CN115611623A - Preparation method of mullite porous microfiltration membrane support ceramic - Google Patents
Preparation method of mullite porous microfiltration membrane support ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 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 title claims abstract description 37
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 35
- 238000001471 micro-filtration Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000010881 fly ash Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 239000008213 purified water Substances 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 239000004005 microsphere Substances 0.000 claims description 23
- 229920002223 polystyrene Polymers 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 6
- 241000872198 Serjania polyphylla Species 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000010189 synthetic method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- -1 sintering aids Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates to the technical field of environment-friendly solid waste comprehensive utilization, and discloses a preparation method of mullite porous microfiltration membrane support ceramic, which comprises the following raw material formula: al (aluminum) 2 O 3 5-15 parts of powder; 60-75 parts of high-alumina fly ash; sintering-assistant type composite pore-forming agent, 10-20 parts; polyvinyl alcohol, 0.5-5 parts; purified water, 12.5-120 parts; adding the raw materials in the proportion into a ball milling tank, drying after ball milling to obtain powder, granulating the powder, sieving, and taking the powder for dry pressingAnd molding, namely preparing a green body, drying, and then sintering in a high-temperature electric furnace to obtain the mullite porous microfiltration membrane support body ceramic. The sintering temperature of the invention is reduced by more than 300 ℃ compared with the alumina ceramics, the dosage of the alumina can be reduced by 80 percent, and the production cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of environment-friendly solid wastes, in particular to a preparation method of mullite porous microfiltration membrane support ceramic.
Background
The ceramic flat membrane support is made of Al 2 O 3 、SiO 2 SiC and the likeThe inorganic powder is a main structure, and various organic adhesives, sintering aids, foaming agents, oil materials and water are added at the same time, and the inorganic powder is prepared by mixing, kneading, vacuum pugging, vacuum extrusion, drying and sintering.
The improvement of the performance of the support is the basis for improving the service performance of the inorganic membrane material. The porous support body in commercial application at present mostly adopts high-purity alumina powder with small grain diameter (30-40 μm), by adding pore-forming agents at elevated temperatures (A), (B), (C)>Calcining at 1800 deg.c to prepare the porous alumina ceramic support with high strength and high permeating flux. However, this method requires expensive and fragile high-temperature equipment and expensive high-purity Al 2 O 3 Powders, which largely limit the commercial application of porous ceramic supports and membrane materials. At present, in order to solve the problems, domestic and foreign enterprises and scientific research institutions often adopt the following two methods to reduce the cost required by production and prepare the porous ceramic support body: firstly, cheap raw materials such as cordierite, mullite, clay and the like are adopted; second, for Al with grain size of 20-30 μm 2 O 3 The modification is carried out to prepare the support body by improving the sintering activity. Although the former method effectively reduces the firing temperature of the ceramic, the former method does not conform to the strategic policy of national resource protection due to the adoption of a large amount of natural mineral resources, and the product strength is greatly reduced; the latter method can also reduce the firing temperature of the ceramic, but the manufacturing cost is not significantly reduced because the expensive ultrafine powder is used as the raw material.
The main chemical composition of the fly ash can be SiO 2 -Al 2 O 3 MeO represents (where MeO can be Na) 2 O、K 2 O、MgO、 CaO、Fe 2 O 3 、MnO、TiO 2 Etc.) is an advantageous raw material for preparing porous ceramics in industrial solid wastes.
Therefore, the ceramic product for the mullite porous microfiltration membrane support body is developed by using the fly ash as a main raw material, and has important environmental protection value and market prospect.
