Preparation method of hydrogel-loaded anti-pollution ceramic membrane
By forming a hydrogel coating on the surface of the ceramic membrane, the problem of ceramic membrane being susceptible to contamination is solved, the anti-pollution performance and service life are improved, the cost is reduced and the separation effect is improved.
Patent Information
- Application Number
- CN202510721953.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2025-07-08
AI Technical Summary
Existing ceramic membranes are susceptible to contamination in water treatment, resulting in reduced separation efficiency and shortened service life, and high-performance ceramic membrane materials are expensive.
A hydrogel coating is formed on the surface of the ceramic film, and the base film is prepared by preparing alumina powder, pore-forming agent and binder, and the hydrogel particles are fixed with ultraviolet crosslinking agent and epoxy resin to form an anti-pollution hydrogel coating.
It improves the anti-pollution performance and service life of ceramic membranes, reduces energy loss and production costs, and improves separation effect and membrane performance.
Abstract
Description
Technical Field
[0001] The present invention relates to a method for preparing a ceramic membrane. Background Art
[0002] Membrane separation technology has been widely used in the water treatment field due to its excellent separation effect and operation flexibility. However, ceramic membranes are prone to fouling in practical applications, resulting in a decrease in separation efficiency and a shortening of service life. Membrane filtration technology is known as the "third-generation water purification process" and is one of the most promising technologies in this century. The performance of membrane materials directly affects the efficiency of membrane processes. Traditional membrane materials are mostly hydrophobic organic polymer materials, which are easily fouled by microorganisms, biological macromolecules, oil stains, etc., leading to a rapid decline in separation efficiency and permeation performance. In addition, frequent cleaning will cause phenomena such as chemical degradation, aging, and swelling, reducing the service life of the membrane and restricting the popularization of membrane technology. Compared with organic membranes, ceramic membranes have stronger corrosion resistance, longer service life, wider application range, and better effluent quality. However, high-performance ceramic membrane materials are expensive and have serious membrane fouling problems, especially in the fields of large-scale municipal water treatment and domestic sewage treatment. Therefore, to solve this problem, the present invention provides a method for preparing a hydrogel-loaded anti-fouling ceramic membrane. Summary of the Invention
[0003] The purpose of the present invention is to solve the problems of poor anti-fouling ability and short service life of existing ceramic membranes, and to provide a method for preparing a hydrogel-loaded anti-fouling ceramic membrane.
[0004] The present invention provides a method for preparing a hydrogel-loaded anti-fouling ceramic membrane, by forming a hydrogel coating with anti-fouling properties on the surface of the ceramic membrane to improve the anti-fouling ability and service life of the ceramic membrane.
[0005] A method for preparing a hydrogel-loaded anti-fouling ceramic membrane is specifically completed according to the following steps: I. Preparation of a ceramic membrane substrate: Add alumina powder, pore-forming agent, and binder to a ball mill for ball milling, and sieve to obtain a mixed powder; add water to the mixed powder for blending to obtain a blended material; use a vacuum pug mill to pug the blended material to obtain a blended pug; fire the blended pug to obtain a ceramic membrane substrate; II. Preparation of hydrogel: ①. Dissolve polyethylene glycol diacrylate and [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide in water to obtain a mixed solution A; ②. Dissolve 1-hydroxycyclohexyl phenyl ketone and hexafluorobutyl methacrylate in Isopar-G to obtain a mixed solution B; ③ Add the mixed solution A into a container, then inject the mixed solution B from the edge of the container onto the top of the mixed solution A, and then place the water-oil two-phase system under ultraviolet light for reaction for a period of time to obtain a hydrogel. III. Add component A and component B of the epoxy resin into acetone at a mass ratio of 1:(1 - 4), and stir to obtain a binder solution. IV. Place the hydrogel in a freeze-drying oven for vacuum freeze-drying, and then ball-mill it to obtain dry gel particles. V. Spray the binder solution on the ceramic membrane support membrane, cure for a period of time, then sprinkle the dry gel particles on the surface of the epoxy resin, react for a period of time, and then cure for another period of time to obtain a dry gel layer on the ceramic membrane support membrane. VI. Rinse the dry gel layer with water, and then immerse it in deionized water for a period of time to form an anti-fouling hydrogel coating on the ceramic membrane support membrane, and obtain a ceramic membrane loaded with an anti-fouling hydrogel.
