CN110606768A - Cordierite porous ceramic membrane support and near-net-size preparation method thereof - Google Patents
Cordierite porous ceramic membrane support and near-net-size preparation method thereof Download PDFInfo
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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Abstract
The invention provides a cordierite porous ceramic membrane support and a near net size preparation method thereof, wherein the preparation method comprises the following steps: step S10, batching magnesium oxide, aluminum oxide and silicon dioxide according to the molar ratio of 2:2:5, and preparing the batching and water into slurry; step S20, pouring out the slurry, and carrying out foaming treatment to obtain foam slurry; step S30, pouring the foam slurry into a mold and carrying out gel reaction to obtain a blank; step S40, the blank body is subjected to microwave drying treatment to dry the blank body; and S50, sintering the dried green body in a sintering furnace, wherein in the sintering process, the temperature is respectively kept for 1-2h at 80-120 ℃, 350-.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a cordierite porous ceramic membrane support and a near net size preparation method thereof.
Background
The porous ceramic membrane has the advantages of good chemical stability, high temperature resistance, high filtration efficiency, easy cleaning and regeneration and the like, so that the porous ceramic membrane is increasingly widely applied to various fields of energy, medicines, chemical engineering, bioengineering, foods and the like. The porous ceramic membrane consists of a porous ceramic membrane support, an intermediate layer and a membrane layer, wherein the support is the basis of preparation and application of the porous ceramic membrane, and the high-performance support must meet the requirements of high strength, high porosity, controllable microstructure and the like.
According to different shapes of the support body, the ceramic membrane can be divided into a flat plate, a tubular type and a multi-channel type; the conventional production methods mainly include a dry press molding method, an extrusion molding method, a tape casting method, a slip casting method, and the like. One of the problems is that the ceramic body obtained by the method has the defects of low porosity, uneven pore size distribution, poor permeability, short ceramic membrane service life and the like, so that the preparation of the ceramic membrane support body with high porosity and high compressive strength is a key point of research.
Another major problem is that most of the existing porous ceramic membrane supports are pure alumina, which has the disadvantage of high firing temperature, so in recent years, many research institutes have tried to prepare porous ceramic membrane supports from other ceramic raw materials, such as mullite, silicon carbide, etc.
In addition, the re-processing after sintering is a difficulty in the sample processing process due to the brittleness of the ceramic material itself.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a cordierite porous ceramic membrane support with near net size, which has a high porosity and a high strength well matched with each other, has a relatively low firing temperature, and does not need to be processed after sintering.
The invention also provides a cordierite porous ceramic membrane support.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for preparing the near-net size of the cordierite porous ceramic membrane support according to the embodiment of the first aspect of the invention comprises the following steps:
step S10, batching magnesium oxide, aluminum oxide and silicon dioxide according to the molar ratio of 2:2:5, and preparing the batching and water into slurry;
step S20, pouring out the slurry, and carrying out foaming treatment to obtain foam slurry;
step S30, pouring the foam slurry into a mold and carrying out gel reaction to obtain a blank;
step S40, the blank body is subjected to microwave drying treatment to dry the blank body;
and S50, sintering the dried green body in a sintering furnace, wherein in the sintering process, the temperature is respectively kept for 1-2h at 80-120 ℃, 350-.
Further, in step S50, the absolute value of the linear shrinkage rate of sintering is 2% or less.
Further, in the step S10, the solid content of the slurry is 20 vol% to 30 vol%.
Further, in the step S10, the particle size of the magnesium oxide is 50nm to 1500nm, the particle size of the aluminum oxide is 300nm to 1000nm, and the particle size of the silicon dioxide is 100nm to 500 nm.
Further, the step S10 includes:
step S11, adding the monomer, the cross-linking agent and the dispersing agent into water and mechanically stirring to form a premixed solution;
step S12, adding the ingredients of magnesium oxide, aluminum oxide and silicon dioxide into the premixed solution, ball-milling for 15-20 h by a roller ball mill,
the monomer is acrylamide, the cross-linking agent is N, N-methylene bisacrylamide, the dispersing agent is ammonium polyacrylate, the monomer accounts for 5% -15% of the mass of water in the slurry, the cross-linking agent accounts for 0.5% -1.5% of the mass of water in the slurry, and the dispersing agent accounts for 0.5% -1.5% of the total mass of the magnesium oxide, the aluminum oxide and the silicon dioxide.
