CN114933481A - Ceramic membrane preparation method - Google Patents
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Abstract
A method of preparing a ceramic membrane by comprising the steps of: preparing a first filter membrane layer slurry through the first ceramic particles; preparing a first filtering membrane layer blank body through the first filtering membrane layer slurry; preparing second ceramic particles by a granulation method; preparing a second filter membrane layer slurry from the ceramic particles; preparing a second filtering membrane layer green body on the surface of the first filtering membrane layer green body subjected to glue removal through the second filtering membrane layer slurry, or preparing a second filtering membrane layer green body on the surface of the pre-sintered first filtering membrane layer green body through the second filtering membrane layer slurry to obtain a filtering membrane layer green body; therefore, the ceramic membrane has higher filtering efficiency, and the problem that the ceramic membrane is blocked in a short time when the ceramic membrane is used is avoided, and the problem that the ceramic membrane is damaged when impurities attached to the surface of the ceramic membrane are cleaned is avoided.
Description
Technical Field
The invention relates to the field of ceramic preparation, in particular to the field of a ceramic membrane preparation method for filtering.
Background
The ceramic membrane material has the advantages of high mechanical strength, good chemical stability, large pure water flux, oxidation resistance, good pollution resistance, easy cleaning and regeneration, long service life and the like, and is the key point of membrane technology research and development and application. So far, ceramic membrane separation technology has been developed greatly, and has been popularized and applied in the fields of food industry, petrochemical industry, medical health, bio-pharmaceuticals, environmental engineering and the like, and has been developed rapidly.
In engineering application, in order to improve filtration efficiency, the ceramic flat membrane has higher porosity, but when filtering sewage, the phenomenon that impurities in the sewage enter the pores of the ceramic membrane to block the ceramic membrane easily occurs, or the problem that the ceramic membrane is damaged when the impurities attached to the surface of the ceramic membrane are cleaned exists, so that the service life of the ceramic membrane is shortened.
Therefore, how to realize that the ceramic membrane has higher filtering efficiency, and simultaneously avoid the problem that the ceramic membrane is blocked in a short time of use, and avoid the problem that the ceramic membrane is damaged when impurities attached to the surface of the ceramic membrane are cleaned, so that the service life of the ceramic membrane is prolonged, and the technical problem in the field is solved.
Disclosure of Invention
The invention aims to realize that a ceramic membrane has higher filtering efficiency and the service life of the ceramic membrane is prolonged, and provides a preparation method of the ceramic membrane, which comprises the following steps: preparing a first filter membrane layer slurry through the first ceramic particles; preparing a first filtering membrane layer blank body by the first filtering membrane layer slurry; preparing second ceramic particles by a granulation method; preparing a second filter membrane layer slurry from the ceramic particles; preparing a second filtering membrane layer green body on the first filtering membrane layer green body through the second filtering membrane layer slurry to obtain a filtering membrane layer green body; therefore, the ceramic membrane has higher filtering efficiency, the problem that the ceramic membrane is blocked in a short time when the ceramic membrane is used is avoided, and the problem that the ceramic membrane is damaged when impurities attached to the surface of the ceramic membrane are cleaned is avoided.
In order to achieve the above object, the present invention provides a method for preparing a ceramic film, comprising the steps of: preparing a first filter membrane layer slurry through the first ceramic particles; preparing a first filtering membrane layer blank body through the first filtering membrane layer slurry; preparing second ceramic particles by a granulation method; preparing a second filter membrane layer slurry from the ceramic particles; preparing a second filtering membrane layer green body on the surface of the first filtering membrane layer green body subjected to glue removal through the second filtering membrane layer slurry, or preparing a second filtering membrane layer green body on the surface of the pre-sintered first filtering membrane layer green body through the second filtering membrane layer slurry to obtain a filtering membrane layer green body; finally sintering the filtering film layer green body to obtain the filter membrane; the ceramic film comprises a first film layer and a second film layer tightly connected with the first film layer; the first film layer green body is subjected to final sintering to obtain the first film layer, and the second film layer green body is subjected to final sintering to obtain the second film layer; the first ceramic particles and the second ceramic particles are SiC ceramic particles; preferably, the first ceramic particles are prepared without ceramic powder granulation, the density of the first ceramic particles is high, and the density of the first ceramic particles is more than or equal to 96% of the theoretical density; the porosity of the first film layer is 45-50%, the pore diameter is 1-10um, and the flexural strength is more than or equal to 23 MPa; the porosity of the second film layer is 50-55%, the pore diameter is 0.05-0.09um, and the flexural strength is more than or equal to 25 MPa; the second film thickness is 3-10um, preferably the second film thickness is 3-6 um.