[0006] Principle of the present invention: The present invention uses alumina powder, pore-forming agent and binder to prepare a ceramic membrane support membrane by ball-milling and sintering; generates organic free radicals through ultraviolet light, uses cross-linking agent polyethylene glycol diacrylate and hydrophilic monomer [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide to prepare an anti-fouling hydrogel layer, prepares dry gel particles by freeze-drying and ball-milling, uses epoxy resin to fix the dry gel particles on the surface of the ceramic membrane support membrane, and hydrates the dry gel to obtain an anti-fouling hydrogel coating loaded on the surface of the ceramic membrane; the ceramic membrane prepared by this method has enhanced hydrophilicity and improved anti-fouling performance.
[0007] The preparation method of the ceramic membrane loaded with an anti-fouling hydrogel of the present invention has the following beneficial effects: I. The present invention adheres the hydrogel layer on the surface of the inorganic ceramic membrane through epoxy resin, improves the anti-fouling performance of the ceramic membrane, and does not need to be loaded by sintering, achieving the goal of reducing energy consumption and production cost. II. The thickness of the anti-fouling hydrogel coating grown on the surface of the ceramic membrane support membrane of the present invention is 40 nm, which reduces the roughness and pore size of the ceramic membrane. The pure water flux of the membrane is 3000 - 500 L / (m 2 ·h·bar), and the membrane performance is good. III. The present invention composes a hydrophilic hydrogel layer on the support membrane to improve the filtration effect of the separation layer and enhance the anti-fouling performance of the ceramic membrane; for the anti-fouling evaluation of the ceramic membrane loaded with an anti-fouling hydrogel prepared by the present invention, when continuously operating under the condition of humic acid pollution, the flux decays to 31% and then reaches a plateau, and can be restored to about 85% after backwashing; when the ordinary ceramic membrane operates under the same conditions, the flux decays to less than 18% before reaching the plateau, and cannot be effectively restored after backwashing. Specific embodiments
[0008] Embodiment 1: A preparation method of a hydrogel-loaded anti-pollution ceramic membrane is specifically completed according to the following steps: I. Preparation of the ceramic membrane substrate: Add alumina powder, pore-forming agent and binder into a ball mill for ball milling, and then sieve to obtain a mixed powder; add water to the mixed powder for blending to obtain a blended material; use a vacuum pug mill to pug the blended material to obtain a blended mud; fire the blended mud to obtain the ceramic membrane substrate; II. Preparation of the hydrogel: ①. Dissolve polyethylene glycol diacrylate and [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide in water to obtain a mixed solution A; ②. Dissolve 1-hydroxycyclohexyl phenyl ketone and hexafluorobutyl methacrylate in Isopar-G to obtain a mixed solution B; ③. Add the mixed solution A into a container, then inject the mixed solution B from the edge of the container to the top of the mixed solution A, and then place the water-oil two-phase system under ultraviolet light for reaction for a period of time to obtain the hydrogel; III. Add component A and component B of the epoxy resin to acetone according to a mass ratio of 1:(1~4), and stir to obtain a binder solution; IV. Place the hydrogel in a freeze-drying oven for vacuum freeze-drying, and then ball mill to obtain dry gel particles; V. Spray the binder solution on the ceramic membrane substrate, cure for a period of time, then sprinkle the dry gel particles on the surface of the epoxy resin, react for a period of time, and then cure for a period of time to obtain a dry gel layer on the ceramic membrane substrate; VI. Rinse the dry gel layer with water, and then immerse it in deionized water for a period of time to form an anti-pollution hydrogel coating on the ceramic membrane substrate, and obtain the hydrogel-loaded anti-pollution ceramic membrane.
[0009] Embodiment 2: The difference between this embodiment and Embodiment 1 is that: the pore-forming agent described in step I is starch or carbon powder; the binder described in step I is methyl cellulose or polyvinyl alcohol. Other steps are the same as those in Embodiment 1.