Disclosure of Invention
The product of the invention is intended to replace the product with extremely high sintering temperature and manufactureAs cost of Al 2 O 3 The porous ceramic support body is applied to sewage filtration and purification, is independently developed in a laboratory at first, and then carries out preliminary amplification experiment on the preparation technology, so that a good test result is obtained: high-alumina fly ash and Al less than 100 mu m 2 O 3 The powder is used as a main raw material, a novel sintering-aid type composite pore-forming agent which is independently designed and synthesized is used, and under the condition that the sintering temperature is less than or equal to 1500 ℃ and the heat preservation is carried out for 4 hours, when the addition of the high-alumina fly ash is 70 percent and the addition of the sintering-aid type composite pore-forming agent is 20 percent, the mullite porous microfiltration membrane support ceramic which is subjected to in-situ reaction sintering and has uniform pore distribution and 0.5-1 mu m size can be obtained, the sintering temperature is reduced by more than 300 ℃ compared with the alumina ceramic, the alumina dosage can be reduced by 80 percent, and the production cost is greatly reduced.
In order to realize the aim, the invention provides a preparation method of mullite porous microfiltration membrane support body ceramic, which comprises the following specific steps:
step one, preparing raw materials of the mullite porous microfiltration membrane support body ceramic according to the following raw material formula:<100 μm of Al 2 O 3 5-15g of powder; 60-75g of high-alumina fly ash; sintering-assisting type composite pore-forming agent 10-20g; polyvinyl alcohol, 0.5-5g; purified water, 12.5-120g;
wherein the high-alumina fly ash contains glass phase and mullite (3 Al) 2 O 3 ·2SiO 2 ) Corundum (alpha-Al) 2 O 3 ) And a small amount of quartz, which is irregular spherical particles with the particle size of less than 200 mu m;
the alcoholysis degree of the polyvinyl alcohol is 87-89%;
the synthesis method of the sintering-assisting type composite pore-forming agent comprises the following steps: preparing monodisperse polystyrene microspheres with the particle size of less than or equal to 2 microns, growing sol silicon dioxide on the monodisperse polystyrene microspheres in situ, and then compounding the polystyrene microspheres with carbon black with the nano particle size;
adding the raw materials in the proportion into a ball milling tank, drying after ball milling to obtain powder, granulating the powder, sieving the powder with a 40-80-mesh sieve, taking the powder for dry pressing and forming to prepare a green body, drying, and sintering in a high-temperature electric furnace to obtain the mullite porous microfiltration membrane support body ceramic;
wherein the sintering process parameters are as follows: heating from room temperature to 250 ℃ at a heating rate of 5-10 ℃/min, heating from 250 ℃ to 500 ℃ at a heating rate of 1-5 ℃/min, keeping the temperature at 500 ℃ for 0.5-1h, heating from 500 ℃ to 800 ℃ at a heating rate of 1-5 ℃/min, keeping the temperature at 800 ℃ for 0.5-1h, heating from 800 ℃ to 1500 ℃ at a heating rate of 1-5 ℃/min, and keeping the temperature at 1500 ℃ for 3-5h.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The sintering-aid type composite pore-forming agent is designed and synthesized, and is formed by compounding polystyrene microspheres coated with nano silicon dioxide and carbon black, a pore structure is formed in a forming stage, the idea of curing the pore structure in a sintering stage is utilized, the carbon black with pyrolysis temperature concentrated in the range of 500-700 ℃ and the polystyrene microspheres with pyrolysis temperature concentrated in the range of less than 500 ℃ are utilized to be matched, the pyrolysis temperature range of the pore-forming agent is widened by utilizing the matching of the carbon black and the polystyrene microspheres, so that gas generated by decomposition and oxidation of the pore-forming agent is controllably discharged, and the problems that a single pore-forming agent is relatively narrow in decomposition temperature range and generates a large amount of gaseous products in a short time in a burning loss process can be avoided; and the nano-silica is used for reducing the crystallization temperature, thereby realizing the technical effects of promoting sintering and reducing the sintering temperature.
