CN115888409A - Preparation method of titanium dioxide modified silicon carbide ceramic fiber membrane - Google Patents
Preparation method of titanium dioxide modified silicon carbide ceramic fiber membrane Download PDFInfo
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- CN115888409A CN115888409A CN202211325482.9A CN202211325482A CN115888409A CN 115888409 A CN115888409 A CN 115888409A CN 202211325482 A CN202211325482 A CN 202211325482A CN 115888409 A CN115888409 A CN 115888409A
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- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- -1 titanium dioxide modified silicon carbide Chemical class 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 56
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002110 nanocone Substances 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a titanium dioxide modified silicon carbide ceramic fiber membrane. TiO grows by solvothermal reaction and calcination on the surface of a silicon carbide support 2 The nano-cone can increase the surface roughness of the support, so that the contact site between the membrane layer fiber and the support is increased, and the membrane-based binding force of the membrane is increased. The support body is sprayed with the silicon carbide fiber membrane-forming liquid, and then the silicon carbide fiber membrane is sintered by a program to prepare the complete defect-free silicon carbide fiber membrane, and the prepared silicon carbide fiber membrane has high gas permeability and good back-blowing stability.
Description
Technical Field
The invention relates to a titanium dioxide modified silicon carbide ceramic fiber membrane and a preparation method thereof, belonging to the field of preparation of porous ceramic separation membranes.
Background
The porous ceramic membrane is an important material which can be used for dedusting high-temperature gas. In order to improve the separation accuracy, a granular membrane layer is usually prepared on a ceramic support layer. However, the ceramic membrane separation layer prepared by the method has low porosity (below 35 percent) and low gas permeability, which limits the popularization and application of the ceramic membrane.
The silicon carbide fiber has the characteristics of high temperature resistance, high strength, good chemical stability and the like. The porosity of the membrane layer can be obviously improved by constructing the membrane layer through the fibers, so that the gas permeability of the membrane material is improved. However, the connection strength between fibers is weak, and the connection strength can be enhanced by adding a sintering aid into the fiber aggregate to promote the reaction at high temperature to generate neck connection between fibers.
Cuo (Ceramics International, 2018,44, 11778-11782) et al successfully produced homogeneous porous mullite fiber Ceramics with high porosity but with a bending strength of only 1.19 MPa using mullite fibers in a templating agent process. Ke et al (j. Phys. Chem. B, 2008, 112: 5000-5006) use titanate nanofibers and boehmite nanofibers to build layered structural separation layers on porous ceramic supports with relatively high water flux and good integrity. In order to improve the bonding strength between fibers, small particles and sintering aids are often doped in fiber materials to promote the reaction of the fiber materials at high temperature so as to promote the generation of neck connection between fibers to enhance the connection strength. The support of the Dia-Schumalitith series filter tube manufactured by Pall corporation (Fuel, 2013, 108. The filter is suitable for high-temperature flue gas purification, and the thermal shock resistance is particularly excellent, however, how to efficiently improve the bonding strength between the fiber membrane layer and the particle supporting layer and further improve the blowback stability of the membrane is a great problem in the field of ceramic fiber membranes.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium dioxide modified silicon carbide ceramic fiber membrane for improving the low gas permeability and poor membrane blowback stability of a ceramic separation membrane in the prior art.
The technical scheme of the invention is as follows: a preparation method of a titanium dioxide modified silicon carbide ceramic fiber membrane comprises the following specific steps: a, uniformly mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio (3-5): 1, magnetically stirring to obtain a clear and transparent titanium sol, immersing a silicon carbide support in the titanium sol, performing ultrasonic treatment for 2-10 min, then lifting and vertically placing in a beaker, and placing in an oven at 80-150 ℃ for 10-60 min. Obtaining a silicon carbide support body a; mixing and stirring the glycerol and the tetrabutyl titanate uniformly according to the volume ratio of (10-20) to 1, pouring the mixture into a polytetrafluoroethylene lining, and vertically placing the silicon carbide support body a into the polytetrafluoroethylene lining. Carrying out hydrothermal treatment at 150-210 ℃ for 18-26 h, taking out, and then washing with absolute ethyl alcohol for 1-5 times to obtain a silicon carbide support body b; placing the silicon carbide support body b on a ceramic burning platform, and preserving heat for 1-3 h in a muffle furnace at the temperature of 300-600 ℃ to obtain a support body c with an anatase crystal form; b, adding a certain amount of silicon carbide fiber and nano zirconia into a 0.5-2wt% of pre-prepared methyl cellulose solution according to the mass ratio of (8-20): 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 4-8wt%; and spraying the membrane-making solution on a silicon carbide support body c, drying in a constant-temperature drying oven, and finally sintering in a high-temperature furnace to obtain the silicon carbide fiber membrane.
