CN107973615B - Mesoporous gamma-Al2O3Ceramic membrane and preparation method thereof - Google Patents
Mesoporous gamma-Al2O3Ceramic membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to mesoporous gamma-Al2O3The ceramic membrane and the preparation method thereof are characterized in that aluminum isopropoxide is used as a precursor, boehmite sol is formed through hydrolysis at high temperature, hydrophilic nano-scale flexible polymer microspheres accounting for 10-30% of the total weight of boehmite in the mixed sol are added as a template agent, and the porosity of the composite membrane is improved. Putting the uniformly mixed sol into a culture dish coated with solid paraffin at the bottom, and drying at room temperature, freeze-drying and calcining at high temperature to obtain the gamma-Al with smooth surface and uniform pore size distribution2O3A ceramic membrane.
Description
Technical Field
The invention relates to mesoporous gamma-Al2O3A ceramic membrane and its preparing process, especially a mesoporous gamma-Al prepared from hydrophilic cross-linked polymer microspheres as template by sol-gel method2O3Ceramic membrane belongs to porous ceramic membrane field.
Background
The ceramic membrane has the characteristics of strong mechanical property, high thermal stability, excellent pollution resistance and the like, so that the ceramic membrane can be widely applied to high-temperature environmental conditions, and the preparation method comprises a solid particle sintering method, a thin film precipitation method, a sol-gel method and the like. The solid particle sintering method is characterized in that inorganic powder micro-particles or superfine particles (the particle size is 0.1-10 mu m) and a proper medium are mixed and dispersed to form a stable suspension, the stable suspension is formed to be made into a green body, the green body is dried, and then sintering treatment is carried out at high temperature (1000-1600 ℃), so that the method not only can be used for preparing a microporous ceramic membrane or a ceramic support body, but also can be used for a microporous metal membrane. The thin film deposition method is a method of depositing a film on a support by sputtering, ion plating, metal plating, i.e., vapor deposition, or the like to prepare a thin film. The sol-gel technology is a new process for obtaining oxides or other compounds from metal organic compounds, metal inorganic compounds or their mixture through hydrolytic polycondensation, gradual gelation and corresponding post-treatment. The sol-gel method has the following advantages: (1) the process is simple, and the equipment requirement is low; (2) the method is suitable for large-area film preparation, and the film thickness can be controlled at micron level; (3) the chemical composition of the film is easy to control, and the preparation material can be designed on the molecular level; (4) more methods are provided for introducing catalyst for top layer membrane modification.
The permeability of a ceramic membrane is determined primarily by factors such as the porosity, connectivity, and pore morphology of the membrane. At present, a high-permeability ceramic membrane is prepared by adopting a fiber building technology and a pore-forming agent method. The fiber construction technology adopts nano metal oxide fibers as raw materials, and the fiber layers are arranged on the support body in a disordered way, so that the pore forms of the fiber layers are diversified, and the porosity is improved. The pore former method increases the number of pores by adding a pore former, thereby increasing porosity. The template method is a special pore-forming agent method, and the pore-forming agent has specific size and shape, so that pore ordering can be achieved, and the porosity can also be improved. The template method adopts the pore-forming agent with uniform particle size, can effectively control the shape, structure and size of the material, and prepares a series of nanofiltration, ultrafiltration and microfiltration porous ceramic membranes with uniform pore size, high selectivity and large porosity. The commonly used template agent mainly comprises two main types of organic microspheres and surface active agents. Sadakane et al [ j.chem.mater., 2007, 19 (23): 5779-5785]The metal oxide material with three-dimensional ordered macropores is prepared by taking polymethyl methacrylate (PMMA) microspheres as a template agent, and the porosity range is 66-81%. Pia et al (J.Ceram. Inter., 2015, 41: 11097-11105) respectively use polypropylene (PP) with a particle size of 250-450 μm and PMMA powder with a particle size of 250-450 μm as templates to prepare the porous ceramic material, and the results show that when the content of the templates is increased, the porosity is increased. Zhao et al [ j.chem. let., 2007, 36 (3):464～465、J.Chem.Let.，2008，37(4)：420-421]uses PMMA microspheres as a template agent to form pores, and adopts a codeposition method to prepare three-dimensional ordered macroporous ZrO2、SiO2And Al2O3Symmetrical ceramic film of which ZrO2The porosity of the film reaches 60 percent, and SiO is2The porosity of the film reaches 48.1%, but PMMA is insoluble in water and is difficult to disperse uniformly in solution or sol. Yun et Al (J.Ceram.Inter., 2015, 41: 10788-10794) at a diameter of 5 μm α -Al2O3PMMA powder with the diameter of 20 mu m is doped as a template agent as a main body, and the porosity of the prepared support body is about 40 percent. Xu jian et al [ j.r.met.mater. engin, 2008, 37 (2): 196 to 200]Polystyrene (PS) microspheres or aggregated colloid are used as template agent, TiO is adopted2-SiO2The sol and PS microsphere aggregate are mixed and spin-coated to prepare the porous TiO2-SiO2The membrane has a pore size of 200 to 300 nm. Xunanping et al (Chinese patent No. 200510038695.3) add PMMA or PS powder with a particle size of 100-1000 nm as a template agent into a coating solution on a porous metal or ceramic support, and the porosity of the obtained ceramic film reaches 60-80%.