Further, the step S20 specifically includes:
and adding a foaming agent into the slurry and uniformly stirring to obtain the foam slurry, wherein the foaming agent is sodium dodecyl sulfate, and the volume concentration of the foaming agent in the foam slurry is 1g/L-8 g/L.
Further, the step S30 includes:
step S31, adding a catalyst into the foam slurry;
step S32, adding an initiator after the foam slurry is stable and uniformly stirring;
step S33, pouring the foam slurry added with the catalyst and the initiator into a mould to carry out gel reaction to obtain a blank body;
wherein, in the step S31, the catalyst is tetramethylethylenediamine, and the mass ratio of the catalyst to the monomer is 4-8 wt%;
in the step S32, the initiator is ammonium persulfate, and the mass ratio of the initiator to the monomer is 15% to 25 wt%.
Further, in the step S40, performing intermittent microwave drying treatment on the blank, wherein the total drying time is 40h-60h, the microwave treatment is performed at a power of 8KW-15KW, the time of each microwave treatment is 5 seconds-15 seconds, and the interval between the two microwave treatments is 5 minutes-15 minutes.
The cordierite porous ceramic membrane support according to the second aspect of the present invention is prepared by any one of the above-described near-net-size methods for preparing a cordierite porous ceramic membrane support.
Furthermore, the cordierite porous ceramic membrane support has the open porosity of 82-86% and the volume density of 0.35-0.46g/cm3The compression strength is 1.81-4.23MPa, the median pore diameter is 40-119 μm, and the permeability is (0.025-3.654) × 10-11m2The coefficient of thermal expansion is (1.61-3.19) × 10-6The thermal conductivity is 0.13-0.26W/m.K.
The technical scheme of the invention at least has one of the following beneficial effects:
(1) the invention takes high-purity oxide as raw material, and carries out proportioning according to the stoichiometric proportion, thereby obtaining cordierite with a single phase without any impurity phase; the cordierite has a low thermal expansion coefficient, so that in the practical application process, the ceramic membrane support body has a good thermal shock resistance effect and good stability in the process of filtering a high-temperature solution;
(2) the invention controls the technological parameters in the whole preparation process, and utilizes the phase change of silicon dioxide in the sintering process of the sample and the expansion caused by the density change accompanied by the chemical reaction to offset the shrinkage expansion in the drying and sintering processes, thereby realizing the near-net-size preparation;
(3) the invention adopts the injection coagulation method to ensure that the porous material microscopically presents uniform micron-sized spherical pores, thereby ensuring that the ceramic membrane support body obtains stable mechanical properties. The invention combines the characteristics of mechanical stirring and gel injection molding, and adopts an acrylamide gel system to obtain the cordierite porous ceramic support body with good matching of porosity and compressive strength and better permeability. The porous ceramic support body material with different pore diameters and porosity can be obtained by adjusting the preparation process.
(4) The cordierite porous ceramic membrane support prepared by the near-net-size preparation method has the advantages that the shrinkage of a sintering line is-1.45-1.43%, the open porosity is 82-86%, and the bulk density is 0.35g/cm3-0.46g/cm3The compression strength is 1.81MPa to 4.23MPa, the median pore diameter is 40 to 119 mu m, and the permeability is 0.025 to 3.654 multiplied by 10-11m2Coefficient of thermal expansionIs 1.61-3.19X 10-6The thermal conductivity is 0.13-0.26W/m.K. On the basis of meeting the mechanical properties of the material, the porous ceramic also has better permeability and can meet the requirements of the filter material.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cordierite porous ceramic membrane support according to example 1;
FIG. 2 is a graph showing the variation of sintering temperature and linear shrinkage of a slurry at different solid contents according to a near net-size preparation method of a cordierite porous ceramic membrane support according to the present invention;
FIG. 3 is a photograph of a cordierite porous ceramic membrane support obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
First, a method for producing a cordierite porous ceramic membrane support according to an embodiment of the present invention in a near-net-size manner will be described in detail.