The magnetic stirring speed in the step (1) is 400-600 r/min, and the stirring time is 1-3 min.
The magnetic stirring speed in the step (2) is 400-600 r/min, and the stirring time is 10-50 min.
And (3) the calcining procedure of the support body b is to heat up to 300-600 ℃ at the rate of 4-6 ℃/min at room temperature, preserve heat for 1-3 h at 300-600 ℃, and naturally cool to room temperature.
The average diameter of the silicon carbide fiber in the step (4) is 0.5-2 μm, the length-diameter ratio is 10-25, and the average particle size of the nano zirconia is about 400-600 nm.
The spraying times of the membrane-forming liquid in the step (5) are 2-4 times, each spraying time is 0.5-2 s, the spraying pressure is 0.4-0.6 MPa, the spraying distance is 15-25 cm, the drying temperature of a wet membrane is 40-80 ℃, and the drying time is 5-12 h.
The sintering procedure of the silicon carbide fiber membrane in the step (5) is to heat up to 90-110 ℃ at room temperature at a heating rate of 0.5-2 ℃/min, then heat up to 600-800 ℃ at a heating rate of 1-3 ℃/min, then heat up to 1100-1200 ℃ at a heating rate of 0.5-2 ℃/min, keep the temperature at 1100-1200 ℃ for 1-3 h, and naturally cool to room temperature.
The thickness of the film layer of the silicon carbide ceramic film prepared by the invention is 90-240 mu m, the average aperture is 4.8-13 mu m, and the gas permeability is 308-616 m 3 ·m -2 ·h -1 ·kPa -1
Has the beneficial effects that:
the invention grows TiO by the hydrothermal reaction and calcination of a solvent on the surface of a silicon carbide support 2 The nano-cone can increase the surface roughness of the support, so that the contact site between the membrane layer fiber and the support is increased, and the membrane-based binding force of the membrane is increased. And spraying a silicon carbide fiber membrane-forming solution on the support, and then sintering the solution by a program to prepare a complete flawless silicon carbide fiber membrane, wherein the prepared silicon carbide fiber membrane has high gas permeability and good back-blowing stability.
Drawings
FIG. 1 is a surface topography of support c grown with the anatase form of example 2.
Fig. 2 is an XRD pattern of the support c grown with anatase modification in example 2.
FIG. 3 is a graph showing the distribution of pore diameters of the support c grown with the anatase modification in example 2.
FIG. 4 is a cross-sectional profile of the titanium dioxide modified silicon carbide ceramic fiber membrane of example 2.
FIG. 5 is a surface topography of the titanium dioxide modified silicon carbide ceramic fiber membrane of example 2.
FIG. 6 is a graph showing the pore size distribution of the titania-modified silicon carbide ceramic fiber membrane in example 2.
FIG. 7 is a graph showing the dust filtration performance of the titania-modified silicon carbide ceramic fiber membrane of example 2.
FIG. 8 is a graph comparing the Darcy permeability of the titanium dioxide modified silicon carbide ceramic fiber membrane of example 2 with that of the related art.
Detailed Description
Example 1
The preparation method comprises the following steps of mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of 3. Obtaining a silicon carbide support body a; mixing and stirring glycerol and tetrabutyl titanate uniformly according to a volume ratio of 15. Hydrothermal for 16 h at 150 ℃, taking out, and then washing for 3 times by using absolute ethyl alcohol to obtain a silicon carbide support body b; placing the support body b on a ceramic burning platform, and preserving heat for 2 hours in a muffle furnace at 400 ℃ to obtain a support body c with an anatase crystal form; adding a certain amount of silicon carbide fiber and nano zirconia into a 0.5wt% of pre-prepared methyl cellulose solution according to the mass ratio of 8; and spraying the membrane-forming liquid on a silicon carbide support c for 2 times, wherein the spraying time is 1 s each time, the spraying pressure is 0.4 MPa, and the spraying distance is 20 cm. Then placing the substrate in a constant-temperature drying oven for drying to obtain a coated substrate d; and (3) placing the coated substrate d in a high-temperature furnace, and sintering at 1150 ℃ in an air atmosphere to obtain the silicon carbide fiber membrane.
