CN110743385A - Preparation method of titanium oxide-silicon oxide composite ceramic ultrafiltration membrane - Google Patents
Preparation method of titanium oxide-silicon oxide composite ceramic ultrafiltration membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/027—Silicium oxide
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Abstract
The invention discloses a preparation method of a titanium oxide-silicon oxide composite ceramic ultrafiltration membrane. The method utilizes sol formed by a modified sol-gel method as a precursor, then carries out hydrothermal treatment, and adopts a two-step method to obtain TiO with uniform particle size2‑SiO2The composite nano solution is added with a proper amount of additive to directly prepare a coating solution, the coating solution is coated for one time, and then the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane can be prepared by drying and calciningAnd (3) preparing the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane, and simultaneously adding hydrophilic silicon dioxide to improve the surface acidity of the membrane layer so as to adsorb more hydroxyl groups, thereby showing stronger hydrophilic performance and preparing the super-hydrophilic anti-pollution titanium oxide-silicon oxide composite ceramic ultrafiltration membrane.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membrane preparation, and particularly relates to a preparation method of a titanium oxide-silicon oxide composite ceramic ultrafiltration membrane.
Background
Membrane separation techniques are defined as selective media between two phases, and are mainly classified into microfiltration, ultrafiltration, nanofiltration and reverse osmosis, depending on the pore size. 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 ceramic ultrafiltration membrane has the characteristics of good chemical stability, strong biological resistance, high mechanical strength, no toxicity, high temperature resistance and the like, and is widely applied to the fields of environment-harsh organisms, foods, chemical industry and the like.
The sol-gel method is the most important method for preparing the ceramic ultrafiltration membrane. The sol-gel method has simple preparation process and easily controlled process, and can be used for preparing film layers on substrates with different shapes and different base materials in a large area, but the sol obtained by the sol-gel method has serious shrinkage in the calcining process and needs coating for many times, and the stability of the prepared sol has great influence on the coating effect, thereby limiting the expanded production of the sol-gel method to a certain extent.
In order to avoid the cracking of the film layer, the drying process is accurately controlled by methods such as drying under a constant temperature and humidity environment, sectional drying, drying time prolonging, drying under a supercritical condition and the like, so that the cracking of the film layer is prevented, but the methods need to precisely control the temperature and the humidity of the production process, so that the equipment investment cost and the production cost are greatly increased. Therefore, there is a need to develop a high-performance ceramic ultrafiltration membrane technology with simple process, low equipment investment and low cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a titanium oxide-silicon oxide composite ceramic ultrafiltration membrane.
The technical scheme of the invention is as follows:
a preparation method of a titanium oxide-silicon oxide composite ceramic ultrafiltration membrane comprises the following steps:
(1) adding polyethylene glycol with the weight-average molecular weight of 350-500 into an alcoholic solution of organic salt, and dropwise adding an alcoholic solution containing 4-6 wt% of water into the alcoholic solution of organic salt at the temperature of 75-85 ℃ according to the molar ratio of the organic salt to the water of 1: 10-100; after the dropwise adding is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 2-3; adding a dispersing agent to a final concentration of 0.8-1.2 wt%, and uniformly mixing to obtain TiO2-SiO2Compounding sol; the organic salt consists of organic titanium salt and organic silicon salt in the molar ratio of 2 to 1-3;
(2) TiO obtained in the step (1)2-SiO2The composite sol is put into a hydrothermal reaction kettle with the filling degree of 50-60 percent, and is subjected to heat preservation reaction for 8-10h at the temperature of 120-plus-150 ℃, and then is cooled to prepare TiO2-SiO2Compounding the nano solution;
(3) adding the TiO obtained in the step (2)2-SiO2Adding polyethylene glycol with the weight-average molecular weight of 350-450 and a binder serving as a plasticizer into the composite nano solution, respectively enabling the final concentrations of the plasticizer and the binder to be 3-5 wt% and 0.1-0.5 wt%, adding a defoaming agent until the final concentration is 0.01-0.1 wt%, and uniformly mixing to obtain a coating solution;
(4) coating the film coating liquid on a porous alumina ceramic membrane support, heating to 80-120 ℃ at the speed of 1-3 ℃/min, preserving heat, drying for 2-5h, then heating to 350-600 ℃ at the speed of 1-5 ℃/min, preserving heat, calcining for 2-5h, and cooling to obtain the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane.
