydroxyethyl cellulose, and its addition amount is preferably 0.1-5 wt% of the titanium oxide nano solution.
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％。In a preferred embodiment of the present invention, the defoaming agent is a silicone defoaming agent, and its addition amount is preferably 0.01-0.1 wt% of the titanium oxide nano solution.
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。In a preferred embodiment of the present invention, the drying temperature is 80-120°C, and the time is 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。。In a preferred embodiment of the present invention, the calcination temperature is 350-500° C., and the time is 2-5 h. .
本发明的有益效果是：The beneficial effects of the present invention are:
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。1. In the present invention, the sol-gel method is combined with the microemulsion medium hydrothermal method to prepare titanium oxide nano sol, additives are added to the titania sol to make a coating liquid, which is dipped and coated on the porous alumina ceramic membrane, and then dried and calcined Obtain the titanium oxide ultrafiltration membrane layer.
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。2. In the present invention, by adding a specific emulsifier to the titania sol, the titania nano sol is prepared under a shorter time and a lower temperature hydrothermal reaction. The coating solution is prepared, dried, dried, and calcined. It is possible to prepare defect-free, high-quality titanium oxide ultrafiltration membranes without multiple coatings.
附图说明Description of the drawings
图1为本发明对比例1制得的对比膜的扫描电镜照片。Figure 1 is a scanning electron micrograph of the contrast film prepared in Comparative Example 1 of the present invention.
图2为本发明对比例2制得的对比膜的扫描电镜照片。Figure 2 is a scanning electron micrograph of the contrast film prepared in Comparative Example 2 of the present invention.
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。Fig. 3 is a scanning electron microscope photograph of the titanium oxide ceramic ultrafiltration membrane prepared in Examples 1 to 3 of the present invention.
具体实施方式detailed description
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。The technical solutions of the present invention will be further illustrated and described below through specific implementations in conjunction with the accompanying drawings.
对比例1Comparative example 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；(1) Mix n-butyl titanate and water at a molar ratio of 1:10 for sol-gel reaction, then add acid for degelling, the pH of the material after degelling is 3, and then add 1wt% sodium citrate , After mixing uniformly, a well-dispersed titanium oxide sol is obtained;
(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；(2) Add 0.5wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2:1) to the above-mentioned titanium oxide sol, and conduct a hydrothermal reaction at 100°C for 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；(3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
(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；(4) Add 1wt% polyethylene glycol, 3wt% polyvinyl alcohol and 0.3wt% hydroxyethyl cellulose to the above titanium oxide nano solution, mix well and add 0.01wt% silicone defoamer, Stir fully to obtain the coating liquid;
(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，(5) Dip coating the above-mentioned coating liquid on a porous ceramic membrane support with an average pore diameter of 0.1um, followed by drying, calcination and natural cooling to obtain a comparative membrane; where,
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；The above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。The above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
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％。The comparative film prepared in this comparative example is shown in Fig. 1, the film layer is cracked, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 0%.
对比例2Comparative example 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；(1) Mix n-butyl titanate and water at a molar ratio of 1:10 to carry out the sol-gel reaction, then add acid to degelatinize, the pH of the degelled material is 3, and then add 1wt% sodium polyacrylate , After mixing uniformly, a well-dispersed titanium oxide sol is obtained;
(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；(2) Add 7wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2:1) to the above-mentioned titanium oxide sol, and conduct a hydrothermal reaction at 100°C for 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；(3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
(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；(4) Add 1wt% polyethylene glycol, 3wt% polyvinyl alcohol and 0.3wt% hydroxyethyl cellulose to the above titanium oxide nano solution, mix well and add 0.01wt% silicone defoamer, Stir fully to obtain the coating liquid;
(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，(5) Dip coating the above-mentioned coating liquid on a porous ceramic membrane support with an average pore diameter of 0.1um, followed by drying, calcination and natural cooling to obtain a comparative membrane; where,
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；The above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。The above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
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％。The comparative film prepared in this comparative example is shown in Fig. 2, the film layer is cracked, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 15%.
