CN115364677B - Preparation method of thermal stability modified spherical alumina ceramic microfiltration membrane - Google Patents
Preparation method of thermal stability modified spherical alumina ceramic microfiltration membrane Download PDFInfo
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- CN115364677B CN115364677B CN202110562022.7A CN202110562022A CN115364677B CN 115364677 B CN115364677 B CN 115364677B CN 202110562022 A CN202110562022 A CN 202110562022A CN 115364677 B CN115364677 B CN 115364677B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000012528 membrane Substances 0.000 title claims abstract description 112
- 238000001471 micro-filtration Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 26
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000919 ceramic Substances 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 239000013530 defoamer Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 17
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 17
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000007888 film coating Substances 0.000 claims description 6
- 238000009501 film coating Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000003618 dip coating Methods 0.000 abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 230000004907 flux Effects 0.000 description 15
- 235000020183 skimmed milk Nutrition 0.000 description 13
- 230000001580 bacterial effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 235000020247 cow milk Nutrition 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 8
- 238000004659 sterilization and disinfection Methods 0.000 description 8
- 244000005700 microbiome Species 0.000 description 5
- 235000013336 milk Nutrition 0.000 description 5
- 239000008267 milk Substances 0.000 description 5
- 210000004080 milk Anatomy 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 210000001082 somatic cell Anatomy 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- 102000010445 Lactoferrin Human genes 0.000 description 1
- 108010063045 Lactoferrin Proteins 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- CSSYQJWUGATIHM-IKGCZBKSSA-N l-phenylalanyl-l-lysyl-l-cysteinyl-l-arginyl-l-arginyl-l-tryptophyl-l-glutaminyl-l-tryptophyl-l-arginyl-l-methionyl-l-lysyl-l-lysyl-l-leucylglycyl-l-alanyl-l-prolyl-l-seryl-l-isoleucyl-l-threonyl-l-cysteinyl-l-valyl-l-arginyl-l-arginyl-l-alanyl-l-phenylal Chemical compound C([C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CS)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)C1=CC=CC=C1 CSSYQJWUGATIHM-IKGCZBKSSA-N 0.000 description 1
- 235000021242 lactoferrin Nutrition 0.000 description 1
- 229940078795 lactoferrin Drugs 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000020185 raw untreated milk Nutrition 0.000 description 1
- 230000000392 somatic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- 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
- C04B35/10—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 aluminium oxide
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- C—CHEMISTRY; METALLURGY
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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
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B35/64—Burning or sintering processes
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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
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a preparation method of a thermal stability modified spherical alumina ceramic microfiltration membrane, which comprises the following steps: (1) Placing spherical alumina and nano sintering auxiliary agent in RO water to obtain spherical alumina dispersion liquid; (2) Adding a thickening agent and a pore-forming agent into the spherical alumina dispersion liquid obtained in the step (1), and then adding an organosilicon defoaming agent to obtain a coating liquid; (3) Dip-coating the coating liquid on a tubular porous ceramic membrane support, drying and sintering to obtain an alumina microfiltration membrane; (4) Soaking the alumina microfiltration membrane in sodium hydroxide solution, and washing to obtain a pretreated alumina microfiltration membrane; (5) Adjusting the pH of the ethanol water solution to be acidic, and then adding polyethylene oxide siloxane to obtain a polyethylene oxide siloxane solution; (6) And soaking the alumina micro-filtration membrane in a polyethylene oxide siloxane solution, and curing to obtain the thermal stability modified spherical alumina ceramic micro-filtration membrane.
Description
Technical Field
The invention belongs to the technical field of microfiltration membranes, and particularly relates to a preparation method of a thermal stability modified spherical alumina ceramic microfiltration membrane.
Background
Milk is a food with high nutritive value and contains many substances necessary for human body, such as protein, fat, lactose, minerals, etc. With the continuous improvement of the living standard of people, people put forth higher requirements on the milk quality, and the pollution of microorganisms in raw milk and the quantity of somatic bodies have important influences on the quality, flavor and shelf life of the dairy products. The presence of microorganisms and somatic cells in cow's milk affects the quality and flavor of the product, since the microorganisms and somatic cells release many enzymes with high heat resistance and decompose milk components in raw cow's milk, and thus effective removal of microorganisms and somatic cells in cow's milk is of great significance in improving the flavor and quality of the product.