In a preferred embodiment of the invention, the dispersant is sodium citrate or sodium polyacrylate.
In a preferred embodiment of the present invention, the organic titanium salt is n-butyl titanate or isopropyl titanate.
In a preferred embodiment of the invention, the organosilicate is tetraethylorthosilicate.
In a preferred embodiment of the present invention, the binder is a cellulose-based compound having a molecular weight of 6000-10000, which is hydroxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose.
In a preferred embodiment of the present invention, the defoamer is a silicone defoamer.
In a preferred embodiment of the present invention, the porous alumina ceramic membrane support has an average pore size of 0.1 μm.
The invention has the beneficial effects that: the method utilizes sol formed by a modified sol-gel method as a precursor, then carries out hydrothermal treatment, and adopts a two-step method to obtain TiO with uniform particle size2-SiO2The composite nano solution is added with a proper amount of additive to directly prepare a coating solution, the coating solution is coated for one time, and then the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane is prepared by drying and calcining.
Drawings
FIG. 1 is a scanning electron micrograph of a membrane layer of a titania ceramic ultrafiltration membrane prepared in comparative example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the membrane layer of the titania-silica composite ceramic ultrafiltration membrane prepared in example 1 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) At 0.5moAdding PEG-400 into the alcohol solution of L/L n-butyl titanate to make the final mass concentration 0.3%, and adding the alcohol solution containing 5 wt% of water dropwise into the alcohol solution of the organic salt at 80 ℃ and the molar ratio of the n-butyl titanate to the water of 1: 50; after the dropwise addition is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 2; adding a dispersing agent to enable the final mass concentration to be 1%, and uniformly mixing to obtain TiO2Sol;
(2) TiO obtained in the step (1)2Putting the sol into a hydrothermal reaction kettle with the filling degree of 60 percent, carrying out heat preservation reaction for 10 hours at the temperature of 150 ℃, and cooling to obtain TiO2Nano solution;
(3) adding the TiO obtained in the step (2)2Adding PEG-400 and hydroxymethyl cellulose with the molecular weight of 6000-10000 into the nano solution, respectively setting the final mass concentrations of the PEG-400 and the hydroxymethyl cellulose to be 4 percent and 0.3 percent, adding an organic silicon defoamer byk028 (Germany Bike company) and setting the final mass concentration to be 0.05 percent, and uniformly mixing to prepare a coating solution;
(4) the coating liquid is coated on a porous alumina ceramic membrane support body with the average pore diameter of 0.1 mu m, the temperature is raised to 120 ℃ according to the heating rate of 1 ℃/min, the temperature is preserved and dried for 3h, then the temperature is raised to 450 ℃ according to the heating rate of 1 ℃/min, the temperature is preserved and calcined for 3h, and the titanium oxide ceramic ultrafiltration membrane shown in the figure 1 is obtained after cooling, the pure water flux is 100LH, the molecular weight cutoff is 20KD, and the integral bubble pressure is more than 0.5MPa through a bubble pressure test.
Example 1
(1) Adding PEG-400 into 0.5mol/L alcoholic solution of n-butyl titanate and ethyl orthosilicate to make the final mass concentration of the alcoholic solution be 0.3%, and dropwise adding alcoholic solution containing 5 wt% of water into the alcoholic solution of the organic salt at 80 ℃ according to the molar ratio of the n-butyl titanate, the ethyl orthosilicate and the water being 2: 1: 50; after the dropwise addition is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 2; adding a dispersing agent to enable the final mass concentration to be 1%, and uniformly mixing to obtain TiO2-SiO2Compounding sol;
(2) TiO obtained in the step (1)2-SiO2The sol is put into a hydrothermal reaction kettle, the filling degree is 60 percent, and the filling degree is 1Keeping the temperature at 50 ℃ for 10h, and cooling to obtain TiO2-SiO2Compounding the nano solution;
(3) adding the TiO obtained in the step (2)2-SiO2Adding PEG-400 and hydroxymethyl cellulose with the molecular weight of 6000-10000 into the composite nano solution, respectively setting the final mass concentrations of the PEG-400 and the hydroxymethyl cellulose to be 4 percent and 0.3 percent, adding an organic silicon defoamer byk028, setting the final mass concentration to be 0.05 percent, and uniformly mixing to prepare a coating solution;
(4) the coating liquid is coated on a porous alumina ceramic membrane support body with the average pore diameter of 0.1 mu m, the temperature is raised to 120 ℃ according to the heating rate of 1 ℃/min, the temperature is preserved and dried for 3h, then the temperature is raised to 450 according to the heating rate of 1 ℃/min, the temperature is preserved and calcined for 3h, and the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane shown in figure 2 is obtained after cooling, the pure water flux is 150LH, the molecular weight cutoff is 20KD, and no defect pore bubbles appear through a bubble pressure test.