The average pore diameter of the obtained titanium dioxide modified silicon carbide ceramic fiber membrane is 13 mu m through detection. Gas permeability of 616 m 3 ·m -2 ·h -1 ·kPa -1 And after back flushing for 30 times under the condition of 0.5 MPa, the shape structure, the pore size distribution and the gas permeability of the material have no obvious change.
Example 2
The preparation method comprises the following steps of mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of 4. Obtaining a silicon carbide support body a; mixing and stirring glycerol and tetrabutyl titanate uniformly according to a volume ratio of 15. Hydrothermal at 180 ℃ for 24 h, taking out, and washing with absolute ethyl alcohol for 3 times to obtain a silicon carbide support body b; placing the support body b on a ceramic burning platform, and preserving heat for 2 hours in a muffle furnace at 450 ℃ to obtain a support body c with an anatase crystal form; adding a certain amount of silicon carbide fiber and nano zirconia into a pre-prepared 1wt% methyl cellulose solution according to the mass ratio of 10 to 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 6wt%; and spraying the membrane-forming liquid on a silicon carbide support c for 2 times, wherein the spraying time is 1 s each time, the spraying pressure is 0.5 MPa, and the spraying distance is 20 cm. Then placing the substrate in a constant-temperature drying oven for drying to obtain a coated substrate d; and (3) placing the coated substrate d in a high-temperature furnace, and sintering at 1150 ℃ in an air atmosphere to obtain the silicon carbide fiber membrane.
The average pore diameter of the obtained titanium dioxide modified silicon carbide ceramic fiber membrane is 6.8 mu m through detection. Gas permeability of 440 m 3 ·m -2 ·h -1 ·kPa -1 And after back flushing for 30 times under the condition of 0.5 MPa, the shape structure, the pore size distribution and the gas permeability of the material have no obvious change.
FIG. 1 is a surface topography of a support c grown with anatase type in example 2, and titanium dioxide nanocones are uniformly covered on the surface of the support; FIG. 2 is an XRD analysis of the support c grown with anatase modification in example 2, from which it can be seen that anatase TiO modification exists at 2 θ =24 ° and 2 θ =55 ° 2 Diffraction peaks. FIG. 3 is a distribution diagram of the pore diameters of a support c grown with anatase modification in example 2, from which it can be seen that the support exhibits a monomodal distribution with an average pore diameter of 35.7 μm; FIG. 4 is a cross-sectional view of the titanium dioxide-modified silicon carbide ceramic fiber membrane of example 2, from which it can be seen that the membrane layer has a thickness of about 120 μm and that the bonding between the fibers of the membrane layer and the support is strong; FIG. 5 is a surface topography of a titanium dioxide modified silicon carbide ceramic fiber membrane in example 2, from which it can be seen that the fibers on the surface of the membrane are interlaced to form a three-dimensional network-like interconnected pore structure; FIG. 6 is a distribution diagram of pore sizes of the titania-modified silicon carbide ceramic fiber membrane of example 2, from which it can be seen that the fiber membrane exhibits a monomodal distribution with an average pore size of 6.8 μm, and FIG. 7 is a graph of dust filtration performance of the titania-modified silicon carbide ceramic fiber membrane of example 2, with a dust rejection of 99.93% or more, a filtration pressure drop of 0.82 kPa after 80 min filtration and 4 blowbacks. In the filtering period after each back flushing, the pressure drop always keeps the trend of increasing and then stabilizing, and the membrane is shown to haveAnd (4) good back flushing stability. FIG. 8 is a graph comparing the Darcy permeability of the titanium dioxide modified silicon carbide ceramic fiber membrane of example 2 with that of the related art. The fibrous membrane has a Darcy permeability coefficient higher than that of a filter of similar porosity and pore size, and thus has a relatively lower gas permeation resistance than a filter of similar porosity and pore size.