When the ceramic membrane is applied to the field of filtration, the second membrane layer is directly contacted with liquid to be filtered, and the liquid is filtered by the first filter layer after passing through the second filter layer.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that a second filtering membrane layer blank body is prepared on the first filtering membrane layer blank body through the second filtering membrane layer slurry, so that the ceramic membrane comprises a first membrane layer and a second membrane layer tightly connected with the first membrane layer;
the first ceramic particles for preparing the first membrane layer are different from the second ceramic particles for preparing the second membrane layer; the second ceramic particles are prepared by the granulation method, so that the first film layer is high in density and not easy to block, the filtering efficiency of the second filtering layer is not reduced, the ceramic film has a high filtering effect, and the service life of the ceramic film is obviously prolonged.
Meanwhile, the second filtering membrane layer blank body is prepared on the surface of the first filtering membrane layer blank body of the second filtering membrane layer slurry after glue discharging, so that the bonding strength of the first filtering layer and the second filtering layer is favorably improved, the second membrane layer slurry is favorably and uniformly dispersed on the surface of the first membrane layer blank body, the phenomenon of coating leakage or excessive coating on the surface of the first membrane layer of the second membrane layer slurry is avoided, and the thickness reduction of the coated second membrane layer is favorably realized.
Further, the specific process for preparing the first filter membrane layer slurry is that the first ceramic particles are mixed with a first pore-forming agent, a first dispersing agent and a first binder and then ground, a first solvent is added, and the grinding is continued to obtain first filter membrane layer slurry; and/or
The specific process for preparing the second filter membrane layer slurry comprises the steps of mixing and grinding the second ceramic particles, a second pore-forming agent, a second dispersing agent and a second binder, then adding a second solvent, and continuously grinding to obtain the second filter membrane layer slurry.
The filter membrane layer slurry preparation method has the beneficial effects that the first pore-forming agent in the first filter membrane layer slurry is different from the second pore-forming agent in the second filter membrane layer slurry, so that the pore size difference between the first filter membrane layer and the second filter membrane layer is favorably realized.
Further, the specific process for preparing the second ceramic particles is to disperse ceramic powder into a solvent to obtain ceramic slurry, and add a second pore-forming agent to obtain second ceramic particle slurry; granulating, drying, sintering and screening the second ceramic particle slurry to obtain second ceramic particles;
the grain diameter D50 of the ceramic powder is 0.1-0.3 um; preferably, the ceramic powder particle size D50 is 0.1-0.2 um;
the particle size D50 of the second ceramic particles is 0.5-1.5 um; preferably, the particle size D50 of the second ceramic particles is 0.5-0.9 um; the volatile content in the second ceramic particles is 10-16%; preferably, the second pore-forming agent comprises one or more of ammonium bicarbonate and petroleum ether; the solvent is absolute ethyl alcohol; when the second pore-forming agent is ammonium bicarbonate, the preparation temperature of the second ceramic particle slurry is lower than 20 ℃;
and/or
The drying temperature of the particles is 100-;
the sintering temperature of the particles is 2200-2400 ℃, the heating rate from the room temperature to 950-1200 ℃ is 8-10 ℃/min, and the heating rate from 950-1200 ℃ to 2200-2400 ℃ is 3-5 ℃.
The further technical scheme has the beneficial effects that the grain diameter D50 of the ceramic powder for preparing the second ceramic particles is 0.2-1.0 um; the second ceramic particles which are beneficial to preparation have high strength;
preferably, the second pore-forming agent comprises one or more of ammonium bicarbonate and petroleum ether; the solvent is absolute ethyl alcohol, so that the ceramic powder is uniformly dispersed, and the problem of disorder in volatilization caused by excessive volatile matters is avoided during preparation of the second ceramic particles, so that the problem of non-uniform pores of the second ceramic particles is avoided, and the strength reduction of the second ceramic particles is avoided;
the second pore-forming agent comprises one or more of ammonium bicarbonate and petroleum ether, so that the pore diameter of pores is small, and the strength is high on the premise of high porosity of the second ceramic particles;
the temperature is 100-200 ℃ during drying, the heating rate is 8-10 ℃/min, and the heating rate is high, so that pores generated in the second ceramic particles are favorable as through holes, the generation of closed holes is avoided, and the problem of invalid closed holes is avoided;
the sintering temperature of the particles is 2200-2400 ℃, which is favorable for realizing high strength of the second ceramic particles obtained after sintering; the temperature rise rate from room temperature to 950 ℃ and 1200 ℃ is 8-10 ℃/min, which is beneficial to small crystal grains generated during sintering and avoiding closed pores; the temperature rise rate of 950-1200-2200-2400 ℃ is 3-5 ℃, so that the problem of closed pores caused by excessively high grain boundary migration rate at high temperature is avoided on the premise of facilitating the strength of the second ceramic particles;
therefore, the obtained second ceramic particles have high porosity and small pore diameter, the ratio of closed pores in the second ceramic particles is obviously reduced, and the strength of the second ceramic particles is higher.