Example 2
(1) Adding PEG-400 into 0.2mol/L alcoholic solution of n-butyl titanate and ethyl orthosilicate to make the final mass concentration of the alcoholic solution be 0.3%, and dropwise adding alcoholic solution containing 5 wt% of water into the alcoholic solution of the organic salt at 75 ℃ according to the molar ratio of the n-butyl titanate, the ethyl orthosilicate and the water being 2: 3: 10; after the dropwise addition is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 3; then adding a dispersing agent to ensure that the final mass concentration is 0.8 percent, and uniformly mixing to prepare TiO2-SiO2Compounding sol;
(2) TiO obtained in the step (1)2-SiO2Putting the sol into a hydrothermal reaction kettle with the filling degree of 50 percent, carrying out heat preservation reaction for 10 hours at the temperature of 120 ℃, and cooling to obtain TiO2-SiO2Compounding the nano solution;
(3) adding the TiO obtained in the step (2)2-SiO2Adding PEG-400 and hydroxymethyl cellulose with the molecular weight of 6000-10000 into the composite nano solution, respectively ensuring that the final mass concentrations of the PEG-400 and the hydroxymethyl cellulose are 3 percent and 0.2 percent, adding an organic silicon defoamer byk028, ensuring that the final mass concentration is 0.01 percent, and uniformly mixing to prepare a coating solution; the coating liquid is coated on the surface of a substrate with the average aperture of 0Heating to 120 ℃ according to the heating rate of 1 ℃/min on a porous alumina ceramic membrane support body with the diameter of 1 mu m, preserving heat, drying for 3h, then heating to 350 ℃ according to the heating rate of 1 ℃/min, preserving heat, calcining for 3h, and cooling to obtain the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane, wherein the pure water flux is 160LH, the molecular weight cutoff is 20KD, and no defect hole bubble appears through a bubble pressure test.
Example 3
(1) Adding PEG-400 into 0.8mol/L alcoholic solution of n-butyl titanate and ethyl orthosilicate to make the final mass concentration of the alcoholic solution be 0.5%, and dropwise adding alcoholic solution containing 5 wt% of water into the alcoholic solution of the organic salt at 85 ℃ according to the molar ratio of the n-butyl titanate, the ethyl orthosilicate and the water being 2: 100; after the dropwise addition is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 3; then adding a dispersing agent to enable the final mass concentration of the dispersing agent to be 1.2%, and uniformly mixing to obtain TiO2-SiO2 composite sol;
(2) TiO obtained in the step (1)2-SiO2Putting the sol into a hydrothermal reaction kettle with the filling degree of 60 percent, carrying out heat preservation reaction for 8 hours at the temperature of 150 ℃, and cooling to obtain TiO2-SiO2Compounding the nano solution;
(3) adding the TiO obtained in the step (2)2-SiO2Adding PEG-400 and hydroxymethyl cellulose with the molecular weight of 6000-10000 into the composite nano solution, respectively setting the final mass concentrations of the PEG-400 and the hydroxymethyl cellulose to be 5% and 0.5%, adding an organic silicon defoamer byk028, setting the final mass concentration to be 0.1%, and uniformly mixing to prepare a coating solution;
(4) the coating liquid is coated on a porous alumina ceramic membrane support body with the average pore diameter of 0.1 mu m, the temperature is raised to 100 ℃ according to the heating rate of 3 ℃/min, the temperature is preserved and dried for 3h, then the temperature is raised to 600 ℃ according to the heating rate of 3 ℃/min, the temperature is preserved and calcined for 3h, and the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane is obtained after cooling, wherein the pure water flux is 148LH, the molecular weight cutoff is 20KD, and no defect pore bubbles appear through a bubble pressure test.
The hydroxymethyl cellulose in the above embodiments may also be replaced with hydroxyethyl cellulose or hydroxypropyl cellulose.