Methods for reducing and killing microorganisms in cow milk include heat sterilization, centrifugal sterilization, filtration sterilization, autoclaving, ultraviolet sterilization, etc. The existing sterilization method of cow milk can kill bacteria and simultaneously inevitably damages nutrient components in the cow milk to different degrees. With the improvement of ceramic membrane technology, the application of the microfiltration sterilization method in cow milk products is promoted, and as the microfiltration membrane can effectively intercept bacteria, saccharomycetes, mould and the like in the milk, the effective components in the cow milk can permeate, so that the ceramic membrane has the advantage of cold sterilization, prevents the thermal denaturation of protein while ensuring the safety, and comprehensively retains 99% of active immunoglobulin, 95% of lactoferrin, various natural vitamins, milk calcium, mineral substances, trace elements and other nutritional components; the original taste of the fresh cow milk is almost maintained, and the ceramic membrane treatment process can also effectively control the microbial index of the final product, so that the shelf life of the product is prolonged, and the shelf life of the pasteurized 2-day product is prolonged to 21 days. However, the ceramic microfiltration membrane has the problems of easy blockage, low flux and the like at present, so that the improvement of the pollution resistance and the flux of the ceramic microfiltration membrane has important significance for a microfiltration sterilization method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a thermal stability modified spherical alumina ceramic microfiltration membrane.
The technical scheme of the invention is as follows:
a preparation method of a heat stability modified spherical alumina ceramic microfiltration membrane comprises the following steps:
(1) Placing spherical alumina and nano sintering auxiliary agent in RO water, shearing and dispersing to obtain spherical alumina dispersion liquid; the nanometer sintering aid is nanometer titanium oxide, nanometer cerium oxide, nanometer magnesium oxide or nanometer zirconium oxide; in the spherical alumina dispersion liquid, the content of the spherical alumina is 9-11wt percent, and the content of the nano sintering auxiliary agent is 1-3wt percent;
(2) Adding a thickening agent and a pore-forming agent into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoaming agent KH550 to obtain a coating liquid; the thickening agent is cellulose, methyl cellulose or hydroxyethyl cellulose, and the pore-forming agent is polyvinyl alcohol or glycerol; in the film coating liquid, the content of the thickening agent is 2-5wt%, the content of the pore-forming agent is 1-3wt%, and the content of the organosilicon defoamer KH550 is 0.008-0.012wt%;
(3) Coating the coating liquid on a tubular porous ceramic membrane support body, and drying and sintering to obtain an alumina microfiltration membrane;
(4) Soaking the alumina microfiltration membrane in 0.08-0.12mol/L sodium hydroxide solution at 79-81 ℃ for 10-13h, and then washing with RO water to obtain a pretreated alumina microfiltration membrane;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 94-96% to be acidic by using a nitric acid aqueous solution with the concentration of 0.08-0.12mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 6-12 to the concentration of 1-5mol/L to obtain a polyethylene oxide siloxane solution;
(6) Soaking the pretreated alumina microfiltration membrane obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 10-13h, and curing at 105-115 ℃ for 0.8-1.2h to obtain the heat stability modified spherical alumina ceramic microfiltration membrane.
In a preferred embodiment of the present invention, the spherical alumina has a particle size of 1 to 2. Mu.m.
In a preferred embodiment of the present invention, the nano-sintering aid is nano-zirconia.
In a preferred embodiment of the invention, the thickener is hydroxyethyl cellulose.
In a preferred embodiment of the present invention, the porogen is polyvinyl alcohol.
In a preferred embodiment of the present invention, the nano-sintering aid is nano-zirconia, the thickener is hydroxyethyl cellulose, and the porogen is polyvinyl alcohol.
In a preferred embodiment of the present invention, the drying in step (3) is: heating to 80-120deg.C at a speed of 1-3deg.C/min at room temperature, and drying at a constant temperature for 2-5h.
