CN102701778A - Preparation method for ceramic film with hierarchical pore structure - Google Patents
Preparation method for ceramic film with hierarchical pore structure Download PDFInfo
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Abstract
The invention relates to a preparation method for a ceramic film with a hierarchical pore structure, which belongs to the technical field of preparation of ceramic films. The method comprises the following steps of: selecting raw material powder of different grain diameters and pore forming agents of different acid-base properties and grain diameters respectively by optimizing the grain diameter of a ceramic aggregate, and performing ball milling to obtain a film coating suspension which is uniformly dispersed; coating films according to the granularity and acid-base properties of the pore-forming agents in sequence by adopting a steeping-coating process, curing, drying and sintering, wherein every layer of film is required to be prepared by steeping and coating in a film making liquid prepared from acid and basic pore-forming agents of the same grain diameter in sequence, the aim of forming pores is fulfilled by performing an acid-alkali neutralizing reaction subsequently, and the grain diameters of selected pore-forming agents are gradually reduced according to the variations of the film layers; and preparing a ceramic film with controllable grain diameter and a gradually-distributed hierarchical pore structure through the variations of the grain diameters of the pore-forming agents. In the method, the thickness, porosity and pore diameter of a separating film are controlled reasonably, so that a material has the advantages of high mechanical performance, low cost and high permeation separation efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of porous ceramic film, especially a kind of controllable aperture and have the preparation method of Gradient distribution hierarchical porous structure ceramic membrane.
Background technology
The porous, inorganic ceramic membrane is owing to have excellent high separating efficiency, high temperature resistant, anti-solvent, antimicrobial, resistance to acids and bases, high mechanical strength and be prone to clean advantages such as renewable; Its application has been penetrated into food, beverage, has planted various fields such as the processing of (medicine) object depth, biological medicine, fermentation, fine chemistry industry, can be used in the technological process separation, clarification, purifying, concentrate, degerming, desalination etc.It mainly is made up of supporter, middle layer and separating layer, and three layers generally have the hole gradient, and the aperture so that can accomplish isolating purpose, can reach the requirement of saving power consumption with the variation of thickness rule again.The Gradient distribution aperture is continuous more, and its pressure-losses in use is more little; Pore size distribution is narrow more, and its separation efficiency is high more.Receive raw-material restriction; The preparation of porous ceramic support at present mainly is that to adopt size distribution be that the powder of 1～20 μ m is a raw material; Forming method such as extrude through dry-pressing, slip casting and plasticity and prepare, then above that through repeatedly applying finely dispersed preparation liquid.The shortcoming of this method is that pore size distribution is wayward, cause its separation efficiency lower, and pore size distribution is wide, causes causing easily in the membrane process in follow-up further being coated with blending problems such as rete is imperfect in the preparation liquid, influences the quality of porous ceramic film.
In order to obtain to have the ceramic membrane of multistage gradient pore structure, CN101670244A makes the particle of different-grain diameter size in the suspension-s get off according to descending sequential aggradation through gravity settling and vacuum take-off, thereby obtains the ceramic membrane of graded pore structure.CN101182233A discloses and has a kind ofly adopted the preparation of casting molding processes and freeze drying process to have opening directional hole structure and high porosity and the aperture preparation method at the porous ceramic film of film thickness direction graded.Though aforesaid method can be simplified the preparation technology of ceramic membrane to a certain extent, only is applicable to planar ceramic membrane, to present normally used tubular type hyperchannel ceramic-film tube and inapplicable.CN101323528A discloses a kind of preparation method of continuous hole graded ceramic tube; It has combined the advantage of centrifugal casting and gel injection, and mould is centrifugal, the postheating curing molding obtains continuous hole graded vitrified pipe through homodisperse gel injection suspension-s is injected.Though this method can be saved the vacuum stripping program of conventional gel injection molding; And easy handling, efficient height; But on the one hand; Centrifuging process needs rotating speed high, and on the other hand, this method is difficult to prepare the major diameter hyperchannel ceramic-film tube that is suitable in the application of engineering fields such as WWT and sea water desaltination.In addition, adopt the pore-forming material of different shapes and granularity can obtain the pore structure in different shapes and aperture, but owing to the restriction of pore-forming material granularity, particle diameter is that the following pore-forming material of 50nm is less, this has limited the preparation of porous ceramic ultra-filtering membrane, nf membrane.