Further, the specific process for preparing the first filtering membrane layer blank body is that the first filtering membrane layer slurry is injected into the bottom of a first mould, and is heated at the temperature of 40-100 ℃ after standing to obtain a first filtering membrane layer blank body;
the specific preparation process of the filtering membrane layer blank body comprises the following steps of carrying out primary glue removal on the first filtering membrane layer blank body; coating the second filtering membrane layer slurry on the surface of the first filtering membrane layer blank subjected to primary glue removal, standing, and heating at the temperature of 40-100 ℃ to obtain a filtering membrane layer blank; the filtering membrane layer blank comprises a first filtering membrane layer blank subjected to primary glue removal and the surface of the first filtering membrane layer blank attached to the surface subjected to the primary glue removal, and the filtering membrane layer blank is heated at the temperature of 40-100 ℃ after standing to obtain a second filtering membrane layer blank;
and performing secondary glue removal before final sintering of the filtering membrane layer green body.
The further technical scheme has the advantages that the first filtering membrane layer blank is subjected to primary glue removal before the second filtering membrane layer blank is prepared on the first filtering membrane layer blank, the second filtering membrane layer slurry part permeates into pores after the glue removal of the first filtering membrane layer blank, and a certain transition layer is formed between the first filtering layer and the second filtering layer, so that the bonding strength between the first filtering layer and the second filtering layer is improved, and meanwhile, the problem that the glue removal is simultaneously carried out on the first filtering membrane layer blank and the second filtering membrane layer blank after the second filtering membrane layer blank is prepared on the first filtering membrane layer blank is avoided, and further the problems that the pore distribution in the second filtering membrane layer blank is uneven and the pore diameter of pores is increased due to the influence of a pore-forming agent or other volatile matters in the first filtering membrane layer blank are avoided; and the second film layer slurry is favorably and uniformly dispersed on the surface of the first film layer blank, the phenomenon of coating leakage or excessive coating on the surface of the first film layer by the second film layer slurry is avoided, and the thickness reduction of the coated second film layer is favorably realized.
Further, the specific preparation process of the filtering membrane layer blank body is that after the first filtering membrane layer blank body is subjected to primary glue removal, the first filtering membrane layer blank body is subjected to presintering; and coating the second filtering membrane layer slurry on the surface of the pre-sintered first filtering membrane layer blank, preferably spraying the second filtering membrane layer slurry on the surface of the pre-sintered first filtering membrane layer blank.
The further technical scheme has the advantages that the second film layer slurry can be uniformly dispersed on the surface of the first film layer blank, the phenomenon of coating leakage or excessive coating on the surface of the first film layer slurry by the second film layer slurry is avoided, and the thickness of the coated second film layer is reduced; meanwhile, the first film layer blank has certain strength, and the first film layer blank is prevented from being damaged in the machining process.
Further, the specific process of the first filtering membrane layer for one-time glue discharging is as follows
The specific process of the first filtering membrane layer for primary glue removal is that the first filtering membrane layer is subjected to heating treatment at the temperature of 300-600 ℃;
the second glue discharging specifically comprises the step of performing heating treatment on the second filtering membrane layer slurry after preparing a second filtering membrane layer blank on the first filtering membrane layer blank, wherein the heating temperature is 120-200 ℃.
And/or
The pre-sintering temperature of the first filtering membrane layer blank is 800-1000 ℃.
The beneficial effect of adopting the above-mentioned further technical scheme lies in, is favorable to combining with first pore-forming agent, second pore-forming agent to realize that aperture is big in the first filtration rete, and aperture is little in the second filtration layer to be favorable to avoiding the problem of the great range increase of filtrating liquid pressure that leads to because the aperture of pore is little in the first filtration layer.
Furthermore, a first supporting strip and a second supporting strip are arranged on two sides of the second filtering membrane layer blank; the first support strip green body, the second support strip green body and the second filter membrane layer green body are matched to form a concave structure; the first filtering membrane layer green body is positioned in the groove of the concave-character-shaped structure, and three surfaces of the first filtering membrane layer green body are respectively connected with the first supporting strip green body, the second supporting strip green body and the second filtering membrane layer green body;
forming the first filtering membrane layer green body in a first die, removing glue once or pre-sintering, taking out, placing the first filtering membrane layer green body in a second die, wherein the second die is provided with a concave-shaped accommodating space, part or all of the second filtering membrane layer green body is positioned in the concave-shaped accommodating space, the first filtering membrane layer green body is positioned at the opening of a groove of the concave-shaped accommodating space, and the first filtering membrane layer green body is parallel to the bottom surface of the groove of the concave-shaped accommodating space; injecting second membrane layer slurry into spaces on two sides of the first filtering membrane layer green body, wherein the surfaces of the second membrane layer slurry on two sides of the first filtering membrane layer green body are not higher than that of the first membrane layer green body, standing and heating at the temperature of 40-100 ℃, and obtaining a first supporting strip green body and a second supporting strip green body on two sides of the first membrane layer green body;
and then spraying second film layer slurry on the surface of the first film layer green body, and then spraying the second film layer slurry on the surfaces of the first supporting strip green body and the second supporting strip green body.