[0010] Embodiment 3: The difference between this embodiment and one of Embodiment 1 or 2 is that: the mass ratio of the alumina powder, pore-forming agent and binder described in step I is 8:1:1; the mass ratio of the mixed powder to water in the blended material described in step I is 1:1. Other steps are the same as those in Embodiment 1 or 2.
[0011] Embodiment 4: The differences between this embodiment and any one of Embodiments 1 to 3 are as follows: In Step 1, the ball milling speed is 400 r / min to 500 r / min, the ball milling time is 2 h to 4 h, and the ball-to-material ratio is 0.5:1; the sieving in Step 1 is through a 100-mesh to 200-mesh sieve; the firing temperature in Step 1 is 1200 °C to 1600 °C, and the firing time is 2 h to 3 h. Other steps are the same as those in Embodiments 1 to 3.
[0012] Embodiment 5: The differences between this embodiment and any one of Embodiments 1 to 4 are as follows: In the mixed solution A in Step 2①, the mass fraction of polyethylene glycol diacrylate is 0.1% to 0.5%, and the mass fraction of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide is 0.5% to 4.5%; in the mixed solution B in Step 2②, the concentration of 1-hydroxycyclohexyl phenyl ketone is 0.01 g / mL, and the mass fraction of hexafluorobutyl methacrylate is 0.5% to 4.5%. Other steps are the same as those in Embodiments 1 to 4.
[0013] Embodiment 6: The differences between this embodiment and any one of Embodiments 1 to 5 are as follows: In Step 2③, the volume ratio of the mixed solution A to the mixed solution B is 1:1; the reaction time under ultraviolet light in Step 2③ is 5 min to 10 min. Other steps are the same as those in Embodiments 1 to 5.
[0014] Embodiment 7: The differences between this embodiment and any one of Embodiments 1 to 6 are as follows: In Step 3, the volume ratio of the total mass of Component A and Component B of the epoxy resin to acetone is (1 g to 5 g):(1 mL to 10 mL). Other steps are the same as those in Embodiments 1 to 6.
[0015] Embodiment 8: The differences between this embodiment and any one of Embodiments 1 to 7 are as follows: In Step 4, the temperature of vacuum freeze-drying is -40 °C, and the vacuum freeze-drying time is 12 h to 48 h; the ball milling speed in Step 4 is 200 r / min to 300 r / min; the size of the dry gel particles in Step 4 is 1 μm to 5 μm. Other steps are the same as those in Embodiments 1 to 7.
[0016] Embodiment 9: The differences between this embodiment and any one of Embodiments 1 to 8 are as follows: In Step 5, the mass ratio of the dry gel particles to the volume of the binder solution is (1 g to 5 g):(1 mL to 10 mL); the thickness of the dry gel layer on the ceramic membrane substrate in Step 5 is 20 nm to 40 nm. Other steps are the same as those in Embodiments 1 to 8.
[0017] Embodiment 10: The difference between this embodiment and any one of Embodiments 1 to 9 is that: in Step 5, the binder solution is sprayed on the ceramic membrane substrate, cured at room temperature for 30 min to 45 min, then the dry gel particles are sprayed on the surface of the epoxy resin, reacted for 15 min to 30 min, and then cured for 3 h to 4 h to obtain a dry gel layer on the ceramic membrane substrate; in Step 6, the dry gel layer is washed 3 to 5 times with water and then immersed in deionized water for 12 h to 24 h. Other steps are the same as those in Embodiments 1 to 9.