Example 3
The preparation method comprises the following steps of mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of 5. Obtaining a silicon carbide support body a; mixing and stirring glycerol and tetrabutyl titanate uniformly according to the volume ratio of 20. Carrying out hydrothermal treatment at 210 ℃ for 26 h, taking out, and washing with absolute ethyl alcohol for 5 times to obtain a silicon carbide support body b; placing the support body b on a ceramic burning platform, and preserving heat for 2 hours in a muffle furnace at 500 ℃ to obtain a support body c with an anatase crystal form; adding a certain amount of silicon carbide fiber and nano zirconia into a pre-prepared 1.5wt% methyl cellulose solution according to the mass ratio of 12 to 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 8wt%; and spraying the membrane-forming liquid on a silicon carbide support c for 2 times, wherein the spraying time is 2 s each time, the spraying pressure is 0.6 MPa, and the spraying distance is 25 cm. Then placing the substrate in a constant-temperature drying oven for drying to obtain a coated substrate d; and (3) placing the coated substrate d in a high-temperature furnace, and sintering at 1200 ℃ in an air atmosphere to obtain the silicon carbide fiber membrane.
The average pore diameter of the obtained titanium dioxide modified silicon carbide ceramic fiber membrane is 4.8 mu m through detection. Gas permeability of 308 m 3 ·m -2 ·h -1 ·kPa -1 And after back flushing for 30 times under the condition of 0.5 MPa, the shape structure, the pore size distribution and the gas permeability of the material have no obvious change.
Example 4
The preparation method comprises the following steps of mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of 3. Obtaining a silicon carbide support body a; mixing and stirring glycerol and tetrabutyl titanate uniformly according to a volume ratio of 10. Hydrothermal for 18 h at 150 ℃, taking out, and then washing with absolute ethyl alcohol for 1 time to obtain a silicon carbide support body b; placing the support body b on a ceramic burning platform, and preserving heat for 2 hours in a muffle furnace at 550 ℃ to obtain a support body c with an anatase crystal form; adding a certain amount of silicon carbide fiber and nano zirconia into a pre-prepared 2wt% methyl cellulose solution according to the mass ratio of 16 to 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 6wt%; and spraying the membrane-forming liquid on a silicon carbide support c for 3 times, wherein the spraying time is 0.5s each time, the spraying pressure is 0.4 MPa, and the spraying distance is 15 cm. Then placing the substrate in a constant-temperature drying oven for drying to obtain a coated substrate d; and (3) placing the coated substrate d in a high-temperature furnace, and sintering at 1100 ℃ in an air atmosphere to obtain the silicon carbide fiber membrane.
The average pore diameter of the obtained titanium dioxide modified silicon carbide ceramic fiber membrane is 6.3 mu m through detection. Gas permeability of 308 m 3 ·m -2 ·h -1 ·kPa -1 And after back flushing for 30 times under the condition of 0.5 MPa, the shape structure, the pore size distribution and the gas permeability of the material have no obvious change.
Example 5
The preparation method comprises the following steps of mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of 4. Obtaining a silicon carbide support body a; mixing and stirring glycerol and tetrabutyl titanate uniformly according to a volume ratio of 15. Carrying out hydrothermal treatment at 180 ℃ for 24 h, taking out, and then washing with absolute ethyl alcohol for 3 times to obtain a silicon carbide support body b; placing the support body b on a ceramic burning platform, and preserving heat for 2 hours in a muffle furnace at the temperature of 600 ℃ to obtain a support body c with an anatase crystal form; adding a certain amount of silicon carbide fiber and nano zirconia into a pre-prepared 2.5wt% methyl cellulose solution according to the mass ratio of 20 to 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 6wt%; and spraying the membrane-forming liquid on a silicon carbide support body c for 4 times, wherein the spraying time is 2 s each time, the spraying pressure is 0.5 MPa, and the spraying distance is 25 cm. Then placing the substrate in a constant-temperature drying box for drying to obtain a coated substrate d; and (3) placing the coated substrate d in a high-temperature furnace, and sintering at 1200 ℃ in an air atmosphere to obtain the silicon carbide fiber membrane.
