CN113058447B - 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 PDF

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CN113058447B
CN113058447B CN202110439624.3A CN202110439624A CN113058447B CN 113058447 B CN113058447 B CN 113058447B CN 202110439624 A CN202110439624 A CN 202110439624A CN 113058447 B CN113058447 B CN 113058447B
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zirconium
porous flat
sol
silicon
flat ceramic
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CN113058447A (en
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钟璟
沈敏
蒋建锋
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Changzhou Sunan Water Environment Research Institute Co ltd
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Changzhou Sunan Water Environment Research Institute Co ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • 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 zirconium silicate 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 conventional inorganic nanofiltration membrane, and adopts the following scheme: the preparation method comprises the following steps: (1) Dissolving tetraethoxysilane and n-butyl zirconium into a solvent, then adding a catalyst and water, and stirring at a variable temperature to form a 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

Preparation method of porous flat plate ceramic nanofiltration body based on silicon-zirconium sol
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 zirconium silicate 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 treatment 2 、TiO 2 、ZrO 2 When 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 problem 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 tetraethoxysilane and n-butyl zirconium into a solvent, then adding a catalyst and water, and stirring at a variable temperature to form a 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 tetraethoxysilane, zirconium n-butoxide, 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 to form the silicon-zirconium sol with mixed particle size of which the particle size is distributed between 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 0.5-5wt% through water content adjustment.
Specifically, in the step (2), the porous flat ceramic membrane support material is Al 2 O 3 The 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 30min.
Specifically, the dipping time in the step (3) is 10-60s.
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 ℃ for calcination for 15-60min.
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 2-10nm.
The beneficial effects of the invention are:
1. the tetraethoxysilane and the n-butyl zirconium are jointly hydrolyzed and condensed to form SiO 2 -ZrO 2 When sol is prepared, the forming speed of the sol is controlled by using a temperature changing method to obtain the sol with mixed particle size, 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 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 into the large and medium particle size sol to make up the defect of uneven filter pores;
2. forming a covalent bond between the sol and the carrier to prepare a film tightly combined with the support body;
3. using SiO 2 -ZrO 2 The mixed particle size sol is directly loaded on a porous ceramic carrier, so that the pre-loading is reduced, and the doping of a zirconium source increases the hydrothermal stability of the nanofiltration membrane.
Drawings
FIG. 1 SiO on porous support 2 -ZrO 2 A schematic of a nanofiltration membrane;
FIG. 2 is 1wt% SiO produced in example 1 2 -ZrO 2 The particle size distribution diagram of the sol;
FIG. 3 is 2wt% SiO prepared in example 2 2 -ZrO 2 Particle 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)SiO 2 -ZrO 2 Preparation 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 1wt%, 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 SiO 2 -ZrO 2 And (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 placed into a hydrochloric acid solution with pH =3 to be soaked for 30min, then placed into a sodium hydroxide solution with pH =10 to be soaked for 30min, finally washed to be neutral by deionized water and then placed into an oven to be dried, and the drying temperature is 80 ℃.
(3)SiO 2 -ZrO 2 Preparation of porous flat ceramic membrane
Soaking the support body into 1wt% 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 SiO 2 -ZrO 2 The pore diameter of the porous flat plate ceramic membrane is 6nm.
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 content 2 -ZrO 2 The sol was a mixed sol particle size of 40nm,600nm and 5000nm as shown in FIG. 3, by particle size test. In SiO 2 -ZrO 2 Preparation of porous plate ceramic Membrane by impregnating support with 2wt% SiO 2 -ZrO 2 In the sol, the number of dipping times is 5, and SiO is formed 2 -ZrO 2 The pore diameter of the porous flat ceramic membrane is 10nm.
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 (6)

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 preparation processes 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) Repeating the steps (3) and (4) at least once to form the porous flat ceramic nanofiltration body with the surface provided with the silicon-zirconium adhesive film;
stirring under the temperature-changing condition in the step (1), namely heating a solution containing ethyl orthosilicate, zirconium n-butyl alcohol, a solvent, a catalyst and water to boil at 100 ℃ while stirring, keeping boiling for at least 5 minutes, then supplementing water with the same mass as boiling evaporation for cooling, repeating the heating and boiling process after cooling, wherein the repetition times ensure that the whole temperature-changing stirring process reaches 8-14 hours, and forming silicon-zirconium sol with mixed particle size distributed between 20-5000 nm;
in the step (2), the pretreatment of the support body is acid-base soaking, the preheating temperature is 50-100 ℃, and the time is 30min;
the temperature of the solution after the cooling water is supplemented in the step (1) is 40-60 ℃;
in the step (2), the porous flat ceramic membrane support body material is Al 2 O 3 The average pore diameter was 300nm and the porosity was 35%.
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: 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.
4. 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 10-60s.
5. 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) in the heat treatment in the step (4), the porous flat plate ceramic support body coated with the silicon-zirconium sol is placed into a muffle furnace at 550 ℃ to be calcined for 15-60min.
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: 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 2-10nm.
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FR1327835A (en) * 1962-04-10 1963-05-24 Nalco Chemical Co Composition containing colloidal silica and its preparation process
CN1623905A (en) * 2004-10-25 2005-06-08 河北鹏达新材料科技有限公司 Method for preparing zirconium oxide micro powder
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CN101379211A (en) * 2006-02-06 2009-03-04 中央精机株式会社 Preform for composite material and process for producing the same
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