(2) The mullite porous microfiltration membrane support body ceramic is prepared by taking the high-alumina fly ash as a main raw material, so that the utilization value of the high-alumina fly ash is improved, the raw material does not contain any natural resource, the performance of the same kind of products sold in the market is achieved or approached, and the environmental pollution caused by industrial solid waste-the high-alumina fly ash is eliminated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments in the present application may be combined with each other without conflict. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The starting materials and reagents used in the following examples were all commercially available from conventional manufacturers in the art; the experimental methods used are all routine experimental methods known to those skilled in the art.
Example 1
The invention provides a preparation method of a mullite porous microfiltration membrane support ceramic, which comprises the following specific process steps:
step one, proportioning raw materials of the mullite porous microfiltration membrane support body ceramic according to the following raw material formula: 20 μm Al 2 O 3 10g of powder; 70g of high-alumina fly ash; 15g of sintering-assisting composite pore-forming agent; polyvinyl alcohol, 2.5g; purified water, 50g;
the sintering-assisting type composite pore-forming agent comprises the following specific synthesis steps:
adding 8g of PVP and 150mL of mixed solvent consisting of ethanol and 2-methoxyethanol according to a volume ratio of 2;
dispersing 10g of monodisperse polystyrene microspheres in 150mL of absolute ethanol, adjusting the pH value to 11 by using a mixed aqueous solution of ammonia and ethanol, adding a mixed solution consisting of 30mL of tetraethyl orthosilicate TEOS, 15mL of ammonia water and 120mL of purified water under magnetic stirring at 40 ℃, fully reacting for 4h, standing for 3h at room temperature, washing for 3-5 times by using ethanol and deionized water respectively, and performing spray drying to obtain the polystyrene microspheres loaded with silicon dioxide;
compounding 10g of polystyrene microspheres loaded with silicon dioxide and 10g of carbon black with the particle size of 200-300nm to obtain a sintering-assisting type composite pore-forming agent;
step two, adding the raw materials in the proportion into a ball milling tank, carrying out ball milling for 2 hours, drying at 60 ℃ to obtain powder, granulating the powder, sieving with a 80-mesh sieve, taking the powder for dry press molding, preparing into green bodies, drying at 60 ℃, and then sintering in a high-temperature electric furnace, wherein the sintering process parameters are as follows: keeping the temperature at 500 ℃ for 0.5h at the temperature rising rate of 8 ℃/min from room temperature to 250 ℃ and at the temperature rising rate of 3 ℃/min from 250 ℃ to 500 ℃, keeping the temperature at 800 ℃ for 0.5h at the temperature rising rate of 3 ℃/min from 500 ℃ to 800 ℃, keeping the temperature at 1500 ℃ for 4h at the temperature rising rate of 5 ℃/min from 800 ℃ to 1500 ℃, and obtaining the mullite porous microfiltration membrane support body ceramic;
and (3) performance testing:
1. and (3) porosity testing: according to the Archimedes principle, the porosity is calculated by the following formula:
P＝{[(m 1 -m 0 )×ρ]/[m 0 +(m 1 -m 0 )×ρ]}×100％；
in the formula: p represents porosity, in%; m is 0 Represents the mass after drying, in g; m is 1 The mass is measured by putting a sample into purified water, taking out the sample after soaking for 2 hours, quickly wiping the surface of the sample with water, and the unit of the mass is g; ρ represents the density of the sample measured by a 3H-2000TD1 full-automatic true density analyzer, and the unit is g/cm 3 ；
2. And (3) testing the bending strength: the three-point bending strength of the sample is tested by using a CKZ-10000 intelligent ceramic tile fracture modulus tester, and the calculation formula is as follows:
R＝3FL/2BH 2 ；
wherein R is the three-point bending strength with the unit of MPa; f is the load of the sample to be destroyed and has the unit of N; l is the span in mm; b is the fracture section width of the sample, mm; h is the fracture section height of the sample, and the unit is mm;
3. and (3) testing the pore diameter: carrying out vacuum infiltration on a sample by using absolute ethyl alcohol, and then testing the aperture of the sample by using a 3H-2000PB bubble pressure method filter membrane aperture analyzer, wherein the calculation formula is as follows:
D＝2.86γ/ΔP；
wherein D is the pore diameter in μm; gamma is the surface tension of the liquid, in dny/cm; Δ P is the test differential pressure in KPa.