The invention adopts hydrophilic flexible polymer microspheres as a template agent, which is easy to uniformly disperse in boehmite sol and can shrink in the gel drying and calcining processes, so that the aperture of the prepared ceramic membrane is far smaller than the particle size of the flexible microspheres.
Disclosure of Invention
The preparation method adopted by the invention mainly comprises the following steps: preparing boehmite sol by taking aluminum isopropoxide as a precursor; preparing Polyacrylamide (PAM) microspheres by a dispersion polymerization method, preparing poly N-isopropyl acrylamide (PNIPAM) microspheres by an emulsion polymerization method, and adding a spherical polymer serving as a template agent into mixed sol; drying and calcining the gel. The method comprises the following specific steps:
1. preparation of boehmite sol: taking aluminum isopropoxide as a precursor, isopropanol or ethanol as a solvent, water as a hydrolysis reactant, nitric acid or acetic acid as a peptizing agent, adjusting the pH to 3.5-4.0, taking polyvinyl alcohol (PVA) as a dispersing agent, controlling the hydrolysis and aging temperature to 85-92 ℃, hydrolyzing for 3-6 h, aging for 10-16 h, and then performing ultrasonic treatment at 70-90 ℃ for a period of time until a transparent and stable sol is formed;
2. preparing PAM microspheres: sequentially adding a mixed solvent of ethyl acetate and ethanol, monomer Acrylamide (AM), dispersant polyvinylpyrrolidone (PVP K30) and initiator Azobisisobutyronitrile (AIBN) in a volume ratio of 7: 3 into a four-mouth bottle, stirring and heating to 70 ℃ under the protection of nitrogen, wherein the system is transparent at the beginning of the reaction, continuing the reaction for 6 hours after forming a microemulsion to obtain a uniformly dispersed milky dispersion liquid, centrifugally settling the dispersion liquid by using an ultracentrifuge, separating out polymer microspheres, washing with absolute ethyl alcohol for multiple times, and then drying in vacuum at 60 ℃ for 48 hours; when the PVP concentration is 0.4X 102g/L, AIBN concentration 4X 10-4mol/L, AM concentration of (1-2) × 102g/L, PAM microspheres with the particle size of 100-200 nm can be obtained, (Caokanli, Stechner, Dian peak, Cao jin Yan, Wang Hualin, and monodisperse submicron polyacrylamide microspheres prepared by dispersion polymerization in an ethyl acetate/ethanol mixed solution, high school science and chemistry report, 2007, 28 (1): 193-198);
3. preparing PNIPAM microspheres: monomer N-isopropyl acrylamide (NIPAM), cross-linking agent N, N' -Methylene Bisacrylamide (MBA) and surfactant Sodium Dodecyl Sulfate (SDS) are added into a three-neck flask provided with a reflux condenser and an air guide device, and water is added for stirring and dissolving. General formula (N)2Heating to 70 deg.C 30min below liquid level, stabilizing for 15min, adding initiator potassium persulfate (KPS) under N2Reacting for 4h under protection to obtain PNIPAM nano-microspheres, and reacting at 0.01 mol/L-1Dialyzing in hydrochloric acid solution to remove unreacted monomers and other small molecular substances, and freeze-drying; when the mass ratio of the monomer NIPAM, the cross-linking agent MBA, the surfactant SDS and the initiator KPS is (1.300-1.372): 0.100: 0.057: 0.069 hours, the particle size of the obtained PNIPAM microsphere is about 90-150 nm (bear micro, spring Yang, Wangxiangqing, Fangjiangguo, Zhao soldier, Yangxianghe, preparation of ionic temperature-sensitive nano gel and evaluation of drug-carrying performance thereof, pharmaceutical journal of Chinese hospital 2015, 35 (10): 897-902);
4. dispersing one of PAM microspheres and PNIPA microspheres in water, then adding the dispersion into the boehmite sol at room temperature, wherein the content of the microspheres is 10-30 wt% of the solid content in the boehmite sol, stirring for a period of time, and performing ultrasonic treatment to uniformly disperse the template in the sol;
5. putting the sol obtained in the step 4 into a culture dish coated with solid paraffin at the bottom, drying at room temperature to form gel, and freeze-drying to obtain boehmite gel containing microspheres;