To the problems referred to above, the present invention proposes to choose the raw material powder of different-grain diameter and the pore-forming material of different acid-basicity and particle diameter respectively through the preferably ceramic aggregate size, prepares the finely dispersed suspension-s of filming through ball milling.Adopt dipping-coating processes to film successively by the granularity and the different of its acid-basicity of pore-forming material; The preparation of each tunic all needs dipping-coating in the preparation liquid of acid and alkaline pore-forming material preparation of being of same particle diameter successively; Rely on acid-base neutralisation subsequently to react the purpose that reaches pore-forming; And press the variation of rete, the granularity of the pore-forming material of choosing reduces gradually, with after solidify, dry, sintering.Variation through the pore-forming material granularity realizes controllable aperture and has the preparation of the ceramic membrane of Gradient distribution hierarchical porous structure.Through each technological parameter of reasonable control, thickness, porosity and the aperture of control separatory membrane make material have high mechanical property, and lower cost and high permeation sepn efficient.
The purpose of this invention is to provide a kind of controllable aperture and have the preparation method of Gradient distribution hierarchical porous structure ceramic membrane, overcome at present because the ceramic membrane separation efficiency that ceramic membrane pore structure and pore size distribution cause is low, the pressure-losses is big and the problem of the difficult preparation in the following hole of 50nm.Through the raw material powder of preferred appropriate particle size and the pore-forming material of different acid-basicity and particle diameter; Through reasonable control process parameters; Prepare the suspension-s of finely dispersed different-grain diameter; Adopt dipping-coating processes on the ceramic film support surface according to the descending order of particle diameter coat film successively; And each tunic all needs in the coating liquid by same particle diameter and the preparation of different acid-basicity pore-forming material, flood certain hour successively, utilizes the acid-base neutralisation reaction that takes place between pore-forming material in the subsequent process to realize controllable aperture and has Gradient distribution hierarchical porous structure, strong mechanical performance and separate the porous ceramic film that permeates efficient.Preparation technology of the present invention is simple, to material system require lowly, production cost is low, is mainly used in water treatment field, also can be used for other various solid-liquid separation filtration procedurees, helps applying.
Summary of the invention
The present invention is directed at present because the ceramic membrane separation efficiency that ceramic membrane pore structure and pore size distribution cause is low, the pressure-losses is big and the problem of the difficult preparation in the following hole of 50nm; Proposition utilizes the acid-base neutralisation reaction between the pore-forming material to realize the purpose of pore-forming, and passes through the particle diameter realization controllable aperture and the Gradient distribution of pore-forming material.Main contents are following:
1. raw material
The ceramic aggregate of porous ceramic film can adopt one or more in aluminum oxide, zirconium white, silicon-dioxide, silit, titanium oxide, mullite, the trichroite, and median size is between 0.02-10 μ m.
Acid pore-forming material: ammonium chloride, aspartic acid, L-glutamic acid, Z 150PH etc., median size is made into the aqueous solution that content is 5-30% (mass ratio) with it between 0.02-1 μ m;
Alkalescence pore-forming material: NaHCO
3, Na
2CO
3, bicarbonate of ammonia, W-Gum, urea, Methionin, l-arginine, Histidine etc., median size is made into the aqueous solution that content is 5-30% (mass ratio) with it between 0.02-1 μ m;
2. flood-film the preparation of slurry
Adopt the mixed powder (ceramic aggregate+pore-forming material) of different-grain diameter to prepare the slurry of filming respectively; Ceramic aggregate accounts for (70-90% mass ratio) in the said mixed powder; Pore-forming material accounts for (10-30% mass ratio), and the volume ratio of mixed powder and water is 1.5-2: 1, and 4-12 hour ball milling time;
It is d that a adopts particle diameter
C1Ceramic aggregate, particle diameter be d
K1Ball mill mixing such as acid pore-forming material, water prepare homodisperse coating slurry A
1, use HCl, L-glutamic acid, nitric acid etc. to regulate the slurry pH value and be 3-6;
It is d that b adopts particle diameter
C1Ceramic aggregate, particle diameter be d
K1Ball mill mixing such as alkalescence pore-forming material, water prepare homodisperse coating slurry B
1, use NaOH, caustic soda etc. to regulate the slurry pH value and be 8-12;
It is d that c adopts particle diameter
C2Ceramic aggregate, particle diameter be d
K2Ball mill mixing such as acid pore-forming material, water prepare homodisperse coating slurry A
2, regulate slurry pH value 3-6 with HCl, L-glutamic acid, nitric acid etc.;
It is d that d adopts particle diameter
C2Ceramic aggregate, particle diameter be d
K2Ball mill mixing such as alkalescence pore-forming material, water prepare homodisperse coating slurry B
2, use NaOH, caustic soda etc. to regulate the slurry pH value and be 8-12;
D wherein
C1＞d
C2, d
K1＞d
K2
If will prepare the littler separating layer of pore size distribution, can continue to choose successively the littler ceramic aggregate of particle diameter, acidity and the preparation of alkaline pore-forming material and apply slurry A
3, B
3, A
4, B
4
3. the coating of film
At porous ceramic film support channel interior applied in two coats film at least, it adopts dipping-coating processes preparation, and the thickness of top layer film is 5-20 μ m, and porosity is 40-80%, and the aperture is between 0.002-0.05 μ m.