The near-net-size preparation method of the cordierite porous ceramic membrane support provided by the embodiment of the invention comprises the following steps:
step S10, batching magnesium oxide, aluminum oxide and silicon dioxide according to the molar ratio of 2:2:5, and preparing the batching and water into slurry.
The invention takes high-purity oxide as raw material, and carries out proportioning according to the stoichiometric proportion, thereby obtaining the cordierite with a single phase without any impurity phase.
Preferably, in the step S10, the solid content of the slurry is 20 vol% to 30 vol%. Since different solid contents affect drying shrinkage and sintering shrinkage, it is preferable to control the sintering shrinkage rate to 2% or less at the firing temperature in the case of 20 vol% to 30 vol%, as can be seen from FIG. 2. In addition, the solid content is adjusted, so that the porosity, the compressive strength, the median pore size distribution and the like of the prepared support body can be controlled.
Preferably, the particle size of the magnesium oxide is 50nm-1500nm, the particle size of the aluminum oxide is 300nm-1000nm, and the particle size of the silicon dioxide is 500nm-5000 nm. By controlling the granularity of the raw materials, the granularity of the ingredients is small, the reaction activity is high, the combination degree of the particles is high, and the foamed ceramic material with high strength is obtained.
Specifically, the step S10 may include:
step S11, adding the monomer, the cross-linking agent and the dispersing agent into water and mechanically stirring to form a premixed solution;
step S12, adding the ingredients of magnesium oxide, aluminum oxide and silicon dioxide into the premixed solution, ball-milling for 15-20 h by a roller ball mill,
the monomer is acrylamide, the cross-linking agent is N, N-methylene bisacrylamide, the dispersing agent is ammonium polyacrylate, the monomer accounts for 5% -15% of the mass of water in the slurry, the cross-linking agent accounts for 0.5% -1.5% of the mass of water in the slurry, and the dispersing agent accounts for 0.5% -1.5% of the total mass of the magnesium oxide, the aluminum oxide and the silicon dioxide.
And step S20, pouring out the slurry, and carrying out foaming treatment to obtain foam slurry.
According to one embodiment of the invention, a foaming agent is added into the slurry and is uniformly stirred to obtain the foam slurry, wherein the foaming agent is sodium dodecyl sulfate, and the volume concentration of the foaming agent in the foam slurry is 1g/L-8 g/L.
And step S30, pouring the foam slurry into a mould and carrying out gel reaction to obtain a blank.
According to an embodiment of the present invention, the method specifically includes the following steps:
step S31, adding a catalyst into the foam slurry;
step S32, adding an initiator after the foam slurry is stable and uniformly stirring;
step S33, pouring the foam slurry added with the catalyst and the initiator into a mould to carry out gel reaction to obtain a blank body;
wherein, in the step S31, the catalyst is tetramethylethylenediamine, and the mass ratio of the catalyst to the monomer is 4-8 wt%;
in the step S32, the initiator is ammonium persulfate, and the mass ratio of the initiator to the monomer is 15% to 25 wt%.
According to the preparation method provided by the embodiment of the invention, the porous material microscopically presents uniform micron-sized spherical pores by adopting an injection coagulation method, so that the ceramic membrane support body obtains stable mechanical properties. The method combines the characteristics of mechanical stirring and gel injection molding, and adopts an acrylamide gel system to obtain the cordierite porous ceramic membrane support body with good matching of porosity and compressive strength and good permeability. The porous ceramic membrane support material with different pore diameters and porosity can be obtained by adjusting the preparation process.
And step S40, performing microwave drying treatment on the green body to dry the green body.
According to one embodiment of the invention, the blank is subjected to intermittent microwave drying treatment, wherein the total drying time is 40-60 h, the microwave treatment is carried out at a power of 8-15 KW, the time of each microwave treatment is 5-15 seconds, and the interval between the two microwave treatments is 5-15 minutes.
By adopting the intermittent microwave action drying process for the green body, the green body is uniformly shrunk from inside to outside in the drying process, and the generation of cracks in the green body is reduced, so that the compressive strength and the thermal shock resistance of the foamed ceramic material are improved, and the service life of the foamed ceramic material is prolonged.