The filter membrane layer blank is positioned in the groove of the concave-character-shaped structure, so that the bonding strength of the first membrane layer and the second membrane layer is further improved; meanwhile, the ceramic membrane wall is used, the first supporting strips and the second supporting strips can serve as clamping parts of the ceramic membrane in the using process, and the first supporting strips and the second supporting strips which are prepared by the second membrane layer slurry are high in density and strength, so that the problem that the clamping parts of the ceramic membrane are damaged when the ceramic membrane clamping parts are disassembled and installed for many times can be solved.
Further, the first filtering membrane layer blank body is provided with a plurality of through liquid through holes, and the first filtering membrane layer blank body is provided with a plurality of through liquid through holes; the connection surface of the first filtering membrane layer blank and the second filtering membrane layer blank is parallel to the liquid through hole; or
The first filtering membrane layer blank body is provided with a plurality of through liquid holes, two ends of each through liquid hole are in contact with the first supporting strip blank body and the second supporting strip blank body, and the first supporting strip blank body and the second supporting strip blank body are provided with through holes communicated with the through liquid holes.
Adopt above-mentioned further technical scheme's beneficial effect to lie in, through first filtration rete body is equipped with a plurality of logical liquid holes that link up, does not influence the liquid flux and the intensity of first filtration rete promptly, avoids under the prerequisite of filterable impurity entering the problem of first filtration rete simultaneously, realizes filterable liquid and has continued the collection, and has avoided because the problem that needs the filtration liquid pressure to increase by a wide margin when the aperture in first filtration rete hole leads to filtering easily.
Further, the first ceramic particles have a particle size D50 of 10 to 40 μm or include ceramic particles having a particle size D50 of 0.5 to 2 μm and ceramic particles of 10 to 40 μm;
the first pore former comprises carbon black and/or starch; the first dispersant is polyacrylic acid or ammonium polyacrylate; the first binder is sodium carboxymethyl cellulose or PVA;
and/or
The second pore-forming agent comprises one or more of ammonium bicarbonate and petroleum ether.
And/or
The mass fraction of the first ceramic particles in the first filter membrane layer slurry is 40-45%; the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 46-55%; the mass fraction of the first ceramic particles in the first filter membrane layer slurry is smaller than the mass fraction of the second ceramic particles in the second filter membrane layer slurry.
The further technical scheme has the advantages that the first ceramic particles with the particle size D50 of 10-40 mu m or the first ceramic particles comprising the ceramic particles with the particle size D50 of 0.5-2 mu m and the ceramic particles with the particle size of 10-40 mu m are beneficial to large pore diameter, and meanwhile, the strength of the second film layer is improved on the premise of high porosity;
by the first pore former comprising carbon black and/or starch; the first dispersing agent is polyacrylic acid or ammonium polyacrylate, namely the first dispersing agent is a macromolecular surfactant, so that the pore size of pores in the first film layer is larger; the problem that the pressure is required to be greatly increased during liquid filtration due to the small pore diameter of the second membrane layer is solved.
Through the second pore-forming agent includes one or more in ammonium bicarbonate, the petroleum ether, and it is little to be favorable to realizing the aperture of second rete mesopore, and when pore-forming agent volatilizees the pore-forming, avoids volatilizing the problem that unordered lead to second rete intensity to reduce.
The mass fraction of the first ceramic particles in the first filter membrane layer slurry is smaller than that of the second ceramic particles in the second filter membrane layer slurry, the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 46-55%, and the second ceramic particles are combined to be prepared through granulation, so that the strength of the second membrane layer can be realized, and meanwhile, the porosity of the second membrane layer can be high.
Further, the specific process of the final sintering of the filter membrane layer green body is that the final sintering temperature is 2200-2400 ℃, the temperature rise rate from the room temperature to 950-1200 ℃ is 8-10 ℃/min, and the temperature rise rate from 950-1200 ℃ to 2200-2400 ℃ is 3-5 ℃; the sintering time is 1-4h at the final sintering temperature of 2200-.
The further technical scheme has the beneficial effects that the final sintering temperature is 2200-2400 ℃, so that the ceramic membrane is high in strength, the temperature rise rate from the room temperature to 950-1200 ℃ is 8-10 ℃/min, so that the ceramic membrane is small in crystal, the temperature rise rate from 950-1200 ℃ to 2200-2400 ℃ is 3-5 ℃, the problem that a large amount of closed pores are formed in the ceramic due to the fact that the crystal boundary migration rate is too high in the final sintering process is avoided, and the problem that the liquid flux is reduced during filtering of the ceramic membrane is avoided.