In order to prevent that slurry from permeating in hole, porous ceramic film support is immersed 2-5h in the ethanol earlier, the air in the hole is substituted by ethanol.If adopt the tubular type supporter, the outside surface of ceramic film support is covered with aluminium foil, if adopt flat supporter, cover with aluminium foil through the two ends of supporter.Successively porous ceramic film support is immersed the slurry A that films according to the descending order of particle diameter then
1With B through preheating
1In the preparation middle layer, subsequent drying 12-60h reacts through the acid-base neutralisation between the pore-forming material and to form hole.After successively above-mentioned ceramic film support is immersed the slurry A that films again
2With B through preheating
2In the preparation separating layer, subsequent drying 12-60h is at last at 1200-1400 ℃ of sintering and be incubated 2h and obtain ceramic membrane.Wherein, be 10-90s the action time of supporter and slurry, and the granularity of action time, raw material and pore-forming material through adjusting both is come the thickness and the aperture of controlling diaphragm.If will prepare the littler separating layer of pore size distribution, then need adopt the littler ceramic aggregate of particle diameter and pore-forming material to prepare to film slurry and repeat above-mentioned dipping-coating step to get final product.
Can obtain controllable aperture and have the ceramic membrane of Gradient distribution hierarchical porous structure through above-mentioned technology, according to varying in size of required separating layer aperture, the rete number is between 2-5.
The present invention improves traditional porous ceramic membrane prepare technology; Through the raw material powder of preferred appropriate particle size and the pore-forming material of different acid-basicity and particle diameter; Through reasonable control process parameters; Prepare the suspension-s of finely dispersed different-grain diameter; Adopt dipping-coating processes on the ceramic film support surface according to the descending order of particle diameter coat film successively, and each tunic all needs in the coating liquid by same particle diameter and the preparation of different acid-basicity pore-forming material, flood certain hour successively, utilizes acid-base neutralisation reaction realization controllable aperture that takes place between pore-forming material in the subsequent process and the porous ceramic film with Gradient distribution hierarchical porous structure.It is cellular uniformly that the hole of prepared porous ceramic film is, and void content can reach 30-60%, and the aperture is between 0.002-0.05 μ m.Utilize can the be supported aperture of body of aforesaid method to be 10-30 μ m; The aperture of first tunic is 0.8-1 μ m; The aperture of second tunic is 0.3-0.5 μ m; The aperture of trilamellar membrane is 0.05-0.1 μ m, and the aperture of the 4th tunic is 0.01-0.05 μ m, and the aperture of layer 5 film is 0.002-0.005 μ m.The ceramic membrane of the present invention's preparation all has very big potential application in various fields such as sea water desaltination, WWT, fine chemistry industries.
Embodiment
Through embodiment the present invention is further specified below.
Embodiment one:
With ceramic aggregate ZrO
2The acid pore-forming material ammonium chloride of (1 μ m, 70%) and 5wt% (1 μ m, 30%) do to mix 4h, is that 1.5: 1 batchings and ball mill mixing 4h prepare the slurry A that films by the volume ratio of mixed powder and water then
1, according to above-mentioned same technology with ceramic aggregate ZrO
2The alkaline pore-forming material yellow soda ash of (1 μ m, 70%), 5wt% (1 μ m, 30%), water for ball milling are mixed 4h and are prepared the slurry B that films
1
With ceramic aggregate ZrO
2The acid pore-forming material ammonium chloride of (0.5 μ m, 70%), 5wt% (0.5 μ m, 30%), water for ball milling are mixed 4h and are prepared the slurry A that films
2, with ceramic aggregate ZrO
2The alkaline pore-forming material yellow soda ash of (0.5 μ m, 70%), 5wt% (0.5 μ m, 30%), water for ball milling are mixed 4h and are prepared the slurry B that films
2
At first the porous ceramic film pipe is dashed at ethanol and soak 3h, then the ceramic-film tube outside is coated with aluminium foil and immersion slurry A
1In 60s, immersing subsequently through preheating is 80 ℃ slurry B
1Middle 60s makes acid-base neutralisation reaction formation hole takes place between the pore-forming material, and dry formation middle layer.Subsequently ceramic-film tube is immersed slurry A
2Behind the middle 60s, immersion is 80 ℃ slurry B through preheating
2Middle 60s makes acid-base neutralisation reaction formation hole takes place between the pore-forming material, and dry formation separating layer, and last sintering obtains ceramic membrane.When sintering temperature is 1400 ℃, gained ceramic foam thickness was 10 μ m when soaking time was 2h, the mean pore size of separating layer is 0.5 μ m, and porosity is 50%, and under the pressure of 0.1MPa, pure water flux is 1000L/m
2H.
