阅读说明：本技术 一种氧化锆陶瓷超滤膜的制备方法 (Preparation method of zirconia ceramic ultrafiltration membrane ) 是由 陈云强 洪昱斌 方富林 蓝伟光 于 2020-06-12 设计创作，主要内容包括：本发明公开了一种氧化锆陶瓷超滤膜的制备方法。本发明将溶胶-凝胶法和微乳介质水热法有机结合,利用溶胶-凝胶法形成的溶胶作为前驱体,然后通过微乳介质于120-150℃进行水热法制得氧化锆纳米溶液,将它直接制成涂膜液,制备出氧化锆陶瓷超滤膜,能解决目前制备陶瓷超滤膜方法的缺点和不足。(The invention discloses a preparation method of a zirconia ceramic ultrafiltration membrane. The method organically combines a sol-gel method and a microemulsion medium hydrothermal method, utilizes sol formed by the sol-gel method as a precursor, then prepares the zirconia nano solution by the microemulsion medium hydrothermal method at the temperature of 120-150 ℃, directly prepares the coating solution, prepares the zirconia ceramic ultrafiltration membrane, and can solve the defects of the existing method for preparing the ceramic ultrafiltration membrane.)

1. A preparation method of a zirconia ceramic ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing zirconia sol by using raw materials including inorganic zirconium salt and a dispersing agent through a sol-gel method;

(2) adding an emulsifier into the zirconia sol, and carrying out hydrothermal reaction for 1-3h at the temperature of 120-150 ℃, wherein the emulsifier consists of cyclohexane, hexanol and OP-10;

(3) shearing or ultrasonically treating the material obtained in the step (2) to obtain a zirconium oxide nano solution;

(4) adding a plasticizer, a binder and a defoaming agent into the zirconia nano solution, and fully stirring to obtain a coating solution;

(5) and coating the coating liquid on a support, and sequentially drying, calcining and naturally cooling to obtain the zirconia ceramic ultrafiltration membrane.

2. The method of claim 1, wherein: the molar ratio of the cyclohexane to the hexanol to the OP-10 is 8-10: 3: 2.

3. The method of claim 2, wherein: the addition amount of the emulsifier is 1-5 wt% of the zirconia sol.

4. The method of claim 1, wherein: the inorganic zirconium salt is zirconium chloride, zirconium oxychloride or zirconyl sulfate.

5. The method of claim 1, wherein: the dispersing agent is polyethylene glycol or nitric acid.

6. The method of claim 1, wherein: the plasticizer is polyvinyl alcohol.

7. The method of claim 1, wherein: the binder is hydroxyethyl cellulose.

8. The method of claim 1, wherein: the defoaming agent is an organic silicon defoaming agent.

9. The production method according to any one of claims 1 to 8, characterized in that: the drying temperature is 80-120 ℃, and the drying time is 2-5 h.

10. The production method according to any one of claims 1 to 8, characterized in that: the calcining temperature is 500-700 ℃, and the time is 2-5 h.

Technical Field

The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of a zirconia ceramic ultrafiltration membrane.

Background

Membrane separation technology is a separation technology that arose in the 60's of the 20 th century and has developed rapidly over decades. The application field of the membrane separation technology is deep in various aspects of life and production of people, such as chemical industry, environmental protection, electronics, textiles, medicines, foods and the like. The organic polymer membrane is always dominant in the field of membrane separation, and although the organic membrane has many advantages, the organic membrane has the defects of no high temperature resistance, no chemical corrosion resistance, easy pollution, swelling and shrinkage in a solvent and the like, so that the application of the organic polymer membrane is limited.

Compared with organic membranes, inorganic membranes have many excellent characteristics as emerging separation media, such as good chemical stability, high mechanical strength, high temperature resistance, microbial corrosion resistance, long service life and the like, so that the inorganic membranes become green and environment-friendly materials. The ceramic membrane preparation process comprises a solid particle sintering method, an anodic oxidation method, a sol-gel method, a chemical vapor deposition method, a thermal decomposition method and the like. Of which the sol-gel method and the hydrothermal method are most widely used. The sol-gel preparation of ceramic films generally requires repeated recoating to form complete films, while the hydrothermal method requires high-temperature and high-pressure equipment to prepare the ceramic films. Therefore, the process of preparing a ceramic film by one-time coating has been a hot spot of research.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of a zirconia ceramic ultrafiltration membrane.