4. And (3) pure water flux test: the pure water flux test is carried out by using a 3H-2000PBL filtering membrane liquid flux tester, and the calculation formula is as follows:
φ＝V/STF；
wherein φ represents the pure water flux in L/(m) 2 H.bar); v is the volume of the filtered pure water, and the unit is L; s is the area in m 2 (ii) a T is the pumping time in units of h; f is the suction pressure in bar;
5. and (3) testing the corrosion resistance: the samples were subjected to corrosion experiments according to GB/T1970-1996 as follows:
the sample was placed in 20wt.% H 2 SO 4 Soaking in water solution at constant temperature of 80 deg.C for 8 hr, ultrasonically cleaning with ultrapure water for 10min, repeating for 3 times, drying in a drying oven at 110 deg.C, measuring the acid-corroded mass, and calculating the mass loss rate;
placing the sample in 10wt.% NaOH aqueous solution, soaking for 8h at a constant temperature of 80 ℃, ultrasonically cleaning for 10min by using ultrapure water, repeating for 3 times, then placing the sample in a drying oven at 110 ℃, drying, measuring the mass of the sample after alkali corrosion, and calculating the mass loss rate;
the results of the above tests are shown in table 1 below;
TABLE 1
| Support prepared according to the invention | Commercial Al 2 O 3 Support body | |
| Porosity/% | 35.6 | 37.1 |
| Flexural strength/MPa | 52.4 | 72.3 |
| Average pore diameter/. Mu.m | 2.0 | 4.7 |
| Acid/base corrosion Rate/%) | 0.79/0.85 | 0.96/0.93 |
| Pure water flux/(. Times.10) 3 L/(m 2 ·h·bar)) | 7.40 | 7.02 |
The first test scheme is as follows:
in order to optimize the components of the pore-forming agent, the following experimental scheme is implemented in the invention:
experiment one:
the synthesis method of the pore-forming agent P-1 comprises the following steps: preparing monodisperse polystyrene microspheres with the particle size of less than or equal to 2 mu m, growing sol-silica on the monodisperse polystyrene microspheres in situ, and then compounding the polystyrene microspheres with the particle size of 200-300nm in a pore-forming agent P-1: silicon dioxide: the mass ratio of the carbon black is 5.53:4.47:10;
the mullite porous microfiltration membrane support ceramic was prepared according to example 1 by using the pore-forming agent P-1, and the porosity of the ceramic was 35.6%.
Experiment two:
the synthetic method of the pore-forming agent P-2 comprises the following steps: preparing monodisperse polystyrene microspheres with the particle size of less than or equal to 2 microns, growing sol silicon dioxide on the monodisperse polystyrene microspheres in situ, and preparing the polystyrene microspheres in the pore-forming agent P-2: the mass ratio of silica is 5.53:4.47;
the mullite porous microfiltration membrane support ceramic was prepared according to example 1 using pore former P-2, and had a porosity of 23.7%.
Experiment three:
the synthesis method of the pore-forming agent P-3 comprises the following steps: preparing monodisperse polystyrene microspheres with the particle size of less than or equal to 2 mu m, and then compounding the monodisperse polystyrene microspheres with carbon black with the particle size of 200-300nm, wherein the polystyrene microspheres in the pore-forming agent P-3 are as follows: the mass ratio of the carbon black is 10:10; (ii) a
The mullite porous microfiltration membrane support ceramic with the porosity of 39.2% is prepared according to the example 1 by using the pore-forming agent P-3.
Experiment four:
the synthetic method of the pore-forming agent P-4 comprises the following steps: preparing monodisperse polystyrene microspheres with the particle size of less than or equal to 2 mu m;
the mullite porous microfiltration membrane support ceramic was prepared according to example 1 using pore former P-4, and had a porosity of 20.4%.