Embodiment two:
With ceramic aggregate Al
2O
3The acid pore-forming material L-glutamic acid of (1 μ m, 90%), 25wt% (1 μ m, 10%) do to mix 6h, is that 2: 1 batchings and ball mill mixing 10h prepare the slurry A that films by the volume ratio of mixed powder and water then
1, according to above-mentioned technology respectively with ceramic aggregate Al
2O
3The alkaline pore-forming material sodium hydrogencarbonate of (1 μ m, 90%), 25wt% (1 μ m, 10%), water prepare the slurry B that films by above-mentioned technology ball mill mixing 10h
1
With ceramic aggregate Al
2O
3The acid pore-forming material L-glutamic acid of (0.5 μ m, 90%), 25wt% (0.5 μ m, 10%) do to mix 6h, is that 2: 1 batchings and ball mill mixing 10h prepare the slurry A that films by the volume ratio of mixed powder and water then
2, according to above-mentioned technology respectively with ceramic aggregate Al
2O
3The alkaline pore-forming material sodium hydrogencarbonate of (0.5 μ m, 90%), 25wt% (0.5 μ m, 10%), water prepare the slurry B that films by above-mentioned technology ball mill mixing 10h
2
With ceramic aggregate Al
2O
3The acid pore-forming material L-glutamic acid of (0.25 μ m, 90%), 25wt% (0.25 μ m, 10%), water for ball milling are mixed 10h and are prepared the slurry A that films
3, with ceramic aggregate Al
2O
3The alkaline pore-forming material sodium hydrogencarbonate of (0.25 μ m, 90%), 25wt% (0.25 μ m, 10%), water for ball milling are mixed 10h and are prepared the slurry B that films
3
At first ceramic-film tube is dashed at ethanol and soak 4h, then the ceramic-film tube outside is coated with aluminium foil and immersion slurry A
1In 90s, immersing subsequently through preheating is 60 ℃ slurry B
1Middle 90s makes acid-base neutralisation reaction formation hole, subsequent drying 48h takes place between the pore-forming material.Subsequently ceramic-film tube is immersed slurry A
2Behind the middle 90s, immersion is 80 ℃ slurry B through preheating
2Middle 90s makes acid-base neutralisation reaction formation hole and dry 48h takes place between the pore-forming material.At last ceramic-film tube is immersed slurry A
3Behind the middle 90s, immersion is 80 ℃ slurry B through preheating
3Middle 90s makes acid-base neutralisation reaction formation hole and dry 48h formation separating layer takes place between the pore-forming material.When sintering temperature is 1380 ℃, gained ceramic foam thickness was 15 μ m when soaking time was 2h, the mean pore size of separating layer is 0.05 μ m, and porosity is 30%, and under the pressure of 0.1MPa, pure water flux is 700L/m
2H.