实施例1Example 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；(1) Mix n-butyl titanate and water at a molar ratio of 1:10 for sol-gel reaction, then add acid for degelling, the pH of the material after degelling is 3, and then add 1wt% sodium citrate , After mixing uniformly, a well-dispersed titanium oxide sol is obtained;
(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；(2) Add 1wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2:1) to the above-mentioned titanium oxide sol, and carry out a hydrothermal reaction at 100°C for 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；(3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
(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；(4) Add 1wt% polyethylene glycol, 3wt% polyvinyl alcohol and 0.3wt% hydroxyethyl cellulose to the above titanium oxide nano solution, mix well and add 0.01wt% silicone defoamer, Stir fully to obtain the coating liquid;
(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，(5) Dip coating the above-mentioned coating liquid on a porous ceramic membrane support with an average pore diameter of 0.1um, followed by drying, calcination and natural cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein,
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；The above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。The above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
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％。The titanium oxide ceramic ultrafiltration membrane prepared in this example is shown in FIG. 3, the membrane layer is complete, and the rejection rate of 2 g/L dextran (molecular weight 20,000) is 94%.
实施例2Example 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；(1) Mix n-butyl titanate and water at a molar ratio of 1:10 for sol-gel reaction, then add acid for degelling, the pH of the material after degelling is 3, and then add 1wt% sodium citrate , After mixing uniformly, a well-dispersed titanium oxide sol is obtained;
(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；(2) Add 3wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2:1) to the above-mentioned titanium oxide sol, and conduct a hydrothermal reaction at 100°C for 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；(3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
(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；(4) Add 1wt% polyethylene glycol, 3wt% polyvinyl alcohol and 0.3wt% hydroxyethyl cellulose to the above titanium oxide nano solution, mix well and add 0.01wt% silicone defoamer, Stir fully to obtain the coating liquid;
(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，(5) Dip coating the above-mentioned coating liquid on a porous ceramic membrane support with an average pore diameter of 0.1um, followed by drying, calcination and natural cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein,
上述干燥为：以3℃/min的速率升温至120℃，保温干燥5h；The above-mentioned drying is: heating up to 120°C at a rate of 3°C/min, holding and drying for 5 hours;
上述煅烧为：以3℃/min的速率升温至350℃，保温煅烧3h。The above-mentioned calcination is: heating up to 350°C at a rate of 3°C/min, heat preservation and calcination for 3 hours.
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％。The titanium oxide ceramic ultrafiltration membrane prepared in this embodiment is shown in FIG. 3, and the membrane layer is complete, and the rejection rate for 2 g/L dextran (molecular weight 20,000) is 95%.
实施例3Example 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；(1) Mix n-butyl titanate and water at a molar ratio of 1:50 to carry out the sol-gel reaction, then add acid to degelatinize, the pH of the degelled material is 3, and then add 1wt% sodium polyacrylate , After mixing uniformly, a well-dispersed titanium oxide sol is obtained;
(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；(2) Add 3wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2:1) to the above-mentioned titanium oxide sol, and conduct a hydrothermal reaction at 150°C for 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；(3) The material obtained in step (2) is naturally cooled and then subjected to shearing or ultrasonic treatment to obtain a translucent titanium oxide nano solution;
(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；(4) Add 1wt% of polyethylene glycol, 5wt% of polyvinyl alcohol and 1wt% of hydroxyethyl cellulose to the above titanium oxide nano solution, mix well and add 0.1wt% of silicone defoamer to fully Stir to obtain a coating liquid;
(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，(5) Dip coating the above-mentioned coating liquid on a porous ceramic membrane support with an average pore diameter of 0.1um, followed by drying, calcination and natural cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein,
上述干燥为：以1℃/min的速率升温至120℃，保温干燥5h；The above-mentioned drying is: heating up to 120°C at a rate of 1°C/min, holding and drying for 5 hours;
上述煅烧为：以5℃/min的速率升温至450℃，保温煅烧5h。The above-mentioned calcination is: heating up to 450°C at a rate of 5°C/min, heat preservation and calcination for 5 hours.