TABLE 1
From the above table, it can be seen that the sol-hydrothermal method is adopted to prepare the nanoparticles, a complete film layer is prepared by one-time film coating, and the flux of the film layer is improved by 50% after the silicon dioxide is added.
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.
Claims (7)
1. A preparation method of a titanium oxide-silicon oxide composite ceramic ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) adding polyethylene glycol with the weight-average molecular weight of 350-500 into an alcoholic solution of organic salt, and dropwise adding an alcoholic solution containing 4-6 wt% of water into the alcoholic solution of organic salt at the temperature of 75-85 ℃ according to the molar ratio of the organic salt to the water of 1: 10-100; after the dropwise adding is finished, adding acid for dispergation, and enabling the pH value of the dispergated solution to be 2-3; adding a dispersing agent to a final concentration of 0.8-1.2 wt%, and uniformly mixing to obtain TiO2-SiO2Compounding sol; the organic salt consists of organic titanium salt and organic silicon salt in the molar ratio of 2 to 1-3;
(2) TiO obtained in the step (1)2-SiO2The composite sol is put into a hydrothermal reaction kettle with the filling degree of 50-60 percent, and is subjected to heat preservation reaction for 8-10h at the temperature of 120-plus-150 ℃, and then is cooled to prepare TiO2-SiO2Compounding the nano solution;
(3) adding the TiO obtained in the step (2)2-SiO2Adding polyethylene glycol with the weight-average molecular weight of 350-450 and a binder serving as a plasticizer into the composite nano solution, respectively enabling the final concentrations of the plasticizer and the binder to be 3-5 wt% and 0.1-0.5 wt%, adding a defoaming agent until the final concentration is 0.01-0.1 wt%, and uniformly mixing to obtain a coating solution;
(4) coating the film coating liquid on a porous alumina ceramic membrane support, heating to 80-120 ℃ at the speed of 1-3 ℃/min, preserving heat, drying for 2-5h, then heating to 350-600 ℃ at the speed of 1-5 ℃/min, preserving heat, calcining for 2-5h, and cooling to obtain the titanium oxide-silicon oxide composite ceramic ultrafiltration membrane.
2. The method of claim 1, wherein: the dispersing agent is sodium citrate or sodium polyacrylate.
3. The method of claim 1, wherein: the organic titanium salt is n-butyl titanate or isopropyl titanate.
4. The method of claim 1, wherein: the organic silicate is ethyl orthosilicate.
5. The method of claim 1, wherein: the adhesive is cellulose compound with molecular weight of 6000-10000, wherein the cellulose compound is hydroxymethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose.
6. The method of claim 1, wherein: the defoaming agent is an organic silicon defoaming agent.
7. The method of claim 1, wherein: the average pore diameter of the porous alumina ceramic membrane support is 0.1 mu m.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372109A (en) * | 2021-05-18 | 2021-09-10 | 景德镇陶瓷大学 | Preparation method of large-area defect-free nano-scale thickness compact ceramic film and ceramic film prepared by same |
| WO2021248896A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | Preparation method for titania ceramic ultrafiltration membrane |
| WO2021248897A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | Preparation method for zirconia ceramic ultrafiltration membrane |
| CN114917770A (en) * | 2022-05-07 | 2022-08-19 | 常州大学 | Ternary ceramic nanofiltration membrane, preparation method and application |
| CN115262280A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院过程工程研究所 | Fiber paper and preparation method and application thereof |
| CN115364676A (en) * | 2021-05-21 | 2022-11-22 | 三达膜科技（厦门）有限公司 | Preparation method of high-flux spherical alumina ceramic microfiltration membrane |
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| WO2021248896A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | Preparation method for titania ceramic ultrafiltration membrane |
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| CN115364676A (en) * | 2021-05-21 | 2022-11-22 | 三达膜科技（厦门）有限公司 | Preparation method of high-flux spherical alumina ceramic microfiltration membrane |
| CN115364676B (en) * | 2021-05-21 | 2024-04-19 | 三达膜科技（厦门）有限公司 | Preparation method of high-flux spherical alumina ceramic microfiltration membrane |
| CN114917770A (en) * | 2022-05-07 | 2022-08-19 | 常州大学 | Ternary ceramic nanofiltration membrane, preparation method and application |
| CN114917770B (en) * | 2022-05-07 | 2023-08-29 | 常州大学 | Ternary ceramic nanofiltration membrane, preparation method and application |
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