CN110898683A - Preparation method of ceramic filtering membrane - Google Patents
Preparation method of ceramic filtering membrane Download PDFInfo
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- CN110898683A CN110898683A CN201910999708.5A CN201910999708A CN110898683A CN 110898683 A CN110898683 A CN 110898683A CN 201910999708 A CN201910999708 A CN 201910999708A CN 110898683 A CN110898683 A CN 110898683A
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- ceramic
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- metal oxide
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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
- 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
- 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
- B01D69/02—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
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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
- B01D71/025—Aluminium oxide
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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
Abstract
The invention discloses a preparation method of a ceramic filter membrane, which adopts hollow spherical or ellipsoidal metal oxide aggregate particles as support aggregate, adds ceramic fibers to connect the aggregate particles, thereby forming a three-dimensional network structure ceramic membrane support with high porosity, high structural strength and uniform pore size distribution by taking the hollow ceramic particles as connecting nodes and the ceramic fibers as a connecting network, and effectively overcoming the defects that the ceramic fibers are easy to agglomerate, precipitate and delaminate and are easy to bend and break under the influence of external force in the preparation process by adopting a gel injection molding process to form the ceramic membrane support in situ.
Description
Technical Field
The invention belongs to the technical field of ceramic membrane preparation, and particularly relates to a preparation method of a ceramic filtering membrane.
Background
Membranes and membrane processes are a high technological field that has rapidly developed in the 60 s of the 20 th century. All countries in the world pay high attention to the technology, and the technology is placed in the important position of technological innovation and national economic development. Compared with the traditional polymer separation membrane material, the ceramic membrane has good chemical stability, and can resist acid, alkali and organic solvents; the mechanical strength is high, and the back flushing can be realized; the antimicrobial capability is strong; high temperature resistance; narrow pore size distribution, high separation efficiency and the like, and is widely applied in the fields of food industry, bioengineering, environmental engineering, chemical industry, petrochemical industry, metallurgical industry and the like.
The ceramic membrane is mainly prepared by taking inorganic ceramic materials of alumina, zirconia, titania, silica and the like with different specifications as a support body, coating the surface of the support body and firing the support body at high temperature. The commercial ceramic membrane usually has a three-layer structure (a porous supporting layer, a transition layer and a separation layer), is asymmetrically distributed, has the pore size specification of 0.8 nm-1 mu m, and has the filtration precision covering the micro-filtration, ultra-filtration and nano-filtration levels.
Disclosure of Invention
The invention aims to provide a preparation method of a ceramic filter membrane.
The technical scheme of the invention is as follows:
a preparation method of a ceramic filter membrane comprises the following steps:
(1) fully mixing round or oval hollow metal oxide aggregate particles, ceramic fibers, a nano sintering aid, a forming aid and water to prepare ceramic slurry, wherein the particle size of the hollow metal oxide aggregate particles is 20-50um, the particle size of the nano sintering aid is 10-200m, and the mass ratio of the hollow metal oxide aggregate particles to the ceramic fibers to the nano sintering aid to the forming aid is 50-65: 20-35: 0-5: 10-15;
(2) carrying out in-situ forming on the ceramic slurry by a gel injection molding process to prepare a wet support body blank;
(3) drying, drying and sintering the wet support body blank in the shade in sequence to prepare a support body;
(4) and (4) coating at least one layer of filter membrane on the support obtained in the step (3) to obtain the ceramic filter membrane.
In a preferred embodiment of the present invention, the hollow metal oxide aggregate particles are made of silica or alumina.
In a preferred embodiment of the present invention, the material of the nano-sintering aid is titanium oxide.
In a preferred embodiment of the present invention, the ceramic fiber is an alumina ceramic fiber, an alumina ceramic chopped fiber, or a silica ceramic fiber.
In a preferred embodiment of the present invention, the molding aid in the gelcasting process includes activated carbon powder, PVA powder and gelatin powder.
In a preferred embodiment of the invention, the drying temperature is 75-85 ℃ and the drying time is 48-96 h.
In a preferred embodiment of the invention, the sintering atmosphere is air atmosphere, the temperature is 1500-.
In a preferred embodiment of the present invention, the method of coating in the step (4) is a dipping method or a spraying method.