Detailed Description
In order to better understand the technical solution of the present invention, the present invention is further described below with reference to specific examples.
Example 1:
the embodiment provides a ceramic membrane preparation method, which comprises the following steps: preparing a first filter membrane layer slurry through the first ceramic particles; preparing a first filtering membrane layer blank body through the first filtering membrane layer slurry; preparing second ceramic particles by a granulation method; preparing a second filter membrane layer slurry from the ceramic particles; preparing a second filtering membrane layer green body on the surface of the first filtering membrane layer green body subjected to glue removal through the second filtering membrane layer slurry, or preparing a second filtering membrane layer green body on the surface of the pre-sintered first filtering membrane layer green body through the second filtering membrane layer slurry to obtain a filtering membrane layer green body; finally sintering the filtering film layer green body to obtain the filter membrane; the first ceramic particles and the second ceramic particles are SiC ceramic particles; the first ceramic particles are prepared without ceramic powder granulation, the density of the first ceramic particles is high, and the density of the first ceramic particles is more than or equal to 96% of the theoretical density;
the ceramic film comprises a first film layer and a second film layer tightly connected with the first film layer; the first film layer green body is subjected to final sintering to obtain the first film layer, and the second film layer green body is subjected to final sintering to obtain the second film layer; when the ceramic membrane is applied to the field of filtration, the second membrane layer is directly contacted with liquid to be filtered, and the liquid is filtered by the first filter layer after passing through the second filter layer.
The specific process for preparing the first filtering membrane layer slurry comprises the steps of mixing the first ceramic particles with a first pore-forming agent, a first dispersing agent and a first binder, grinding, adding a first solvent, and continuously grinding to obtain first filtering membrane layer slurry;
the specific process for preparing the second filter membrane layer slurry comprises the steps of mixing and grinding the second ceramic particles, a second pore-forming agent, a second dispersing agent and a second binder, then adding a second solvent, and continuously grinding to obtain the second filter membrane layer slurry.
The specific process for preparing the second ceramic particles comprises the steps of dispersing ceramic powder into a solvent to obtain ceramic slurry, and adding a second pore-forming agent to obtain second ceramic particle slurry; granulating, drying, sintering and screening the second ceramic particle slurry to obtain second ceramic particles; the grain diameter D50 of the ceramic powder is 0.22 um;
the particle size D50 of the second ceramic particles is 0.8 um; the volatile content of the second ceramic particles was 14%; the second pore-forming agent is petroleum ether; the solvent is absolute ethyl alcohol; the drying temperature of the particles is 160 ℃, and the heating rate is 9 ℃/min; the sintering temperature of the particles is 2300 ℃, the heating rate of the temperature ranging from room temperature to 950-1200 ℃ is 9 ℃/min, and the heating rate of the temperature ranging from 950-1200 ℃ to 2300 ℃ is 4 ℃.
The first ceramic particle diameter D50 is 30 μm; the first pore former comprises carbon black; the first dispersant is polyacrylamide; the first binder is sodium carboxymethyl cellulose; the second pore former comprises petroleum ether.
The mass fraction of the first ceramic particles in the first filter membrane layer slurry is 43%; the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 50%; the mass fraction of the first ceramic particles in the first filter membrane layer slurry is smaller than the mass fraction of the second ceramic particles in the second filter membrane layer slurry.
The specific process for preparing the first filtering membrane layer blank body comprises the steps of injecting the first filtering membrane layer slurry into the bottom of a first mold, standing, and heating at the temperature of 50 ℃ to obtain a first filtering membrane layer blank body;
the specific preparation process of the filtering membrane layer blank body comprises the following steps of carrying out primary glue removal on the first filtering membrane layer blank body; spraying the second filtering membrane layer slurry on the surface of the first filtering membrane layer blank subjected to primary degumming in a first mould, standing, and heating at 50 ℃ to obtain a filtering membrane layer blank; the filtering membrane layer blank comprises a first filtering membrane layer blank subjected to primary glue removal and the surface of the first filtering membrane layer blank attached to the surface subjected to the primary glue removal, and is heated at the temperature of 50 ℃ after standing to obtain a second filtering membrane layer blank; and performing secondary glue removal before final sintering of the filtering membrane layer green body.
The specific process of the first filtering membrane layer for primary rubber removal is that the first filtering membrane layer is subjected to heating treatment at the heating temperature of 550 ℃;
and the second glue discharging specifically comprises the step of heating the second filtering membrane layer slurry on the first filtering membrane layer blank to prepare a second filtering membrane layer blank at the heating temperature of 180 ℃.
The specific process of the final sintering of the filter membrane layer green body is that the final sintering temperature is 2300 ℃, the heating rate from room temperature to 950-1200 ℃ is 9 ℃/min, and the heating rate from 950-1200 ℃ to 2300 ℃ is 4 ℃; the sintering time is 2.5h at the final sintering temperature of 2300 ℃.