The average pore diameter of the obtained titanium dioxide modified silicon carbide ceramic fiber membrane is 5.5 mu m through detection. Gas permeability of 336 m 3 ·m -2 ·h -1 ·kPa -1 And after back flushing for 30 times under the condition of 0.5 MPa, the shape structure, the pore size distribution and the gas permeability of the material have no obvious change.
Table 1 shows the comparison between the membrane prepared in example 2 and the literature, and it can be seen that the membrane prepared by the method (average pore size of about 6.8 μm) has higher gas permeability, higher dust retention rate and lower pressure drop than the literature comparison. (unit of pore diameter: μm, unit of gas permeability: m) 3 ·m -2 ·h -1 ·kPa -1 Dust retention unit: % pressure drop unit: kPa).
Table 1 comparison of the properties of the membrane prepared in example 2 with the membrane materials reported in the literature
Claims (7)
1. A preparation method of a titanium dioxide modified silicon carbide ceramic fiber membrane is characterized by comprising the following specific steps:
(1) Uniformly mixing absolute ethyl alcohol, tetrabutyl titanate and polyethylene glycol 600 according to a molar ratio of (3-5) to 1, magnetically stirring to obtain a clear and transparent titanium sol, immersing a silicon carbide support in the titanium sol, performing ultrasonic treatment for 2-10 min, lifting the titanium sol, vertically placing the titanium sol into a beaker, and placing the beaker into an oven at 80-150 ℃ for 10-60 min to obtain a silicon carbide support a;
(2) Mixing glycerol and tetrabutyl titanate according to the volume ratio of (10-20): 1, magnetically stirring uniformly, pouring into a polytetrafluoroethylene lining, vertically placing a silicon carbide support body a into the polytetrafluoroethylene lining, carrying out hydrothermal treatment at 150-210 ℃ for 18-26 h, taking out, and washing for 1-5 times by using absolute ethyl alcohol to obtain a silicon carbide support body b;
(3) Placing the silicon carbide support body b on a ceramic burning platform, and preserving heat for 1-3 h in a muffle furnace at the temperature of 300-600 ℃ to obtain a support body c with an anatase crystal form;
(4) Adding a certain amount of silicon carbide fiber and nano zirconia into a 0.5-2wt% of pre-prepared methyl cellulose solution according to the mass ratio of (8-20): 1 to obtain a membrane-making solution, wherein the solid content of the membrane-making solution is 4-8wt%;
(5) And spraying the membrane-making solution on a silicon carbide support body c, drying in a constant-temperature drying oven, and finally sintering in a high-temperature furnace to obtain the silicon carbide fiber membrane.
2. The method for preparing the titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the magnetic stirring rotation speed in the step (1) is 400-600 r/min, and the stirring time is 1-3 min.
3. The method for preparing the titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the magnetic stirring rotation speed in the step (2) is 400-600 r/min, and the stirring time is 10-50 min.
4. The method for preparing titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the calcination procedure of the support body b in the step (3) is to heat up to 300-600 ℃ at room temperature at a rate of 4-6 ℃/min, keep the temperature at 300-600 ℃ for 1-3 h, and naturally cool to room temperature.
5. The method for preparing a titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the average diameter of the silicon carbide fiber in the step (4) is 0.5-2 μm, the aspect ratio is 10-25, and the average particle size of the nano zirconia is about 400-600 nm.
6. The method for preparing the titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the membrane forming solution in the step (5) is sprayed for 2-4 times, each spraying time is 0.5-2 s, the spraying pressure is 0.4-0.6 MPa, the spraying distance is 15-25 cm, the wet membrane drying temperature is 40-80 ℃, and the drying time is 5-12 h.
7. The method for preparing a titanium dioxide modified silicon carbide ceramic fiber membrane according to claim 1, wherein the sintering procedure of the silicon carbide ceramic fiber membrane in the step (5) is to heat up to 90-110 ℃ at room temperature at a heating rate of 0.5-2 ℃/min, then heat up to 600-800 ℃ at a heating rate of 1-3 ℃/min, then heat up to 1100-1200 ℃ at a heating rate of 0.5-2 ℃/min, keep the temperature at 1100-1200 ℃ for 1-3 h, and naturally cool down to room temperature.
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