Embodiment three:
The acid pore-forming material aspartic acid (1 μ m, 25%) of ceramic aggregate mullite (1 μ m, 75%), 15wt% done mix 12h, be that 1.5: 1 batchings and ball mill mixing 12h prepare the slurry A that films by the volume ratio of mixed powder and water then
1, respectively alkaline pore-forming material W-Gum (1 μ m, 25%), the water for ball milling of ceramic aggregate mullite (1 μ m, 75%), 15wt% are mixed 12h according to above-mentioned technology and prepare the slurry B that films
1
The acid pore-forming material aspartic acid (0.5 μ m, 25%) of ceramic aggregate mullite (0.5 μ m, 75%), 15wt% done mix 12h, be that 1.5: 1 batchings and ball mill mixing 12h prepare the slurry A that films by the volume ratio of mixed powder and water then
2, respectively alkaline pore-forming material W-Gum (0.5 μ m, 25%), the water for ball milling of ceramic aggregate mullite (0.5 μ m, 75%), 15wt% are mixed 12h according to above-mentioned technology and prepare the slurry B that films
2
Acid pore-forming material aspartic acid (0.25 μ m, 25%), the water for ball milling of ceramic aggregate mullite (0.25 μ m, 75%), 15wt% are mixed 12h prepare the slurry A that films
3, alkaline pore-forming material W-Gum (0.25 μ m, 25%), the water for ball milling of ceramic aggregate mullite (0.25 μ m, 75%), 15wt% are mixed 12h prepare the slurry B that films
3
Acid pore-forming material aspartic acid (0.1 μ m, 25%), the water for ball milling of ceramic aggregate mullite (0.1 μ m, 75%), 15wt% are mixed 12h prepare the slurry A that films
4, alkaline pore-forming material W-Gum (0.1 μ m, 25%), the water for ball milling of ceramic aggregate mullite (0.1 μ m, 75%), 15wt% are mixed 12h prepare the slurry B that films
4
At first ceramic-film tube is dashed at ethanol and soak 5h, then the ceramic-film tube outside is coated with aluminium foil and immersion slurry A
1In 80s, immersing subsequently through preheating is 80 ℃ slurry B
1Middle 80s after drying 24h makes acid-base neutralisation reaction formation hole takes place between the pore-forming material.Subsequently ceramic-film tube is immersed slurry A
2Behind the middle 80s, immersion is 80 ℃ slurry B through preheating
2Middle 80s after drying 24h repeats said process, then successively at last up to A
3, B
3And A
4, B
4Apply and accomplish.When sintering temperature is 1300 ℃, gained ceramic foam thickness was 15 μ m when soaking time was 2h, the mean pore size of separating layer is 0.01 μ m, and porosity is 50%, and under the pressure of 0.1MPa, pure water flux is 500L/m
2H.
Embodiment four:
The acid pore-forming material Z 150PH (1 μ m, 15%) of ceramic aggregate trichroite (1 μ m, 85%), 10wt% done mix 6h, be that 2: 1 batchings and ball mill mixing 6h prepare the slurry A that films by the volume ratio of mixed powder and water then
1, according to above-mentioned with sampling technology with the alkaline pore-forming material bicarbonate of ammonia (1 μ m, 15%) of ceramic aggregate trichroite (1 μ m, 85%), 10wt%, the water mixing 6h preparation slurry B that films
1
The acid pore-forming material Z 150PH (0.5 μ m, 15%) of ceramic aggregate trichroite (0.5 μ m, 85%), 10wt% done mix 6h, be that 2: 1 batchings and ball mill mixing 6h prepare the slurry A that films by the volume ratio of mixed powder and water then
2, according to above-mentioned with sampling technology with the alkaline pore-forming material bicarbonate of ammonia (0.5 μ m, 15%) of ceramic aggregate trichroite (0.5 μ m, 85%), 10wt%, the water mixing 6h preparation slurry B that films
2
Acid pore-forming material Z 150PH (0.25 μ m, 15%), the water mill mixing 6h of ceramic aggregate trichroite (0.25 μ m, 85%), 10wt% are prepared the slurry A that films
3, alkaline pore-forming material W-Gum (0.25 μ m, 15%), the water for ball milling of ceramic aggregate trichroite (0.25 μ m, 85%), 10wt% are mixed 6h prepare the slurry B that films
3
Acid pore-forming material Z 150PH (0.1 μ m, 15%), the water mill mixing 6h of ceramic aggregate trichroite (0.1 μ m, 85%), 10wt% are prepared the slurry A that films
4, alkaline pore-forming material bicarbonate of ammonia (0.1 μ m, 15%), the water for ball milling of ceramic aggregate trichroite (0.1 μ m, 85%), 10wt% are mixed 6h prepare the slurry B that films
4
Acid pore-forming material Z 150PH (0.05 μ m, 15%), the water mill mixing 6h of ceramic aggregate trichroite (0.05 μ m, 85%), 10wt% are prepared the slurry A that films
5, alkaline pore-forming material bicarbonate of ammonia (0.05 μ m, 15%), the water for ball milling of ceramic aggregate trichroite (0.05 μ m, 85%), 10wt% are mixed 6h prepare the slurry B that films
5
At first ceramic-film tube is dashed at ethanol and soak 3h, then the ceramic-film tube outside is coated with aluminium foil and immersion slurry A
1In 90s, immersing subsequently through preheating is 80 ℃ slurry B
1Middle 90s after drying 12h makes acid-base neutralisation reaction formation hole takes place between the pore-forming material.Subsequently ceramic-film tube is immersed slurry A
2Behind the middle 90s, immersion is 80 ℃ slurry B through preheating
2Middle 90s after drying 12h.Repeat said process then successively, at last up to A
3, B
3, A
4, B
4And A
5, B
5Apply and accomplish.Gained ceramic foam thickness is 15 μ m when sintering temperature is 1250 ℃, and the mean pore size of separating layer is 0.005 μ m, and porosity is 40%, and under the pressure of 0.1MPa, pure water flux is 300L/m
2H.