The porosity of the first film layer in the obtained ceramic film is 46%, the aperture is 1-9um, and the breaking strength is 24 MPa; the porosity of the second film layer is 52%, the pore diameter is 0.05-0.09um, and the flexural strength is 27 MPa; the thickness of the second film layer is 4 um.
Example 2:
the same contents of this embodiment as those of embodiment 1 are not described again, and the different features of this embodiment from those of embodiment 1 are:
the specific process for preparing the second ceramic particles comprises the steps of dispersing ceramic powder into a solvent to obtain ceramic slurry, and adding a second pore-forming agent to obtain second ceramic particle slurry; granulating, drying, sintering and screening the second ceramic particle slurry to obtain second ceramic particles;
the grain diameter D50 of the ceramic powder is 0.2 um;
the particle size D50 of the second ceramic particles is 0.9 um; the volatile content of the second ceramic particles is 15%; the second pore former comprises bicarbonate; when the second pore-forming agent is ammonium bicarbonate, the preparation temperature of the second ceramic particle slurry is lower than 20 ℃; the drying temperature of the particles is 120 ℃, and the heating rate is 8 ℃/min; the sintering temperature of the particles is 2350 deg.C, the heating rate from room temperature to 950-1200 deg.C is 8.5 deg.C/min, and the heating rate from 950-1200 deg.C to 2350 deg.C is 3.5 deg.C.
The first ceramic particle diameter D50 is 35 μm;
the first pore former comprises starch; the first binder is PVA; the second pore-forming agent is ammonium bicarbonate.
The mass fraction of the first ceramic particles in the first filter membrane layer slurry is 44%; the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 52%;
the specific preparation process of the filtering membrane layer blank body is that after the first filtering membrane layer blank body is subjected to primary glue removal, the first filtering membrane layer blank body is subjected to pre-sintering; and injecting the second filtering membrane layer slurry into the surface of the pre-sintered first filtering membrane layer blank in the first die.
The sintering temperature of the first filtering membrane layer blank subjected to pre-sintering is 950 ℃.
The first filtering membrane layer blank body is provided with a plurality of through liquid through holes, and the first filtering membrane layer blank body is provided with a plurality of through liquid through holes; the connecting surface of the first filtering membrane layer blank and the second filtering membrane layer blank is parallel to the liquid through hole;
the specific process of the first filtering membrane layer for primary rubber removal is that the first filtering membrane layer is subjected to heating treatment at the heating temperature of 500 ℃;
the second glue discharging specifically comprises the step of heating the second filtering membrane layer slurry after preparing a second filtering membrane layer green body on the first filtering membrane layer green body at the heating temperature of 160 ℃.
The specific process of the final sintering of the filter membrane layer green body is that the final sintering temperature is 2250 ℃, the temperature rise rate from room temperature to 950-; the sintering time is 3.5h at the final sintering temperature of 2250 ℃;
the porosity of the first film layer in the obtained ceramic film is 45%, the aperture is 1-9um, and the breaking strength is 25 MPa; the porosity of the second film layer is 53%, the pore diameter is 0.05-0.09um, and the flexural strength is more than or equal to 28 MPa; the thickness of the second film layer is 5 um.
Example 3:
the same contents of this embodiment as those of embodiment 1 are not described again, and the different features of this embodiment from those of embodiment 1 are:
the specific process for preparing the second ceramic particles comprises the steps of dispersing ceramic powder into a solvent to obtain ceramic slurry, and adding a second pore-forming agent to obtain second ceramic particle slurry; granulating, drying, sintering and screening the second ceramic particle slurry to obtain second ceramic particles;
the grain diameter D50 of the ceramic powder is 0.28 um;
the particle size D50 of the second ceramic particles is 0.8 um; the volatile content of the second ceramic particles is 15%; the drying temperature of the particles is 120 ℃, and the heating rate is 8.5 ℃/min; the sintering temperature of the particles is 2350 deg.C, the heating rate of the particles from room temperature to 950-.
The first ceramic particle diameter D50 is 38 μm;
the first pore former comprises carbon black and starch;
the mass fraction of the first ceramic particles in the first filter membrane layer slurry is 42%; the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 52%; the mass fraction of the first ceramic particles in the first filter membrane layer slurry is smaller than the mass fraction of the second ceramic particles in the second filter membrane layer slurry.