6. and (3) demolding the boehmite gel obtained in the last step, then placing the boehmite gel into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination, wherein the temperature rise procedure is that the temperature rises to 300 ℃ at 1 ℃/min, keeping the temperature for 1-5 h, then rising to 700-900 ℃ at 1-2 ℃/min, and keeping the temperature for 3-5 h.
The ultrasonic process in the step 1 can enable boehmite colloidal particles to be dispersed more uniformly, remove bubbles in sol, volatilize partial solvent and shorten later-stage drying time.
The polymer microspheres obtained in the steps 2 and 3 have the particle size range of 100-200 nm.
The petri dish containing paraffin wax in said step 5 can reduce stress generated during drying of the gel film, prevent cracking (Gajanan B.Kude, Ganapati D.Yadav, Microporous and Mesoporous Materials, 2016, 224: 43-50), and facilitate demolding after drying.
The freeze-drying molding in the step 5 can reduce the shrinkage of the blank body caused by common drying molding (Chinese patent, patent number 200610119248.5), and prevent the gel film from cracking in the drying process.
According to the invention, the template agent spherical polymer added into the boehmite sol has the characteristics of hydrophilicity, monodispersity and flexibility, the stability of the sol is not influenced in the process of mixing with the boehmite sol, and the microspheres can be uniformly mixed with the sol, and in the drying and calcining processes, the nano microspheres shrink and then decompose, so that the prepared ceramic membrane has very small pore diameter, very high porosity and narrow pore size distribution.
Drawings
FIG. 1 is a sol-gel process for preparing gamma-Al2O3Ceramic membraneThe process flow of (1).
FIG. 2 is a gamma-Al alloy prepared in example 12O3A nitrogen adsorption and desorption isotherm (a) and a pore size distribution curve (b) of the ceramic membrane.
FIG. 3 is a gamma-Al alloy prepared in example 12O3Field emission scanning electron microscopy of ceramic membranes.
Detailed Description
Example 1:
(1) preparation of boehmite sol: dissolving 2.042g of aluminum isopropoxide in 3ml of isopropanol, heating to 80 ℃, dropwise adding 16ml of distilled water into the isopropanol solution and continuously stirring, heating to 90 ℃ after adding, hydrolyzing for 4h, completely volatilizing the isopropanol in the hydrolysis process, then dropwise adding 2ml of 1 mol/L nitric acid solution, stirring for 12h at 90 ℃, ultrasonically treating the sol for 4h at 70 ℃ after the reaction is finished, and volatilizing 40% of distilled water to obtain stable and transparent boehmite sol;
(2) preparation of PAM microspheres: putting 14ml of ethyl acetate, 6ml of ethanol, 2g of AM, 0.8g of PVP and 0.0010g of AIBN into a four-neck flask, uniformly stirring, heating to 70 ℃ under the protection of nitrogen, reacting for 6 hours, after the reaction is finished, carrying out high-speed centrifugal precipitation on the obtained mixed solution, washing with absolute ethyl alcohol for multiple times, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain PAM microspheres with the average particle size of about 100 nm;
(3) preparing a sol containing PAM microspheres: taking 0.08g of PAM microspheres prepared in the step (2) into 2ml of distilled water, uniformly mixing, dropwise adding the PAM microsphere solution into the boehmite sol obtained in the step (1), stirring for 4 hours, and performing ultrasonic treatment at room temperature for 2 hours to obtain stable sol containing microspheres;
(4) drying and calcining: putting the sol obtained in the step (3) into a culture dish with the inner diameter of 5.65cm and the bottom coated with solid paraffin, drying at room temperature to form gel, putting the gel into a refrigerator for freezing, then freeze-drying for 12h, and demoulding after forming; placing the gel film in a ceramic crucible, placing the ceramic crucible in a muffle furnace for calcination, wherein the calcination temperature program is 1 ℃/min, heating to 300 ℃, keeping the temperature for 2 hours, heating to 700 ℃ at 2 ℃/min, keeping the temperature for 3 hours, and naturally cooling to obtain the porous ceramic film with the pore size distributionNarrow in the range of 2-10 nm, and the pore structure is regular and ordered2O3A ceramic membrane.
