CN113058447A - Preparation method of porous flat ceramic nanofiltration body based on silicon-zirconium sol - Google Patents
Preparation method of porous flat ceramic nanofiltration body based on silicon-zirconium sol Download PDFInfo
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- CN113058447A CN113058447A CN202110439624.3A CN202110439624A CN113058447A CN 113058447 A CN113058447 A CN 113058447A CN 202110439624 A CN202110439624 A CN 202110439624A CN 113058447 A CN113058447 A CN 113058447A
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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
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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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
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membrane separation and water treatment filter bodies, and particularly relates to a preparation method of a porous flat ceramic nanofiltration body based on a silicon-zirconium sol, which overcomes the problems of complex preparation process, unstable combination of a filter membrane and a carrier, non-uniform pore diameter of filter pores on the filter membrane and the like of the existing inorganic nanofiltration membrane, and adopts the following scheme: the preparation method comprises the following steps: (1) dissolving ethyl orthosilicate and n-butyl zirconium into a solvent, then adding a catalyst and water, and stirring under a temperature-changing condition to form silicon-zirconium sol; (2) pretreating the porous flat ceramic support body, and then putting the porous flat ceramic support body into an oven for heating; (3) dipping the preheated support body in the step (2) into the silicon-zirconium sol obtained in the step (1), taking out and drying at room temperature; (4) carrying out heat treatment roasting, taking out and cooling to room temperature; (5) and (4) repeating the steps (3) and (4) at least once to form the porous flat plate ceramic nanofiltration body with the surface provided with the silicon-zirconium adhesive film.
Description
Technical Field
The invention belongs to the technical field of membrane separation and water treatment filter bodies, and particularly relates to a preparation method of a porous flat ceramic nanofiltration body based on a silicon-zirconium sol.
Background
Nanofiltration is a novel membrane separation process with the aperture between ultrafiltration and reverse osmosis and the pressure difference as the driving force, and is widely applied and researched in the field of drinking water treatment2、TiO2、ZrO2When the carrier is loaded on a sheet or tubular carrier, the carrier has large permeation resistance, and the preparation is complex because the preparation is required to be modified in advance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the problems of complex preparation process of the existing inorganic nanofiltration membrane, and other problems such as weak combination of the filter membrane and the carrier, non-uniform pore diameter of the filter pores on the filter membrane, and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: a process for preparing porous plate ceramic nano-filter based on a silicon-zirconium sol includes such steps as preparing the porous plate ceramic nano-filter,
(1) dissolving ethyl orthosilicate and n-butyl zirconium into a solvent, then adding a catalyst and water, and stirring under a temperature-changing condition to form silicon-zirconium sol;
(2) pretreating the porous flat ceramic support body, and then putting the porous flat ceramic support body into an oven for heating;
(3) dipping the preheated support body in the step (2) into the silicon-zirconium sol obtained in the step (1), taking out and drying at room temperature;
(4) carrying out heat treatment roasting, taking out and cooling to room temperature;
(5) and (4) repeating the steps (3) and (4) at least once to form the porous flat plate ceramic nanofiltration body with the surface provided with the silicon-zirconium adhesive film.
Specifically, in the step (1), the molar ratio of ethyl orthosilicate to n-butyl alcohol zirconium is 1: 0.5-5, the solvent is ethanol or butanol, and the catalyst is hydrochloric acid or nitric acid.
Specifically, the stirring under the temperature-changing condition in the step (1) is to heat a solution containing ethyl orthosilicate, zirconium n-butyl alcohol, a solvent, a catalyst and water to 100 ℃ for boiling while stirring, keep boiling for at least 5 minutes, then supplement water with the same mass as boiling evaporation for cooling, repeat the heating and boiling process after cooling, and ensure that the whole temperature-changing stirring process reaches 8-14 hours by the repeated times, so as to form the silicon-zirconium sol with mixed particle size of 20-5000 nm.
Specifically, the temperature of the solution after supplementing cooling water in the step (1) is 40-60 ℃.
Specifically, in the step (1), the mass concentration of the sum of the mass of ethyl orthosilicate and zirconium n-butyl alcohol in the system is 0.5-5 wt% through water content adjustment.
Specifically, the porous flat ceramic membrane support material in the step (2) is Al2O3The average pore diameter was 300nm and the porosity was 35%.
Specifically, in the step (2), the pretreatment of the support body is acid-base soaking, the preheating temperature is 50-100 ℃, and the time is 30 min.
Specifically, the dipping time in the step (3) is 10-60 s.
Specifically, the heat treatment in the step (4) is to place the porous flat ceramic support body coated with the silicon-zirconium sol into a muffle furnace at 550 ℃ to calcine for 15-60 min.
Specifically, the repeated preparation in the step (5) is carried out for 5-12 times, and the pore diameter of the filtration pore of the surface zirconium silicate adhesive film is 2-10 nm.
The invention has the beneficial effects that:
firstly, the tetraethoxysilane and the n-butyl zirconium are jointly hydrolyzed and condensed to form SiO2-ZrO2When sol is prepared, the sol with mixed particle size is obtained by controlling the forming speed of the sol by using a temperature changing method, when a nanofiltration membrane is prepared on a ceramic carrier, the sol is loaded on the ceramic through mixing a part of large particle size sol and medium and small particle size sol, the large particle size sol prevents the small particle size sol from entering a pore channel of the ceramic carrier, and the small particle size sol is filled in the large and medium particle size sol, so that the defect of uneven filter pores is overcome;
forming a covalent bond between the sol and the carrier to prepare a film tightly combined with the support body;
III,Using SiO2-ZrO2The mixed particle size sol is directly loaded on the porous ceramic carrier, so that the pre-loading is reduced, and the doping of the zirconium source increases the hydrothermal stability of the nanofiltration membrane.