Experiment five:
the raw material formula of the pore-forming agent P-5 is as follows: carbon black having a particle diameter of 200 to 300 nm;
the mullite porous microfiltration membrane support ceramic is prepared according to the example 1 by using the pore-forming agent P-5, and the porosity of the mullite porous microfiltration membrane support ceramic is 26.1%.
According to the experiment, the sintering-assistant type composite pore-forming agent is used to obtain the mullite porous microfiltration membrane support ceramic with excellent comprehensive performance.
Test scheme two:
in order to optimize the introduction mode of the pore-forming agent, the invention implements the following experimental scheme:
experiment one:
firstly, preparing a polyvinyl alcohol aqueous solution;
dispersing the sintering-assistant type composite pore-forming agent in a polyvinyl alcohol aqueous solution to obtain a pore-forming agent and a binder;
the rest raw materials in the example 1 are firstly added into a ball milling tank, after ball milling is carried out for 1h, pore-forming agent and bonding agent are added, and the mullite porous microfiltration membrane support ceramic is prepared according to the example 1, wherein the porosity of the mullite porous microfiltration membrane support ceramic is 35.6 percent
Experiment two:
the raw material formula in the example 1 is synchronously added into a ball milling tank, and the mullite porous microfiltration membrane support ceramic prepared according to the example 1 is prepared, wherein the porosity of the mullite porous microfiltration membrane support ceramic is 30.8%.
Claims (5)
1. A preparation method of a mullite porous microfiltration membrane support body ceramic is characterized by comprising the following steps:
step one, proportioning raw materials of the mullite porous microfiltration membrane support body ceramic according to the following raw material formula: al (aluminum) 2 O 3 5-15 parts of powder; 60-75 parts of high-alumina fly ash; sintering-assisting type composite pore-forming agent, 10-20 parts; polyvinyl alcohol, 0.5-5 parts; purified water, 12.5-120 parts;
the synthesis method of the sintering-assisting type composite pore-forming agent comprises the following steps: preparing monodisperse polystyrene microspheres, growing sol silicon dioxide on the monodisperse polystyrene microspheres in situ, and then compounding the polystyrene microspheres with carbon black with nano particle size;
and step two, adding the raw materials in the proportion into a ball milling tank, drying the raw materials after ball milling to obtain powder, granulating and sieving the powder, taking the powder for dry pressing and forming to prepare a green body, drying the green body, and sintering the green body in a high-temperature electric furnace to obtain the mullite porous microfiltration membrane support body ceramic.
2. The preparation method of the mullite porous microfiltration membrane support ceramic as claimed in claim 1, wherein the sintering process parameters in the second step are as follows: the temperature is increased from 250 ℃ to 500 ℃ at the rate of 1-5 ℃/min, the temperature is kept for 0.5-1h at 500 ℃, the temperature is increased from 500 ℃ to 800 ℃ at the rate of 1-5 ℃/min, the temperature is kept for 0.5-1h at 800 ℃, the temperature is increased from 800 ℃ to 1500 ℃ at the rate of 1-5 ℃/min, and the temperature is kept for 3-5h at 1500 ℃.
3. The preparation method of the mullite porous microfiltration membrane support ceramic as claimed in claim 1, wherein the high-alumina fly ash contains a glass phase and mullite (3 Al) 2 O 3 ·2SiO 2 ) Corundum (alpha-Al) 2 O 3 ) And quartz, the particle size of which is less than 200 μm.
4. The method for preparing the mullite porous microfiltration membrane support ceramic as claimed in claim 1, wherein the Al is 2 O 3 The grain size of the powder is less than 100 mu m.
5. The method for preparing the mullite porous microfiltration membrane support ceramic according to claim 1, wherein the particle size of the monodisperse polystyrene microspheres is less than or equal to 2 μm.
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