The prepared ceramic membrane is analyzed by adopting BET specific surface area (see the attached figure 2 of the specification), the test condition is at 300 ℃, a figure 1a is a nitrogen adsorption and desorption isotherm, belongs to a class IV isotherm type, is a mesoporous pore structure type, and indicates that the pore diameter range of a sample is 2-50 nm; FIG. 1b is a pore size distribution curve of the sample, from which it can be seen that the pore size of the sample ranges from 2 to 10nm, and the average pore size is 5.5 nm.
The prepared ceramic membrane is observed by a field emission electron microscope (see attached figure 3 in the specification), and the figure shows that the pores on the surface of the membrane are uniformly distributed, the pore size distribution is 2-10 nm, and the pore size distribution is consistent with the BET analysis result.
Example 2:
(1) preparation of boehmite sol: dissolving 2.042g of aluminum isopropoxide in 3ml of ethanol, heating to 80 ℃, dropwise adding 16ml of distilled water into the aluminum isopropoxide solution and continuously stirring, heating to 90 ℃ after the addition, hydrolyzing for 4h, completely volatilizing the ethanol in the hydrolysis process, then dropwise adding 0.252g (0.004mol) of acetic acid, stirring for 12h at 90 ℃ after the addition, carrying out ultrasonic treatment on the sol for 4h at 70 ℃ after the reaction is finished, and volatilizing 40% of distilled water to obtain stable and transparent boehmite sol;
(2) preparation of PNIPAM microspheres: 1.300g of NIPAM, 0.100g of MBA and 0.057g of SDS were put into a three-necked flask equipped with a reflux condenser and an air guide, and dissolved by adding water with stirring. General formula (N)2Heating to 70 deg.C 30min below liquid level, stabilizing for 15min, adding dropwise aqueous solution containing 0.069g KPS, adding water, and adding water to obtain a mixture2Reacting for 4h under protection to obtain PNIPAM nano-microspheres, and reacting at 0.01 mol/L-1Dialyzing in hydrochloric acid solution to remove unreacted monomers and other small molecular substances, and freeze-drying to obtain PNIPAM microspheres with the particle size of about 150 nm;
(3) preparing a PNIPAM microsphere-containing sol: taking 0.08g of PNIPAM microspheres prepared in the step (2) into 2ml of distilled water, uniformly mixing, dropwise adding the PNIPAM microsphere solution into the boehmite sol obtained in the step (1), stirring for 4 hours, and performing ultrasound treatment at room temperature for 2 hours to obtain stable sol containing microspheres;
(4) drying and calcining: putting the sol obtained in the step (3) into a culture dish with the inner diameter of 5.65cm and the bottom coated with solid paraffin, drying at room temperature to form gel, putting the gel into a refrigerator for freezing, then freeze-drying for 12h, and demoulding after forming; placing the gel film in a ceramic crucible, placing the ceramic crucible in a muffle furnace for calcination, wherein the calcination temperature program is that the temperature is increased to 300 ℃ at the speed of 1 ℃/min, keeping the temperature for 3 hours, then the temperature is increased to 700 ℃ at the speed of 1 ℃/min, keeping the temperature for 5 hours, and naturally cooling to obtain the three-dimensional ordered gamma-Al with narrow pore size distribution2O3A ceramic membrane.