[0018] The following examples are used to verify the beneficial effects of the present invention: Example 1: A method for preparing a hydrogel-loaded anti-fouling ceramic membrane is specifically completed according to the following steps: I. Preparation of the ceramic membrane substrate: Aluminum oxide powder, a pore-forming agent, and a binder are added to a ball mill for ball milling, and then sieved to obtain a mixed powder; water is added to the mixed powder for blending to obtain a blended material; a vacuum kneading machine is used to knead the blended material to obtain a blended clay material; the blended clay material is fired to obtain the ceramic membrane substrate; The pore-forming agent described in Step I is starch; The binder described in Step I is methylcellulose; The mass ratio of the aluminum oxide powder, the pore-forming agent, and the binder described in Step I is 8:1:1; The mass ratio of the mixed powder to water in the blended material described in Step I is 1:1; The speed of the ball milling described in Step I is 400 r / min, the time of the ball milling is 2 h, and the ball-to-material ratio is 0.5:1; The sieving described in Step I is through a 200-mesh sieve; The firing temperature described in Step I is 1200 °C, and the firing time is 3 h; II. Preparation of the hydrogel: ①. Polyethylene glycol diacrylate and [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide are dissolved in water to obtain a mixed solution A; The mass fraction of polyethylene glycol diacrylate in the mixed solution A described in Step II ① is 0.1%, and the mass fraction of [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide is 0.5%; ②. 1-Hydroxycyclohexyl phenyl ketone and hexafluorobutyl methacrylate are dissolved in Isopar-G to obtain a mixed solution B; The concentration of 1-hydroxycyclohexyl phenyl ketone in the mixed solution B described in Step II ② is 0.01 g / mL, and the mass fraction of hexafluorobutyl methacrylate is 0.5%; ③ Add the mixed solution A into a container, then inject the mixed solution B from the edge of the container to the top of the mixed solution A, and then place the water-oil two-phase system under ultraviolet light for reaction for 5 min to obtain a hydrogel; In step ②, the volume ratio of the mixed solution A to the mixed solution B is 1:1; III. Add component A and component B of the epoxy resin into acetone according to a mass ratio of 1:1, and stir to obtain a binder solution; In step III, the total mass of component A and component B of the epoxy resin and the volume ratio of acetone is 1 g: 10 mL; IV. Place the hydrogel in a freeze-dryer for vacuum freeze-drying, and then ball-mill to obtain dry gel particles; In step IV, the temperature of the vacuum freeze-drying is -40 °C, and the time of the vacuum freeze-drying is 12 h; In step IV, the speed of the ball-milling is 200 r / min; In step IV, the size of the dry gel particles is 2 μm; V. Spray the binder solution on the ceramic membrane substrate, cure at room temperature for 30 min, then spray the dry gel particles on the surface of the epoxy resin, react for 15 min, and then cure for 3 h to obtain a dry gel layer on the ceramic membrane substrate; In step V, the mass ratio of the dry gel particles to the volume of the binder solution is 1 g: 1 mL; In step V, the thickness of the dry gel layer on the ceramic membrane substrate is 20 nm; VI. Rinse the dry gel layer 3 times with water, and then immerse it in deionized water for 12 h to form an anti-pollution hydrogel coating on the ceramic membrane substrate, and obtain a ceramic membrane loaded with a hydrogel anti-pollution layer.
[0019] For the ceramic membrane loaded with a hydrogel anti-pollution layer prepared in Example 1, the nano-hydrogel thin layer grown on the membrane surface was characterized by atomic force microscopy, with a thickness of 40 nm, which reduced the roughness and pore size of the ceramic membrane; Place the ceramic membrane loaded with a hydrogel anti-pollution layer prepared in Example 1 in a filtration device, introduce nitrogen into the filtration device, maintain the pressure difference on both sides of the ceramic membrane at 0.001 MPa, and the pure water flux of the ceramic membrane loaded with a hydrogel anti-pollution layer prepared in Example 1 is 3000~500 L / (m 2 ·h·bar), and the membrane performance is good.
[0020] Using humic acid with a concentration of 50 mg / L as the retention substance for filtration, nitrogen is introduced into the filtration device to maintain a pressure difference of 0.001 MPa on both sides of the ceramic membrane and run continuously. The flux decays to 31% and then reaches a plateau, and can be restored to about 85% after backwashing; when the ordinary ceramic membrane is operated under the same conditions, the flux decays to less than 18% before reaching a plateau, and cannot be effectively restored after backwashing.