The invention has the beneficial effects that:
1. the invention adopts hollow spherical or ellipsoidal metal oxide aggregate particles as support aggregate, adds ceramic fibers to connect the aggregate particles, thereby forming a three-dimensional network structure with high porosity, high structural strength and uniform pore size distribution by taking the hollow ceramic particles as connecting nodes and taking the ceramic fibers as a connecting network, and effectively overcoming the defects that the ceramic fibers are easy to agglomerate, precipitate and delaminate and are easy to bend and break under the influence of external force in the preparation process by adopting a gel casting process to form the ceramic membrane support in situ.
2. Since the metal oxide aggregate particles of the present invention are hollow spherical or ellipsoidal ceramic particles, they have more excellent suspension and dispersion uniformity in a high-concentration gel-casting slurry than solid ceramic particles because of their light weight. Therefore, the ceramic membrane support prepared by the invention has excellent performance, the aperture of the ceramic membrane support is adjustable within 1-100um, the aperture distribution is uniform, the porosity can reach 40-80%, the breaking strength is 40-60MPa, and the pure water flux is 20000-40000LMH under the pressure of 0.1 MPa.
Drawings
FIG. 1 is a scanning electron micrograph of the ceramic membrane support prepared in examples 1 to 3 of the present invention.
FIG. 2 is a second SEM photograph of the ceramic membrane supports prepared in examples 1 to 3 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1:
hollow spherical alumina (50 μm, 65 wt%), alumina ceramic fiber (25 wt%), activated carbon powder (20 μm, 3 wt%), PVA powder (molecular weight 2000, 2 wt%), gelatin powder (purity 98%, 5 wt%) were ball milled for 2h and mixed uniformly. Adding RO water (the volume ratio of the mixed powder to the RO water solution is 2.2: 1), and performing ball milling dispersion for 22 hours under the condition of heating in a water bath at the temperature of 80 ℃ to prepare uniformly dispersed slurry. The slurry is immediately poured into a mold after vacuum defoaming at the temperature of 80 ℃, and is physically cooled to 20 ℃ and then is solidified in situ to form a wet blank with certain strength. And (3) demoulding the wet blank, drying in the shade for 24h at room temperature, drying for 48h at 80 ℃, and sintering in an air atmosphere at the sintering temperature of 1750 ℃ for 4h to prepare the ceramic membrane support body shown in the figures 1 and 2, wherein the ceramic membrane support body has the average pore diameter of 10 mu m, the porosity of 45 percent, the breaking strength of 50MPa and the pure water flux of 25000LMH under the pressure of 0.1 MPa. And subsequently, coating one or more layers of filter membranes on the support body through ceramic filter membrane preparation processes such as dipping or spraying, and the like, and finally preparing a ceramic membrane product.
Example 2:
hollow ellipsoidal alumina powder (30 μm, 65 wt%), alumina ceramic chopped fiber (20 wt%), titanium oxide powder (100nm, 5 wt%), activated carbon powder (20 μm, 3 wt%), PVA powder (molecular weight 2000, 2 wt%), gelatin powder (purity 98%, 5 wt%) and ball milling for 2 h. Adding RO water (the volume ratio of the mixed powder to the RO water solution is 2.2: 1), and performing ball milling dispersion for 48 hours under the condition of heating in a water bath at 85 ℃ to prepare uniformly dispersed slurry. The slurry is immediately poured into a mold after vacuum defoaming at the temperature of 80 ℃, and is physically cooled to 20 ℃ and then is solidified in situ to form a wet blank with certain strength. The wet blank is demoulded, dried in the shade for 48h at room temperature, dried for 72h at 80 ℃, and then sintered in the air atmosphere, the sintering temperature is 1550 ℃, and the sintering time is 6h, so that the ceramic membrane support shown in the figures 1 and 2 is prepared, the average pore diameter of the ceramic membrane support is 6 mu m, the porosity is 50%, the breaking strength is 45MPa, and the pure water flux is 30000LMH under the pressure of 0.1 MPa. And subsequently, coating one or more layers of filter membranes on the support body through ceramic filter membrane preparation processes such as dipping or spraying, and the like, and finally preparing a ceramic membrane product.