The technical scheme of the invention is as follows:

a preparation method of a zirconia ceramic ultrafiltration membrane comprises the following steps:

(1) preparing zirconia sol by using raw materials including inorganic zirconium salt and a dispersing agent through a sol-gel method;

(2) adding an emulsifier into the zirconia sol, and carrying out hydrothermal reaction for 1-3h at the temperature of 120-150 ℃, wherein the emulsifier consists of cyclohexane, hexanol and OP-10 (a condensation product of alkylphenol and ethylene oxide);

(3) shearing or ultrasonically treating the material obtained in the step (2) to obtain a zirconium oxide nano solution;

(4) adding a plasticizer, a binder and a defoaming agent into the zirconia nano solution, and fully stirring to obtain a coating solution;

(5) and coating the coating liquid on a support, and sequentially drying, calcining and naturally cooling to obtain the zirconia ceramic ultrafiltration membrane.

In a preferred embodiment of the present invention, the molar ratio of cyclohexane, n-hexanol and OP-10 is 8-10: 3: 2.

Further preferably, the emulsifier is added in an amount of 1 to 5 wt% of the zirconia sol.

In a preferred embodiment of the invention, the inorganic zirconium salt is zirconium chloride, zirconium oxychloride or zirconyl sulfate.

In a preferred embodiment of the present invention, the dispersant is polyethylene glycol or nitric acid, and the addition amount thereof is preferably 0.1 to 1.5 wt% of the zirconia sol.

In a preferred embodiment of the present invention, the plasticizer is polyvinyl alcohol, and the addition amount thereof is preferably 2 to 5 wt% of the zirconia nano solution.

In a preferred embodiment of the present invention, the binder is hydroxyethyl cellulose, and the addition amount thereof is preferably 2 to 8 wt% of the zirconia nano solution.

In a preferred embodiment of the present invention, the defoaming agent is a silicone defoaming agent, and the addition amount thereof is preferably 0.01 to 1 wt% of the zirconia nano solution.

In a preferred embodiment of the invention, the drying is carried out at a temperature of from 80 to 120 ℃ for a period of from 2 to 5 hours.

In a preferred embodiment of the present invention, the temperature of the calcination is 500-700 ℃ and the time is 2-5 h.

The invention has the beneficial effects that: the method organically combines a sol-gel method and a microemulsion medium hydrothermal method, utilizes sol formed by the sol-gel method as a precursor, then carries out the hydrothermal method at the temperature of 120 ℃ and 150 ℃ through a microemulsion medium to prepare the zirconia nano solution, directly prepares the zirconia nano solution into a coating liquid, can prepare the flawless and high-quality zirconia ceramic ultrafiltration membrane without coating for many times, and solves the defects of the existing method for preparing the ceramic ultrafiltration membrane.

Drawings

FIG. 1 is a scanning electron micrograph of a comparative film obtained in comparative example 1 of the present invention.

FIG. 2 is a scanning electron micrograph of a comparative film obtained according to comparative example 2 of the present invention.

FIG. 3 is a scanning electron micrograph of the zirconia ceramic ultrafiltration membrane prepared in examples 1 and 2 of the present invention.

Detailed Description

The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.

Comparative example 1

(1) Adding 1.5 wt% of polyethylene glycol into 0.5mol/L zirconium oxychloride solution, uniformly mixing, adjusting the pH to 11 by using 1mol/L ammonia water or 1mol/L sodium hydroxide solution at the reaction temperature of 80 ℃ under the conditions of certain dropping speed and stirring speed, reacting for 4 hours, cooling to obtain gel, drying at the temperature of 60 ℃, re-dissolving the gel in water, and adjusting the pH to 4 by using 1mol/L hydrochloric acid or 1mol/L nitric acid to obtain zirconium oxide sol;

(2) adding 0.5 wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 9: 3: 2) into the zirconia sol, and carrying out hydrothermal reaction for 3h at 120 ℃;

(3) naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent zirconium oxide nano solution;

(4) adding 2 wt% of polyvinyl alcohol and 0.1 wt% of hydroxyethyl cellulose into the zirconia nano solution, fully and uniformly mixing, adding 0.01 wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;

(5) coating the film coating liquid on a porous ceramic film support with the average pore diameter of 0.1um in an immersion manner, and sequentially drying, calcining and naturally cooling to obtain a contrast film; wherein the content of the first and second substances,

the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;

the calcination is as follows: heating to 700 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3 h.

The comparative membrane prepared in this comparative example is shown in FIG. 1, and the membrane layer is easily cracked, and the rejection rate of 2g/L glucan (molecular weight: 4 ten thousand) is 15%.