Claims (3)
1. the preparation method of a hierarchical porous structure ceramic membrane is characterized in that, said preparation method carries out successively as follows:
1. raw material
The ceramic aggregate of ceramic membrane: one or more in employing aluminum oxide, zirconium white, silicon-dioxide, silit, titanium oxide, mullite, the trichroite, median size is between 0.02-10 μ m;
Acid pore-forming material: ammonium chloride, aspartic acid, L-glutamic acid, Z 150PH etc., median size is made into the aqueous solution that content is 5-30% (mass ratio) with it between 0.02-1 μ m;
Alkalescence pore-forming material: NaHCO
3, Na
2CO
3, bicarbonate of ammonia, W-Gum, urea, Methionin, l-arginine, Histidine etc., median size is made into the aqueous solution that content is 5-30% (mass ratio) with it between 0.02-1 μ m;
2. flood-film the preparation of slurry
Adopt the mixed powder (ceramic aggregate+pore-forming material) of different-grain diameter to prepare the slurry of filming respectively; Ceramic aggregate accounts for (70-90% mass ratio) in the said mixed powder; Pore-forming material accounts for (10-30% mass ratio), and the volume ratio of mixed powder and water is 1.5-2: 1, and 4-12 hour ball milling time;
It is d that a adopts particle diameter
C1Ceramic aggregate, particle diameter be d
K1Acid pore-forming material, water for ball milling are mixed with homodisperse coating slurry A
1, use HCl, L-glutamic acid, nitric acid to regulate the slurry pH value and be 3-6;
It is d that b adopts particle diameter
C1Ceramic aggregate, particle diameter be d
K1Alkalescence pore-forming material, water for ball milling are mixed with homodisperse coating slurry B1, use NaOH, caustic soda etc. to regulate the slurry pH value and are 8-12;
It is d that c adopts particle diameter
C2Ceramic aggregate, particle diameter be d
K2Acid pore-forming material, water for ball milling are mixed with homodisperse coating slurry A
2, regulate slurry pH value 3-6 with HCl, L-glutamic acid, nitric acid;
It is d that d adopts particle diameter
C2Ceramic aggregate, particle diameter be d
K2Ball mill mixing such as alkalescence pore-forming material, water prepare homodisperse coating slurry B
2, use NaOH, caustic soda to regulate the slurry pH value and be 8-12;
D wherein
C1＞d
C2, d
K1＞d
K2
If will prepare the littler separating layer of pore size distribution, can continue to choose successively the littler ceramic aggregate of particle diameter, acidity and the preparation of alkaline pore-forming material and apply slurry A
3, B
3, A
4, B
4
3. the coating of film
At porous ceramic film support channel interior applied in two coats film at least, adopt dipping-coating processes to prepare, the thickness of top layer film is 5-20 μ m, and porosity is 40-80%, and the aperture is between 0.002-0.05 μ m.
2. preparation method according to claim 1 is characterized in that: in step 3. in the coating processes of film, porous ceramic film support was immersed earlier in the ethanol 2-5 hour, the air in the hole is substituted by ethanol.
3. preparation method according to claim 1 and 2; It is characterized in that: when porous ceramic film support adopts the tubular type supporter; The outside surface of ceramic film support is covered with aluminium foil; Perhaps when porous ceramic film support adopts flat supporter, the two ends of ceramic film support are covered with aluminium foil, successively porous ceramic film support is immersed the slurry A that films according to the descending order of particle diameter then
1With B through preheating
1The slurry A that films subsequent drying 12-60 hour, is immersed with above-mentioned ceramic film support more successively in middle preparation middle layer
2With B through preheating
2In the preparation separating layer, dry 12-60 hour,, obtain the hierarchical porous structure ceramic membrane at last at 1200-1400 ℃ of sintering and be incubated 2 hours.
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