Example 3:
hollow spherical or ellipsoidal silica (20 μm, 50 wt%), silica ceramic fiber (35 wt%), activated carbon powder (5 μm, 3 wt%), PVA powder (molecular weight 2000, 3 wt%), gelatin powder (purity 98%, 7 wt%) were ball milled for 12h and mixed uniformly. Adding RO water (the volume ratio of the mixed powder to the RO water solution is 2.2: 1), and performing ball milling dispersion for 40 hours under the condition of heating in a water bath at 85 ℃ to prepare uniformly dispersed slurry. The slurry is immediately poured into a mould after vacuum defoaming in a heat preservation state at 80 ℃, and is solidified in situ into a wet blank with certain strength after being physically cooled to 20 ℃. And (3) demoulding the wet blank, drying in the shade for 72h at room temperature, drying for 96h at 80 ℃, and then sintering in an air atmosphere at the sintering temperature of 1500 ℃ for 6h to prepare the ceramic membrane support body shown in the figures 1 and 2, wherein the ceramic membrane support body has an average pore diameter of 5 microns, a porosity of 60 percent, a breaking strength of 40MPa and a pure water flux of 35000LMH under the pressure of 0.1 MPa. And subsequently, coating one or more layers of filter membranes on the support body through ceramic filter membrane preparation processes such as dipping or spraying, and the like, and finally preparing a ceramic membrane product.
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 (8)
1. A preparation method of a ceramic filter membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) fully mixing round or oval hollow metal oxide aggregate particles, ceramic fibers, a nano sintering aid, a forming aid and water to prepare ceramic slurry, wherein the particle size of the hollow metal oxide aggregate particles is 20-50um, the particle size of the nano sintering aid is 10-200nm, and the mass ratio of the hollow metal oxide aggregate particles to the ceramic fibers to the nano sintering aid to the forming aid is 50-65: 20-35: 0-5: 10-15;
(2) carrying out in-situ forming on the ceramic slurry by a gel injection molding process to prepare a wet support body blank;
(3) drying, drying and sintering the wet support body blank in the shade in sequence to prepare a support body;
(4) and (4) coating at least one layer of filter membrane on the support obtained in the step (3) to obtain the ceramic filter membrane.
2. The method of claim 1, wherein: the hollow metal oxide aggregate particles are made of silicon oxide or aluminum oxide.
3. The method of claim 1, wherein: the nano sintering aid is made of titanium oxide.
4. The method of claim 1, wherein: the ceramic fiber is alumina ceramic fiber, alumina ceramic chopped fiber or silica ceramic fiber.
5. The method of claim 1, wherein: the forming auxiliary agent in the gel injection molding process comprises activated carbon powder, PVA powder and gelatin powder.
6. The method of claim 1, wherein: the drying temperature is 75-85 ℃ and the drying time is 48-96 h.
7. The method of claim 1, wherein: the sintering atmosphere is air atmosphere, the temperature is 1500-1750 ℃, and the time is 4-6 h.
8. The method of claim 1, wherein: the coating method in the step (4) is a dipping method or a spraying method.
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| CN201910999708.5A CN110898683B (en) | 2019-10-18 | 2019-10-18 | Preparation method of ceramic filtering membrane |
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| CN108440008A (en) * | 2018-05-04 | 2018-08-24 | 南京工业大学 | A kind of high porosity ceramic filtering material and preparation method thereof |
| CN109095948A (en) * | 2018-08-06 | 2018-12-28 | 清华大学 | A method of there is connection hole wall foamed ceramics using hollow microsphere preparation |
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2019
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Patent Citations (11)
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| CN102241515A (en) * | 2010-05-14 | 2011-11-16 | 河北勇龙邦大新材料有限公司 | Ceramic with light weight, high strength and high toughness and preparation method thereof |
| US20130025459A1 (en) * | 2011-07-31 | 2013-01-31 | Kosuri Madhava R | Hollow ceramic fibers, precursors for manufacture thereof utilizing pore formers, methods of making the same, and methods of using the same |
| CN103524140A (en) * | 2013-09-23 | 2014-01-22 | 天津大学 | Oxide ceramic fiber board |
| CN104387112A (en) * | 2014-10-30 | 2015-03-04 | 朱冲 | Preparation method of ceramic fiber reinforced ceramic membrane supporter |
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