Claims
1. A preparation method of a hydrogel-loaded anti-fouling ceramic membrane, characterized in that The preparation method is specifically completed according to the following steps: I. Preparation of the ceramic membrane support membrane: Add alumina powder, pore-forming agent, and binder into a ball mill for ball milling, then sieve to obtain a mixed powder; add water to the mixed powder for blending to obtain a blended material; use a vacuum pug mill to perform pugging on the blended material to obtain a blended clay material; fire the blended clay material to obtain the ceramic membrane support membrane; II. Preparation of the hydrogel: ①. Dissolve polyethylene glycol diacrylate and [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide in water to obtain a mixed solution A; ②. Dissolve 1-hydroxycyclohexyl phenyl ketone and hexafluorobutyl methacrylate in Isopar-G to obtain a mixed solution B; ③. Add the mixed solution A into a container, then inject the mixed solution B from the edge of the container to the top of the mixed solution A, and then place the water-oil two-phase system under ultraviolet light for reaction for a period of time to obtain the hydrogel; III. Add component A and component B of the epoxy resin into acetone according to a mass ratio of 1:(1~4), and stir to obtain a binder solution; IV. Place the hydrogel in a freeze-drying oven for vacuum freeze-drying, and then ball mill to obtain dry gel particles; V. Spray the binder solution on the ceramic membrane support membrane, cure for a period of time, then sprinkle the dry gel particles on the surface of the epoxy resin, react for a period of time, and then cure for a period of time to obtain a dry gel layer on the ceramic membrane support membrane; VI. Wash the dry gel layer with water, and then immerse it in deionized water for a period of time to form an anti-fouling hydrogel coating on the ceramic membrane support membrane, and obtain a hydrogel-loaded anti-fouling ceramic membrane.
2. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The pore-forming agent described in step I is starch or carbon powder; the binder described in step I is methyl cellulose or polyvinyl alcohol.
3. The preparation method of a loadable hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The mass ratio of the alumina powder, pore-forming agent, and binder described in step I is 8:1:1; the mass ratio of the mixed powder to water in the blended material described in step I is 1:
1.
4. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The speed of the ball milling described in step I is 400 r / min~500 r / min, the time of the ball milling is 2 h~4 h, the ball-to-material ratio is 0.5:1; the sieving described in step I is through 100 mesh~200 mesh; the firing temperature described in step I is 1200 °C~1600 °C, and the firing time is 2 h~3 h.
5. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The mass fraction of polyethylene glycol diacrylate in the mixed solution A described in step II① is 0.1%~0.5%, and the mass fraction of [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide is 0.5%~4.5%; the concentration of 1-hydroxycyclohexyl phenyl ketone in the mixed solution B described in step II② is 0.01 g / mL, and the mass fraction of hexafluorobutyl methacrylate is 0.5%~4.5%.
6. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The volume ratio of the mixed solution A to the mixed solution B described in step II③ is 1:1; the reaction time under ultraviolet light described in step II③ is 5 min~10 min.
7. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The volume ratio of the total mass of component A and component B of the epoxy resin to acetone described in step III is (1 g~5 g):(1 mL~10 mL).
8. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The temperature of the vacuum freeze-drying described in Step 4 is -40°C, and the time of the vacuum freeze-drying is 12 h to 48 h; the speed of the ball milling described in Step 4 is 200 r / min to 300 r / min; the size of the dry gel particles described in Step 4 is 1 μm to 5 μm.
9. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, characterized in that The mass ratio of the dry gel particles to the volume of the binder solution described in Step 5 is (1 g to 5 g):(1 mL to 10 mL); the thickness of the dry gel layer on the ceramic membrane substrate in Step 5 is 20 nm to 40 nm.
10. The preparation method of a load hydrogel anti-pollution ceramic membrane according to claim 1, wherein In Step 5, the binder solution is sprayed on the ceramic membrane substrate, cured at room temperature for 30 min to 45 min, then the dry gel particles are sprayed on the surface of the epoxy resin, reacted for 15 min to 30 min, and then cured for 3 h to 4 h to obtain a dry gel layer on the ceramic membrane substrate; in Step 6, the dry gel layer is rinsed with water 3 to 5 times and then immersed in deionized water for 12 h to 24 h.