Further preferably, the sintering in the step (3) is: heating to 1300-1500 ℃ from the temperature of heat preservation and drying at the speed of 1-5 ℃/min, heat preservation and sintering for 2-5h, and naturally cooling.
Still more preferably, the drying in the step (3) is: heating to 120 ℃ at the speed of 3 ℃/min at room temperature, and then preserving heat and drying for 5 hours; the sintering in the step (3) is as follows: heating to 1300-1400 ℃ from the temperature of heat preservation and drying at the speed of 3 ℃/min, and naturally cooling after heat preservation and sintering for 3 h.
In a preferred embodiment of the present invention, the spherical alumina content in the spherical alumina dispersion is 10wt% and the nano sintering aid content is 1wt%; in the film coating liquid, the content of the thickener is 2-5wt%, the content of the pore-forming agent is 2wt%, and the content of the organic silicon defoamer is 0.01wt%.
The beneficial effects of the invention are as follows:
1. according to the invention, specific spherical alumina is selected as a raw material, and a specific pore-forming agent is added to improve the porosity of the film; adding a specific sintering aid to increase the strength of the film; and a specific thickener is added to improve the flatness of the film layer, so that the anti-pollution capability of the film layer is improved.
2. The spherical alumina is used to make the porosity of the membrane reach 45%, the flux of the membrane is increased, the flatness of the membrane is improved to increase the anti-pollution performance of the membrane, the hydrophilicity of the membrane is increased by grafting the polyethylene oxide siloxane, the water contact angle is reduced to 10 ℃, the organic matter polyethylene oxide siloxane can be kept stable and not fall off under the environment of 120 ℃, and the performance of the membrane is kept unchanged.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
Example 1
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 2wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) Dip-coating the coating liquid on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, heating to 120 ℃ at a speed of 3 ℃/min at room temperature, then preserving heat and drying for 5h, heating to 1300 ℃ at a speed of 3 ℃/min, preserving heat and sintering for 3h, and obtaining an alumina microfiltration membrane tube (membrane layer porosity of 45%);
(4) Soaking the alumina micro-filtration membrane tube in sodium hydroxide solution with the concentration of 0.1mol/L at 80 ℃ for 12 hours, and then washing the tube cleanly with RO water to obtain a pretreated alumina micro-filtration membrane tube;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 95% to be acidic by using a nitric acid aqueous solution with the concentration of 0.1mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 6 to the concentration of 1mol/L to obtain a polyethylene oxide siloxane solution;
(6) And (3) immersing the pretreated alumina micro-filtration membrane tube obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 12 hours, and curing for 1 hour at 110 ℃ to obtain the heat-stability modified spherical alumina ceramic micro-filtration membrane with the membrane tube water contact angle of 10 degrees.
The membrane flux of the thermal stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment is 750LHM after the skim milk is filtered for 30min at the temperature of 0.1MPa and 25 ℃, and the bacterial retention rate is 99%. After the heat-stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment 1 is subjected to oven heat treatment at 120 ℃ for 12 hours, skim milk is filtered for 30 minutes under the conditions of 0.1MPa and 25 ℃ and then the membrane flux is 748LHM, and the bacterial retention rate is 99%.
Example 2
(1) Placing spherical alumina with the particle size of 3 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 2wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) Dip-coating the coating liquid on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, heating to 120 ℃ at a speed of 3 ℃/min at room temperature, then preserving heat and drying for 5h, heating to 1300 ℃ at a speed of 3 ℃/min, preserving heat and sintering for 3h, and obtaining an alumina microfiltration membrane tube (membrane layer porosity of 48%);
(4) Soaking the alumina micro-filtration membrane tube in sodium hydroxide solution with the concentration of 0.1mol/L at 80 ℃ for 12 hours, and then washing the tube cleanly with RO water to obtain a pretreated alumina micro-filtration membrane tube;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 95% to be acidic by using a nitric acid aqueous solution with the concentration of 0.1mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 6 to the concentration of 3mol/L to obtain a polyethylene oxide siloxane solution;
(6) And (3) immersing the pretreated alumina micro-filtration membrane tube obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 12 hours, and curing for 1 hour at 110 ℃ to obtain the heat-stability modified spherical alumina ceramic micro-filtration membrane with the membrane tube water contact angle of 8 degrees.