And S50, sintering the dried green body in a sintering furnace, wherein in the sintering process, the temperature is respectively kept for 1-2h at 80-120 ℃, 350-.
Specifically, the invention controls the temperature by sections, namely, the temperature is respectively kept between 80 and 120 ℃ so as to completely dry the materials; the temperature is maintained at 350-450 ℃ so that the gel in the gel is degraded and then discharged to avoid structural defects caused by rapid gel discharge at a high temperature stage; the temperature is kept at 850-; the heat preservation is carried out at 1250-; and finally, fully sintering at 1370-1450 ℃ to realize the reaction of magnesia-alumina and silica to generate cordierite. According to the method, the influence of various reactions and crystal form transformation on the structure in the sintering process is fully considered, and the near-net-size preparation of cordierite is realized by accurately controlling the sintering system.
And (3) controlling the sintering process to enable magnesium hydroxide to undergo a decomposition reaction to generate magnesium oxide, discharging colloid through cracking, and generating intermediate-phase magnesia-alumina spinel, thereby finally obtaining the cordierite porous ceramic membrane support. By controlling the technological parameters in the whole preparation process, the shrinkage and expansion in the drying and sintering processes are counteracted by utilizing the phase change of silicon dioxide in the sintering process of the sample and the expansion caused by the density change accompanied by the chemical reaction, so that the near-net-size preparation is realized.
The following describes a method for producing a cordierite ceramic foam material according to the present invention with reference to specific examples.
In the following examples, the gelation reaction was described by taking acrylamide as a monomer, N-methylene bisacrylamide as a crosslinking agent, tetramethylethylenediamine as a catalyst, and ammonium persulfate as an initiator as an example, but the present invention is not limited thereto, and any other gelation reaction known to those skilled in the art may be used. In the following examples, sodium lauryl sulfate was used as a foaming agent, but the present invention is not limited thereto, and those skilled in the art can perform foaming treatment using any other foaming agent. Such modifications are to be understood as falling within the scope of the present invention.
Example 1
Firstly, acrylamide (monomer) and N, N-methylene bisacrylamide (cross-linking agent) are respectively added into water according to 10 wt.% and 1 wt.% of the mass of the water, ammonium polyacrylate (dispersing agent) which is equal to 6 wt.% of the total mass of the raw material ceramic powder is added, and the raw material ceramic powder and the ammonium polyacrylate are uniformly mixed to obtain a premixed liquid.
Adding magnesium oxide with the particle size of 50nm, alumina with the particle size of 300-500nm and silicon dioxide with the particle size of 300nm into the premixed liquid according to the molar ratio of the magnesium oxide to the aluminum oxide to the silicon dioxide of 2:2:5, preparing slurry according to the solid content of 25 vol% (the total volume of the slurry is 100ml), placing the mixed materials into a ball milling tank, and placing the ball milling tank on a roller ball mill for mixing for 18 hours.
Then, the mixed slurry was poured into a foaming vessel, 3g/L sodium lauryl sulfate (foaming agent) was added to the slurry to foam, and mechanical stirring was carried out for 10min to obtain a stable foam.
Then, tetramethylethylenediamine (catalyst) with the mass of 22 wt.% of acrylamide is added, ammonium persulfate (initiator) with the mass of 22 wt.% of acrylamide is added after stirring for 5min, the stirring is continued for 3min, the slurry is directly poured into a disposable mold, and destructive demolding is carried out after the gel reaction is finished.
And then, drying the demoulded blank in a microwave drying oven for 30h, wherein the microwave action power is 10KW, the microwave action time is 10s each time, and the interval time between two microwave treatments is 15 min.
Finally, the dried green body is placed in a furnace for sintering: (1) heating to 100 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (2) then heating to 390 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (3) then the temperature is increased to 975 ℃ at the speed of 1 ℃/min and the temperature is kept for 1 h; (4) heating to 1270 ℃ at the speed of 2 ℃/min and preserving heat for 3 h; (5) finally, heating to 1450 ℃ at the speed of 2 ℃/min and preserving heat for 5 h; (6) and finally, cooling to 300 ℃ at the speed of 2 ℃/min, and then cooling to room temperature along with the furnace to obtain the cordierite porous ceramic membrane support body, as shown in figure 3. As can be seen from fig. 3, according to the production method of the present invention, not only can near-net-size production of a cordierite porous ceramic membrane support be achieved, but also, even with a complicated shape, cracking does not occur during sintering (mainly due to shrinkage unevenness or the like).