Comparative example 2

(1) Adding 1.5 wt% of polyethylene glycol into 0.5mol/L zirconium oxychloride solution, uniformly mixing, adjusting the pH to 11 by using 1mol/L ammonia water or 1mol/L sodium hydroxide solution at the reaction temperature of 80 ℃ under the conditions of certain dropping speed and stirring speed, reacting for 4 hours, cooling to obtain gel, drying at the temperature of 60 ℃, re-dissolving the gel in water, and adjusting the pH to 4 by using 1mol/L hydrochloric acid or 1mol/L nitric acid to obtain zirconium oxide sol;

(2) adding 6 wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 9: 3: 2) into the zirconia sol, and carrying out hydrothermal reaction for 3h at 120 ℃;

(3) naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent zirconium oxide nano solution;

(4) adding 2 wt% of polyvinyl alcohol and 0.1 wt% of hydroxyethyl cellulose into the zirconia nano solution, fully and uniformly mixing, adding 0.01 wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;

(5) coating the film coating liquid on a porous ceramic film support with the average pore diameter of 0.1um in an immersion manner, and sequentially drying, calcining and naturally cooling to obtain a contrast film; wherein the content of the first and second substances,

the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;

the calcination is as follows: heating to 700 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3 h.

As shown in FIG. 2, the comparative membrane prepared in this comparative example was easy to crack, and had a retention of 50% for 2g/L of glucan (molecular weight: 4 ten thousand).

Example 1

(1) Adding 1.5 wt% of polyethylene glycol into 0.5mol/L zirconium oxychloride solution, uniformly mixing, adjusting the pH to 11 by using 1mol/L ammonia water or 1mol/L sodium hydroxide solution at the reaction temperature of 80 ℃ under the conditions of certain dropping speed and stirring speed, reacting for 4 hours, cooling to obtain gel, drying at the temperature of 60 ℃, re-dissolving the gel in water, and adjusting the pH to 4 by using 1mol/L hydrochloric acid or 1mol/L nitric acid to obtain zirconium oxide sol;

(2) adding 1 wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 9: 3: 2) into the zirconia sol, and carrying out hydrothermal reaction at 120 ℃ for 3 h;

(3) naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent zirconium oxide nano solution;

(4) adding 2 wt% of polyvinyl alcohol and 0.1 wt% of hydroxyethyl cellulose into the zirconia nano solution, fully and uniformly mixing, adding 0.01 wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;

(5) dipping the coating liquid on a porous ceramic membrane support with the average pore diameter of 0.1um, and sequentially drying, calcining and naturally cooling to obtain a zirconia ceramic ultrafiltration membrane; wherein the content of the first and second substances,

the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;

the calcination is as follows: heating to 700 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3 h.

As shown in FIG. 3, the membrane layer of the zirconia ceramic ultrafiltration membrane prepared in the example is complete, and the retention rate of 2g/L glucan (molecular weight 4 ten thousand) is 96%.

Example 2

(1) Adding 0.1 wt% of polyethylene glycol into 0.5mol/L zirconium oxychloride solution, uniformly mixing, adjusting the pH to 9 by using 1mol/L ammonia water or 1mol/L sodium hydroxide solution at the reaction temperature of 80 ℃ under the conditions of certain dropping speed and stirring speed, reacting for 4 hours, cooling to obtain gel, drying at the temperature of 60 ℃, re-dissolving the gel in water, and adjusting the pH to 4 by using 1mol/L hydrochloric acid or 1mol/L nitric acid to obtain zirconium oxide sol;

(2) adding 1 wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 9: 3: 2) into the zirconia sol, and carrying out hydrothermal reaction for 1h at 150 ℃;

(3) naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent zirconium oxide nano solution;

(4) adding 5 wt% of polyvinyl alcohol and 1 wt% of hydroxyethyl cellulose into the zirconia nano solution, fully and uniformly mixing, adding 1 wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;

(5) dipping the coating liquid on a porous ceramic membrane support with the average pore diameter of 0.1um, and sequentially drying, calcining and naturally cooling to obtain a zirconia ceramic ultrafiltration membrane; wherein the content of the first and second substances,

the drying comprises the following steps: heating to 120 ℃ at the speed of 1 ℃/min, and keeping the temperature and drying for 5 hours;

the calcination is as follows: heating to 600 ℃ at the speed of 5 ℃/min, and carrying out heat preservation and calcination for 3 h.

As shown in FIG. 3, the membrane layer of the zirconia ceramic ultrafiltration membrane prepared in the example is complete, and the rejection rate of 2g/L glucan (molecular weight 4 ten thousand) is 95%.

The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.