A first supporting strip and a second supporting strip are arranged on two sides of the second filtering membrane layer blank; the first supporting strip green body, the second supporting strip green body and the second filtering membrane layer green body are matched to form a concave structure; the first filtering membrane layer green body is positioned in the groove of the concave-character-shaped structure, and three surfaces of the first filtering membrane layer green body are respectively connected with the first supporting strip green body, the second supporting strip green body and the second filtering membrane layer green body;
forming the first filtering membrane layer green body in a first mould, removing glue once, pre-sintering and taking out, placing the first filtering membrane layer green body in a second mould, wherein the second mould is provided with a concave-shaped accommodating space, part or all of the second filtering membrane layer green body is positioned in the concave-shaped accommodating space, the first filtering membrane layer green body is positioned at the opening of a groove of the concave-shaped accommodating space, and the first filtering membrane layer green body is parallel to the bottom surface of the groove of the concave-shaped accommodating space; injecting second membrane layer slurry into spaces on two sides of the first filtering membrane layer green body, wherein the surfaces of the second membrane layer slurry on two sides of the first filtering membrane layer green body are not higher than that of the first membrane layer green body, standing and heating at the temperature of 80 ℃, and obtaining a first supporting strip green body and a second supporting strip green body on two sides of the first membrane layer green body;
and then spraying second film layer slurry on the surface of the first film layer green body, and then spraying the second film layer slurry on the surfaces of the first supporting strip green body and the second supporting strip green body.
The sintering temperature of the first filtering membrane layer blank subjected to pre-sintering is 950 ℃.
First filtration membrane layer blank is equipped with a plurality of logical liquid holes that link up, lead to the contact of liquid hole both ends and first support strip blank, second support strip blank, first support strip blank, second support strip blank be equipped with the through-hole that leads to the liquid hole intercommunication.
The specific process of the first filtering membrane layer for primary rubber removal is that the first filtering membrane layer is subjected to heating treatment at the heating temperature of 500 ℃;
the second glue discharging specifically comprises the step of heating the second filtering membrane layer slurry after preparing a second filtering membrane layer green body on the first filtering membrane layer green body, wherein the heating temperature is 180 ℃.
The specific process of the final sintering of the filtering membrane layer green body is that the final sintering temperature is 2350 ℃, the temperature rise rate from room temperature to 950-1200 ℃ is 9 ℃/min, and the temperature rise rate from 950-1200 ℃ to 2350 ℃ is 3.5 ℃; the sintering time is 3h at the final sintering temperature of 2200-.
The porosity of the first film layer in the obtained ceramic film is 49%, the aperture is 1-9um, and the breaking strength is 23 MPa; the porosity of the second film layer is 51%, the pore diameter is 0.5-0.9um, and the resistance is more than or equal to 28 MPa; the thickness of the second film layer is 5 um.
The foregoing description is only exemplary of the preferred embodiments of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the features described above have similar functions to (but are not limited to) those disclosed in this application.
Claims (10)
1. A ceramic membrane preparation method is characterized by comprising the following steps:
preparing a first filter membrane layer slurry through the first ceramic particles;
preparing a first filtering membrane layer blank body by the first filtering membrane layer slurry;
preparing second ceramic particles by a granulation method;
preparing a second filter membrane layer slurry from the ceramic particles;
preparing a second filtering membrane layer green body on the surface of the first filtering membrane layer green body subjected to glue removal through the second filtering membrane layer slurry, or preparing a second filtering membrane layer green body on the surface of the pre-sintered first filtering membrane layer green body through the second filtering membrane layer slurry to obtain a filtering membrane layer green body;
finally sintering the filtering film layer green body to obtain the filter membrane; the ceramic membrane comprises a first membrane layer and a second membrane layer tightly connected with the first membrane layer.
2. The method for preparing a ceramic membrane according to claim 1, wherein the first filter membrane layer slurry is prepared by mixing the first ceramic particles with a first pore-forming agent, a first dispersing agent and a first binder, grinding, adding a first solvent, and continuously grinding to obtain a first filter membrane layer slurry;
and/or
The specific process for preparing the second filter membrane layer slurry comprises the steps of mixing the second ceramic particles with a second pore-forming agent, a second dispersing agent and a second binder, grinding, adding a second solvent, and continuously grinding to obtain the second filter membrane layer slurry.
3. The ceramic membrane preparation method according to claim 1, wherein the second ceramic particles are prepared by dispersing a ceramic powder in a solvent to obtain a ceramic slurry, and adding a second pore-forming agent to obtain a second ceramic particle slurry; granulating, drying, sintering and screening the second ceramic particle slurry to obtain second ceramic particles;
the grain diameter D50 of the ceramic powder is 0.1-0.3 um;
the particle size D50 of the second ceramic particles is 0.5-1.5 um; the volatile content in the second ceramic particles is 10-16%;
and/or
The drying temperature of the particles is 100-;
the sintering temperature of the particles is 2200-2400 ℃.