The X-ray diffraction (XRD) pattern of the obtained cordierite porous ceramic membrane support is shown in fig. 1(25 vol.%), and it can be seen from fig. 1 that the material is cordierite crystal phase and no other impurity peak appears.
Furthermore, it was found by calculation that the cordierite porous ceramic membrane support had a sintered wire shrinkage of-0.7%, an open porosity of 82.85%, and a bulk density of 0.43g/cm3The compressive strength was 4.23 MPa. The median pore diameter is 40.2 μm, and the permeability is 0.025X 10-11m2Coefficient of thermal expansion of 3.08X 10-6The thermal conductivity was 0.197W/mK.
Example 2
Firstly, acrylamide (monomer) and N, N-methylene bisacrylamide (cross-linking agent) are respectively added into water according to 10 wt.% and 1 wt.% of the mass of the water, ammonium polyacrylate (dispersing agent) with the mass of 6 wt.% of the total mass of the raw material ceramic powder is added, and the raw materials are uniformly mixed to obtain a premixed liquid.
Adding magnesium oxide with the particle size of 50nm, alumina with the particle size of 300-500nm and silicon dioxide with the particle size of 300nm into the premixed liquid according to the molar ratio of the magnesium oxide to the aluminum oxide to the silicon dioxide of 2:2:5, preparing slurry according to the solid content of 25 vol% (the total volume of the slurry is 200ml), placing the mixed material into a ball milling tank, and placing the ball milling tank and the roller ball mill for mixing for 18 hours.
Then, the mixed slurry was poured into a foaming vessel, 4g/L sodium lauryl sulfate (foaming agent) was added to the slurry to foam, and mechanical stirring was carried out for 10min to obtain a stable foam.
Then, tetramethylethylenediamine (catalyst) with the mass of 22 wt.% of acrylamide is added, after stirring for 5min, ammonium persulfate (initiator) with the mass of 23 wt.% of acrylamide is added, after stirring for 3min, the slurry is directly poured into a disposable mold, and after the gel reaction is finished, destructive demolding is carried out.
And then, drying the demoulded blank in a microwave drying oven for 30h with the power of 10KW, wherein the action time of each microwave treatment is 10s, and the interval time between the two microwave treatments is 15 min.
Finally, the dried green body is placed in a furnace for sintering: (1) heating to 100 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (2) then heating to 390 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (3) then the temperature is increased to 975 ℃ at the speed of 1 ℃/min and the temperature is kept for 1 h; (4) heating to 1270 ℃ at the speed of 2 ℃/min and preserving heat for 3 h; (5) finally, heating to 1450 ℃ at the speed of 2 ℃/min and preserving heat for 5 h; (6) and finally, cooling to 300 ℃ at the speed of 2 ℃/min, and then cooling to room temperature along with the furnace to obtain the cordierite porous ceramic membrane support.
The X-ray diffraction (XRD) pattern of the obtained cordierite porous ceramic membrane support was the same as that of example 1, and the material was a single cordierite phase and no other foreign peak was observed.
The obtained cordierite porous ceramic membrane support has a sintering line shrinkage of-0.2%, an open porosity of 85.03%, and a bulk density of 0.38g/cm3The compressive strength is 3.35 MPa. The median pore diameter is 45.33 μm, and the permeability is 0.137 × 10-11m2Coefficient of thermal expansion of 1.61X 10-6The thermal conductivity was 0.177W/m.K.
Example 3
Firstly, acrylamide (monomer) and N, N-methylene bisacrylamide (cross-linking agent) are respectively added into water according to 10 wt.% and 1 wt.% of the mass of the water, ammonium polyacrylate (dispersing agent) with the mass of 6 wt.% of the total mass of the raw material ceramic powder is added, and the raw materials are uniformly mixed to obtain a premixed liquid.