Drawings
FIG. 1 SiO on porous support2-ZrO2A schematic of a nanofiltration membrane;
FIG. 2 is a 1 wt% SiO solid prepared in example 12-ZrO2The particle size distribution diagram of the sol;
FIG. 3 is the 2 wt% SiO produced in example 22-ZrO2Particle size distribution of the sol.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
(1)SiO2-ZrO2Preparation of the Sol
Dissolving tetraethoxysilane and n-butyl zirconium in the same molar ratio in absolute ethyl alcohol, and sequentially adding distilled water and hydrochloric acid under continuous stirring to finally form tetraethoxysilane: n-butyl alcohol zirconium: ethanol: the molar ratio of the hydrochloric acid is 1: 1: 10: 2, regulating the water content to keep the mass fraction of the ethyl orthosilicate and the zirconium n-butoxide at 1 wt%, heating the solution to 100 ℃ for boiling for 15min, supplementing water cooling equivalent to boiling evaporation (about 50 ℃), repeating the steps, and continuously stirring for 8 hours to form stable SiO2-ZrO2And (3) testing the particle size of the sol by adopting a dynamic light scattering technology, and finally forming the mixed sol particle size of 25nm, 300nm and 5000nm as shown in figure 2.
(2) Porous flat ceramic support pretreatment
The porous flat plate ceramic support body is firstly put into hydrochloric acid solution with the pH value of 3 to be soaked for 30min, then put into sodium hydroxide solution with the pH value of 10 to be soaked for 30min, finally washed to be neutral by deionized water and then put into an oven to be dried, wherein the drying temperature is 80 ℃.
(3)SiO2-ZrO2Porous flat potteryPreparation of ceramic film
Soaking the support body into 1 wt% silicon-zirconium sol for 20s, drying at room temperature, then placing the support body into a muffle furnace at 550 ℃ to calcine for 40 min, cooling at room temperature, repeating the step for 10 times to form SiO2-ZrO2The pore diameter of the porous flat plate ceramic membrane is 6 nm.
Example 2
The sol differs from example 1 in that SiO with a mass fraction of 2 wt% of ethyl orthosilicate + zirconium n-butoxide is prepared by reducing the water content2-ZrO2The sol has mixed sol particle sizes of 40nm, 600nm and 5000nm as shown in FIG. 3. In SiO2-ZrO2Preparation of porous plate ceramic Membrane by impregnating support with 2 wt% SiO2-ZrO2In the sol, the number of dipping times is 5, and SiO is formed2-ZrO2The pore diameter of the porous flat plate ceramic membrane is 10 nm.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of a porous flat ceramic nanofiltration body based on a silicon-zirconium sol is characterized by comprising the following steps: the preparation method comprises the following steps of,
(1) dissolving ethyl orthosilicate and n-butyl zirconium into a solvent, then adding a catalyst and water, and stirring under a temperature-changing condition to form silicon-zirconium sol;
(2) pretreating the porous flat ceramic support body, and then putting the porous flat ceramic support body into an oven for heating;
(3) dipping the preheated support body in the step (2) into the silicon-zirconium sol obtained in the step (1), taking out and drying at room temperature;
(4) carrying out heat treatment roasting, taking out and cooling to room temperature;
(5) and (4) repeating the steps (3) and (4) at least once to form the porous flat plate ceramic nanofiltration body with the surface provided with the silicon-zirconium adhesive film.
2. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of ethyl orthosilicate to n-butyl alcohol zirconium is 1: 0.5-5, the solvent is ethanol or butanol, and the catalyst is hydrochloric acid or nitric acid.
3. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: stirring under the temperature-changing condition in the step (1) is to heat a solution containing ethyl orthosilicate, zirconium n-butyl alcohol, a solvent, a catalyst and water to 100 ℃ for boiling while stirring, keep boiling for at least 5 minutes, then supplement water with the same mass as boiling evaporation for cooling, repeat the heating and boiling process after cooling, and ensure that the whole temperature-changing stirring process reaches 8-14 hours by the repeated times, so as to form the silicon-zirconium sol with mixed particle size distributed between 20-5000 nm.
4. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 3, wherein the method comprises the following steps: the temperature of the solution after supplementing cooling water in the step (1) is 40-60 ℃.
5. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 3, wherein the method comprises the following steps: in the step (1), the mass concentration of the sum of the mass of the ethyl orthosilicate and the mass of the n-butyl alcohol zirconium in the system is 0.5 to 5 weight percent through water content adjustment.
6. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: in the step (2), the porous flat ceramic membrane support body material is Al2O3The average pore diameter was 300nm and the porosity was 35%.
7. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: in the step (2), the pretreatment of the support body is acid-base soaking, the preheating temperature is 50-100 ℃, and the time is 30 min.
8. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: the dipping time in the step (3) is 10-60 s.
9. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: and (4) the heat treatment in the step (4) is to place the porous flat ceramic support body coated with the silicon-zirconium sol into a muffle furnace at 550 ℃ to calcine for 15-60 min.
10. The method for preparing a porous flat ceramic nanofiltration body based on a silicozirconium sol according to claim 1, wherein the method comprises the following steps: the repeated preparation in the step (5) is carried out for 5-12 times, and the aperture of the filtration pore of the surface silicon zirconium adhesive film is 2-10 nm.
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Cited By (1)
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| CN114917770A (en) * | 2022-05-07 | 2022-08-19 | 常州大学 | Ternary ceramic nanofiltration membrane, preparation method and application |
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