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％。The titanium oxide ceramic ultrafiltration membrane prepared in this embodiment is shown in FIG. 3, and the membrane layer is complete, and the rejection rate for 2 g/L dextran (molecular weight 20,000) is 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。The above are only the preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly. That is, the equivalent changes and modifications made according to the scope of the patent of the present invention and the contents of the specification should still be covered by the present invention. In the range.
工业实用性Industrial applicability
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,具有工业实用性。The invention discloses a preparation method of a titanium oxide ceramic ultrafiltration membrane. In the present invention, a sol-gel method is combined with a microemulsion medium hydrothermal method to prepare a titanium oxide nano sol, an additive is added to the titania sol to prepare a coating liquid, which is dipped and coated on a porous alumina ceramic membrane, and is dried and calcined to obtain oxidation Titanium ultrafiltration membrane layer. In the present invention, a specific emulsifier is added to the titanium oxide sol, and the titanium oxide nanosol is prepared under a hydrothermal reaction in a shorter time and at a lower temperature. Titanium ultrafiltration membrane has industrial applicability.

Claims (8)

  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：A method for preparing a titanium oxide ceramic ultrafiltration membrane is characterized in that it comprises the following steps:
    (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；(1) Prepare titanium oxide sol by the sol-gel method with raw materials including organic titanium salt and first dispersant;
    (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组成；(2) Add an emulsifier to the above-mentioned titanium oxide sol, and carry out a hydrothermal reaction at 100-150°C for 1-3h. The emulsifier is composed of cyclohexane, n-hexanol and OP-10;
    (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；(3) The material obtained in step (2) is subjected to shearing or ultrasonic treatment to obtain a transparent titanium oxide nano-solution;
    (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；(4) Add the second dispersant, plasticizer, binder and defoamer to the above-mentioned titanium oxide nano solution, and stir it fully to obtain a coating liquid;
    (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所述环己烷、正己醇和OP-10的摩尔比为7-9:2:1；(5) Coating the above-mentioned coating liquid on the support, followed by drying, calcination and natural cooling to obtain a titanium oxide ceramic ultrafiltration membrane. The molar ratio of cyclohexane, n-hexanol and OP-10 is 7-9: 2:1;
    所述乳化剂的加入量为所述氧化钛溶胶的1-5wt％。The added amount of the emulsifier is 1-5% by weight of the titanium oxide sol.
  2. 如权利要求1所述的制备方法，其特征在于：所述有机钛盐为钛酸正丁酯或钛酸异丙醇酯。The preparation method according to claim 1, wherein the organic titanium salt is n-butyl titanate or isopropanol titanate.
  3. 如权利要求1所述的制备方法，其特征在于：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。The preparation method according to claim 1, wherein the first dispersant is sodium citrate or sodium polyacrylate, and the second dispersant is polyethylene glycol.
  4. 如权利要求1所述的制备方法，其特征在于：所述增塑剂为聚乙烯醇。The preparation method according to claim 1, wherein the plasticizer is polyvinyl alcohol.
  5. 如权利要求1所述的制备方法，其特征在于：所述粘结剂为羟乙基纤维素。The preparation method according to claim 1, wherein the binder is hydroxyethyl cellulose.
  6. 如权利要求1所述的制备方法，其特征在于：所述消泡剂为有机硅消泡剂。The preparation method according to claim 1, wherein the defoaming agent is a silicone defoaming agent.
  7. 如权利要求1至8中任一权利要求所述的制备方法，其特征在于：所述干燥的温度为80-120℃，时间为2-5h。The preparation method according to any one of claims 1 to 8, wherein the drying temperature is 80-120°C, and the time is 2-5h.
  8. 如权利要求1至8中任一权利要求所述的制备方法，其特征在于：所述煅烧的温度为350-500℃，时间为2-5h。The preparation method according to any one of claims 1 to 8, wherein the calcination temperature is 350-500° C., and the time is 2-5 h.
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