Adding magnesium oxide with the particle size of 50nm, alumina with the particle size of 300-500nm and silicon dioxide with the particle size of 300nm into the premixed liquid according to the molar ratio of the magnesium oxide to the aluminum oxide to the silicon dioxide of 2:2:5, preparing slurry according to the solid content of 25 vol% (the total volume of the slurry is 200ml), placing the mixed material into a ball milling tank, and placing the ball milling tank and the roller ball mill for mixing for 18 hours.
Then, the mixed slurry was poured into a foaming vessel, 2g/L sodium lauryl sulfate (foaming agent) was added to the slurry to foam, and mechanical stirring was carried out for 10min to obtain a stable foam.
Then, tetramethylethylenediamine (catalyst) with the mass of 22 wt.% of acrylamide is added, ammonium persulfate (initiator) with the mass of 23 wt.% of acrylamide is added after stirring for 5min, the stirring is continued for 3min, the slurry is directly poured into a circular mold, and demolding is carried out after the gel reaction is finished.
And then, drying the demoulded blank in a microwave drying oven for 30h with the power of 10KW, wherein the action time of each microwave treatment is 10s, and the interval time between the two microwave treatments is 15 min.
Finally, the dried green body is placed in a furnace for sintering: (1) heating to 100 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (2) then heating to 390 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (3) then the temperature is increased to 975 ℃ at the speed of 1 ℃/min and the temperature is kept for 1 h; (4) heating to 1270 ℃ at the speed of 2 ℃/min and preserving heat for 3 h; (5) finally, heating to 1450 ℃ at the speed of 2 ℃/min and preserving heat for 5 h; (6) and finally, cooling to 300 ℃ at the speed of 2 ℃/min, and then cooling to room temperature along with the furnace to obtain the cordierite porous ceramic membrane support.
The firing line shrinkage of the obtained cordierite porous ceramic membrane support is-0.77%. Therefore, the method is proved to be capable of forming the cordierite porous ceramic with near net size, and the sample obtained by the preparation method has no cracking phenomenon and is relatively stable in process.
Example 4
Firstly, acrylamide (monomer) and N, N-methylene bisacrylamide (cross-linking agent) are respectively added into water according to 10 wt.% and 1 wt.% of the mass of the water, ammonium polyacrylate (dispersing agent) with the mass of 6 wt.% of the total mass of the raw material ceramic powder is added, and the raw materials are uniformly mixed to obtain a premixed liquid.
Adding magnesium oxide with the particle size of 50nm, alumina with the particle size of 300-500nm and silicon dioxide with the particle size of 300nm into the premixed liquid according to the molar ratio of the magnesium oxide to the aluminum oxide to the silicon dioxide of 2:2:5, preparing slurry according to the solid content of 25 vol% (the total volume of the slurry is 200ml), placing the mixed material into a ball milling tank, and placing the ball milling tank and the roller ball mill for mixing for 18 hours.
Then, the mixed slurry was poured into a foaming vessel, 2g/L sodium lauryl sulfate (foaming agent) was added to the slurry to foam, and mechanical stirring was carried out for 10min to obtain a stable foam.
And then adding tetramethylethylenediamine (catalyst) with the mass of 22 wt.% of acrylamide, stirring for 5min, adding ammonium persulfate (initiator) with the mass of 23 wt.% of acrylamide, continuously stirring for 3min, directly pouring the slurry into a special-shaped mold, and demolding after the gel reaction is finished.
And then, drying the demoulded blank in a microwave drying oven for 30h with the power of 10KW, wherein the action time of each microwave treatment is 10s, and the interval time between the two microwave treatments is 15 min.