Example 3:
(1) preparation of boehmite sol: the same as the step (1) in example 1;
(2) preparing PAM microspheres: putting 14ml of ethyl acetate, 6ml of ethanol, 4g of AM, 0.8g of PVP and 0.0010g of AIBN into a four-neck flask, uniformly stirring, heating to 70 ℃ under the protection of nitrogen, reacting for 6 hours, after the reaction is finished, carrying out high-speed centrifugal precipitation on the obtained mixed solution, washing with absolute ethyl alcohol for multiple times, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain PAM microspheres with the average particle size of about 180 nm;
(3) preparing PAM microsphere sol: taking 0.13g of PAM microspheres prepared in the step (2) into 2ml of distilled water, uniformly mixing, dropwise adding the PAM microsphere solution into the boehmite sol obtained in the step (1), stirring for 4 hours, and performing ultrasonic treatment at room temperature for a period of time to obtain stable sol containing microspheres;
(4) drying and calcining: the same procedure as in step (4) of example 1.
Claims (6)
1. Mesoporous gamma-Al2O3The ceramic membrane is characterized in that aluminum isopropoxide is used as a precursor, isopropanol or ethanol is used as a solvent, nitric acid or acetic acid is used as a peptizing agent, water is used as a hydrolysis reactant, nano-scale hydrophilic flexible polymer cross-linked microspheres are used as a template agent, a gel membrane is prepared by a sol-gel method, and then the ceramic membrane with small aperture, high porosity and narrow aperture distribution is obtained by drying and calcining, wherein the specific preparation steps are as follows:
(1) preparation of boehmite sol:
dissolving a certain proportion of aluminum isopropoxide in isopropanol, adjusting the pH value to 3.5-4.0, using polyvinyl alcohol as a dispersing agent, controlling the hydrolysis and aging temperature to be above 80 ℃, the hydrolysis time to be 3-6 h and the aging time to be 10-16 h, and then performing ultrasonic treatment at 70-90 ℃ for a period of time until a transparent and stable sol is formed;
(2) adding a template agent:
dispersing the nano hydrophilic flexible polymer microspheres in water, then adding the dispersion into the boehmite sol prepared in the step (1) at room temperature, magnetically stirring for a period of time, and then carrying out ultrasonic treatment to uniformly disperse the template agent in the sol;
(3) and (3) drying:
putting the sol obtained in the step (2) into a culture dish coated with solid paraffin at the bottom, drying at room temperature to form gel, and freeze-drying;
(4) and (3) calcining:
demolding the xerogel obtained in the step (3), calcining the xerogel in a muffle furnace, raising the temperature to 700-900 ℃ by program, and keeping the temperature for a period of time to obtain gamma crystal form Al2O3A ceramic membrane.
2. The mesoporous gamma-Al of claim 12O3A ceramic membrane, characterized by: in the step (1), the mass ratio of aluminum isopropoxide to water to nitric acid is 204.24 to (1494-1800) to (6.30-16.38); the polyvinyl alcohol is added in an amount of 5-10% by weight of the solid content in the mixed sol, and is used as a dispersing agent in a sol system and as a binder and a forming agent in a drying process.
3. The mesoporous gamma-Al of claim 12O3A ceramic membrane, characterized by: the hydrophilic flexible polymer microspheres added in the step (2) can be one of Polyacrylamide (PAM) microspheres and poly-N-isopropylacrylamide (PNIPAM) microspheres, the particle size is 100-200 nm, and the PAM microspheres and the PNIPAM microspheres are prepared by a dispersion polymerization method and an emulsion polymerization method respectively.
4. The mesoporous gamma-Al of claim 12O3A ceramic membrane, characterized by: and (3) coating solid paraffin on the bottom of the culture dish in the step (3) is favorable for reducing the friction force generated by the shrinkage of the gel in the drying process and is also favorable for demoulding after the gel is formed.
5. The mesoporous gamma-Al of claim 12O3A ceramic membrane, characterized by: in the step (4), the temperature rise procedure of calcination is to heat up to 300 ℃ at a speed of 1-2 ℃/min, keep the temperature for 1-5 h, heat up to 700-900 ℃ at a speed of 1-2 ℃/min, and keep the temperature for 3-5 h.
6. The mesoporous gamma-Al of claim 12O3A ceramic membrane, characterized by: the alumina obtained after calcination in the step (4) is in a gamma crystal form, and the pore size distribution of the alumina is narrower than that of the alpha crystal form.
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