4. The ceramic membrane preparation method according to claim 1, wherein the first filtering membrane layer blank is prepared by pouring the first filtering membrane layer slurry into the bottom of a first mold, standing, and heating at 40-100 ℃ to obtain a first filtering membrane layer blank;
the specific preparation process of the filtering membrane layer blank body comprises the following steps of carrying out primary glue removal on the first filtering membrane layer blank body; coating the second filtering membrane layer slurry on the surface of the first filtering membrane layer blank subjected to primary glue removal, standing, and heating at the temperature of 40-100 ℃ to obtain a filtering membrane layer blank; the filtering membrane layer blank comprises a first filtering membrane layer blank subjected to primary glue removal and the surface of the first filtering membrane layer blank attached to the surface subjected to the primary glue removal, and the filtering membrane layer blank is heated at the temperature of 40-100 ℃ after standing to obtain a second filtering membrane layer blank;
and performing secondary glue removal before final sintering of the filtering membrane layer green body.
5. The ceramic membrane preparation method according to claim 4, wherein the filter membrane layer blank is prepared by pre-sintering the first filter membrane layer blank after the first filter membrane layer blank is subjected to primary glue removal; and coating the second filtering membrane layer slurry on the surface of the pre-sintered first filtering membrane layer blank.
6. The ceramic membrane preparation method as claimed in claim 4 or 5, wherein the first filtration membrane layer is subjected to a primary degumming process by heating the first filtration membrane layer at a temperature of 300 ℃ to 600 ℃;
the second glue discharging specifically comprises the step of performing heating treatment on the second filtering membrane layer slurry after preparing a second filtering membrane layer blank on the first filtering membrane layer blank, wherein the heating temperature is 120-200 ℃.
And/or
The pre-sintering temperature of the first filtering membrane layer blank is 800-1000 ℃.
7. The ceramic membrane preparation method according to claim 1, wherein first and second support strips are provided on both sides of the second filtration membrane layer blank; the first support strip green body, the second support strip green body and the second filter membrane layer green body are matched to form a concave structure; the first filtering membrane layer green body is located in the groove of the concave-character-shaped structure, and three surfaces of the first filtering membrane layer green body are connected with the first supporting strip green body, the second supporting strip green body and the second filtering membrane layer green body respectively.
8. A ceramic membrane preparation method as claimed in claim 1 or 7, wherein the first filtration membrane layer blank is provided with a plurality of through liquid holes; the connection surface of the first filtering membrane layer blank and the second filtering membrane layer blank is parallel to the liquid through hole;
or
The first filtering membrane layer blank body is provided with a plurality of through liquid holes, two ends of each through liquid hole are in contact with the first supporting strip blank body and the second supporting strip blank body, and the first supporting strip blank body and the second supporting strip blank body are provided with through holes communicated with the through liquid holes.
9. A ceramic membrane production method according to claim 2, wherein the first ceramic particle size D50 is 10-40 μm;
the first pore former comprises carbon black and/or starch; the first dispersant is polyacrylic acid or ammonium polyacrylate; the first binder is sodium carboxymethyl cellulose or PVA;
and/or
The second pore-forming agent comprises one or more of ammonium bicarbonate and petroleum ether.
And/or
The mass fraction of the first ceramic particles in the first filter membrane layer slurry is 40-45%; the mass fraction of the second ceramic particles in the second filter membrane layer slurry is 46-55%; the mass fraction of the first ceramic particles in the first filter membrane layer slurry is smaller than the mass fraction of the second ceramic particles in the second filter membrane layer slurry.
10. The ceramic film preparation method as claimed in claim 1, wherein the final sintering temperature of the filter film layer blank is 2200-2400 ℃, the temperature rising rate from room temperature to 950-1200 ℃ is 8-10 ℃/min, and the temperature rising rate from 950-1200 ℃ to 2200-2400 ℃ is 3-5 ℃; the final sintering time is 1-4h at the final sintering temperature of 2200-.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113110A (en) * | 2012-12-04 | 2013-05-22 | 海南大学 | Application method of composite silicon carbide ceramic fiber transition layer |
| CN105236986A (en) * | 2015-09-09 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Preparation method and application of multi-channel silicon carbide plate ceramic membrane support |
| CN112537959A (en) * | 2020-12-15 | 2021-03-23 | 辽宁省轻工科学研究院有限公司 | Preparation method of ceramic powder for plasma physical vapor deposition |
| CN215249737U (en) * | 2021-07-19 | 2021-12-21 | 哈尔滨乐普实业有限公司 | Ceramic membrane filter equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113110A (en) * | 2012-12-04 | 2013-05-22 | 海南大学 | Application method of composite silicon carbide ceramic fiber transition layer |
| CN105236986A (en) * | 2015-09-09 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Preparation method and application of multi-channel silicon carbide plate ceramic membrane support |
| CN112537959A (en) * | 2020-12-15 | 2021-03-23 | 辽宁省轻工科学研究院有限公司 | Preparation method of ceramic powder for plasma physical vapor deposition |
| CN215249737U (en) * | 2021-07-19 | 2021-12-21 | 哈尔滨乐普实业有限公司 | Ceramic membrane filter equipment |
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