Finally, the dried green body is placed in a furnace for sintering: (1) heating to 100 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (2) then heating to 390 ℃ at the speed of 1 ℃/min and preserving heat for 1 h; (3) then the temperature is increased to 975 ℃ at the speed of 1 ℃/min and the temperature is kept for 1 h; (4) heating to 1270 ℃ at the speed of 2 ℃/min and preserving heat for 3 h; (5) finally, heating to 1450 ℃ at the speed of 2 ℃/min and preserving heat for 5 h; (6) finally, the temperature is reduced to 300 ℃ at the speed of 2 ℃/min, and then the cordierite foam ceramic filter material is obtained after the temperature is cooled to the room temperature along with the furnace.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A near-net-size preparation method of a cordierite porous ceramic membrane support is characterized by comprising the following steps:
step S10, batching magnesium oxide, aluminum oxide and silicon dioxide according to the molar ratio of 2:2:5, and preparing the batching and water into slurry;
step S20, pouring out the slurry, and carrying out foaming treatment to obtain foam slurry;
step S30, pouring the foam slurry into a mold and carrying out gel reaction to obtain a blank;
step S40, the blank body is subjected to microwave drying treatment to dry the blank body;
and S50, sintering the dried green body in a sintering furnace, wherein in the sintering process, the temperature is respectively kept for 1-2h at 80-120 ℃, 350-.
2. The method for producing a near-net-shape cordierite porous ceramic membrane support according to claim 1, wherein the absolute value of the sintered linear shrinkage rate in step S50 is 2% or less.
3. The method of producing a near-net-size cordierite porous ceramic membrane support according to claim 1, wherein the slurry has a solid content of 20 vol% to 30 vol% in step S10.
4. The method for producing a near-net-size cordierite porous ceramic membrane support according to claim 3, wherein in step S10, the magnesia has a particle size of 50nm to 1500nm, the alumina has a particle size of 300nm to 1000nm, and the silica has a particle size of 100nm to 500 nm.
5. The method for near-net-size production of a cordierite porous ceramic membrane support according to claim 1, wherein the step S10 includes:
step S11, adding the monomer, the cross-linking agent and the dispersing agent into water and mechanically stirring to form a premixed solution;
step S12, adding the ingredients of magnesium oxide, aluminum oxide and silicon dioxide into the premixed solution, ball-milling for 15-20 h by a roller ball mill,
the monomer is acrylamide, the cross-linking agent is N, N-methylene bisacrylamide, the dispersing agent is ammonium polyacrylate, the monomer accounts for 5% -15% of the mass of water in the slurry, the cross-linking agent accounts for 0.5% -1.5% of the mass of water in the slurry, and the dispersing agent accounts for 0.5% -1.5% of the total mass of the magnesium oxide, the aluminum oxide and the silicon dioxide.
6. The method for near-net-size production of a cordierite porous ceramic membrane support according to claim 5, wherein the step S20 specifically comprises:
and adding a foaming agent into the slurry and uniformly stirring to obtain the foam slurry, wherein the foaming agent is sodium dodecyl sulfate, and the volume concentration of the foaming agent in the foam slurry is 1g/L-8 g/L.
7. The method for near-net-size production of a cordierite porous ceramic membrane support according to claim 5, wherein the step S30 includes:
step S31, adding a catalyst into the foam slurry;
step S32, adding an initiator after the foam slurry is stable and uniformly stirring;
step S33, pouring the foam slurry added with the catalyst and the initiator into a mould to carry out gel reaction to obtain a blank body;
wherein, in the step S31, the catalyst is tetramethylethylenediamine, and the mass ratio of the catalyst to the monomer is 4-8 wt%;
in the step S32, the initiator is ammonium persulfate, and the mass ratio of the initiator to the monomer is 15% to 25 wt%.
8. The method of preparing a near-net-size cordierite porous ceramic membrane support according to claim 5, wherein the green body is subjected to intermittent microwave drying treatment in step S40, wherein the total drying time is 40-60 h, the microwave treatment is performed at a power of 8-15 KW, the time of each microwave treatment is 5-15 seconds, and the interval between the two microwave treatments is 5-15 minutes.
9. A cordierite porous ceramic membrane support produced by the near-net-size production method for a cordierite porous ceramic membrane support according to any one of claims 1 to 8.
10. The cordierite porous ceramic membrane support of claim 9, having an open porosity of 82-86% and a bulk density of 0.35-0.46g/cm3The compression strength is 1.81-4.23MPa, the median pore diameter is 40-119 μm, and the permeability is (0.025-3.654) × 10-11m2The coefficient of thermal expansion is (1.61-3.19) × 10-6The thermal conductivity is 0.13-0.26W/m.K.
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