The membrane flux of the thermal stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment is 800LHM after the skim milk is filtered for 30min at the temperature of 0.1MPa and 25 ℃, and the bacterial retention rate is 99%. After the heat-stability modified spherical alumina ceramic microfiltration membrane prepared in the example 1 is subjected to oven heat treatment at 120 ℃ for 12 hours, skim milk is filtered for 30 minutes under the conditions of 0.1MPa and 25 ℃ and then the membrane flux is 795LHM, and the bacterial retention rate is 99%.
Example 3
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 5wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) Dip-coating the coating liquid on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, heating to 120 ℃ at a speed of 3 ℃/min at room temperature, then preserving heat and drying for 5h, heating to 1400 ℃ at a speed of 3 ℃/min, preserving heat and sintering for 3h, and obtaining an alumina microfiltration membrane tube (membrane layer porosity 44%); (4) Soaking the alumina micro-filtration membrane tube in sodium hydroxide solution with the concentration of 0.1mol/L at 80 ℃ for 12 hours, and then washing the tube cleanly with RO water to obtain a pretreated alumina micro-filtration membrane tube;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 95% to be acidic by using a nitric acid aqueous solution with the concentration of 0.1mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 6 to the concentration of 5mol/L to obtain a polyethylene oxide siloxane solution;
(6) And (3) immersing the pretreated alumina micro-filtration membrane tube obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 12 hours, and curing for 1 hour at 110 ℃ to obtain the heat-stability modified spherical alumina ceramic micro-filtration membrane with the membrane tube water contact angle of 7 degrees.
The membrane flux of the thermal stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment is 830LHM and the bacterial retention rate is 99% after the thermal stability modified spherical alumina ceramic microfiltration membrane is used for filtering skim milk for 30min under the conditions of 0.1MPa and 25 ℃. After the heat-stability modified spherical alumina ceramic microfiltration membrane prepared in the example 1 is subjected to oven heat treatment at 120 ℃ for 12 hours, skim milk is filtered for 30 minutes under the conditions of 0.1MPa and 25 ℃ and then the membrane flux is 831LHM, and the bacterial retention rate is 99%.
Example 4
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 5wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) Dip-coating the coating liquid on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, heating to 120 ℃ at a speed of 3 ℃/min at room temperature, then preserving heat and drying for 5h, heating to 1400 ℃ at a speed of 3 ℃/min, preserving heat and sintering for 3h, and obtaining an alumina microfiltration membrane tube (membrane layer porosity of 45%);
(4) Soaking the alumina micro-filtration membrane tube in sodium hydroxide solution with the concentration of 0.1mol/L at 80 ℃ for 12 hours, and then washing the tube cleanly with RO water to obtain a pretreated alumina micro-filtration membrane tube;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 95% to be acidic by using a nitric acid aqueous solution with the concentration of 0.1mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 9 to the concentration of 3mol/L to obtain a polyethylene oxide siloxane solution;
(6) And (3) immersing the pretreated alumina micro-filtration membrane tube obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 12 hours, and curing for 1 hour at 110 ℃ to obtain the heat-stability modified spherical alumina ceramic micro-filtration membrane with the membrane tube water contact angle of 12 degrees.
The membrane flux of the thermal stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment is 810LHM after the skim milk is filtered for 30min at the temperature of 0.1MPa and 25 ℃, and the bacterial retention rate is 99%. After the heat-stability modified spherical alumina ceramic microfiltration membrane prepared in the example 1 is subjected to oven heat treatment at 120 ℃ for 12 hours, skim milk is filtered for 30 minutes under the conditions of 0.1MPa and 25 ℃ and then the membrane flux is 792LHM, and the bacterial retention rate is 99%.
Example 5
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 5wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) Dip-coating the coating liquid on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, heating to 120 ℃ at a speed of 3 ℃/min at room temperature, then preserving heat and drying for 5h, heating to 1400 ℃ at a speed of 3 ℃/min, preserving heat and sintering for 3h, and obtaining an alumina microfiltration membrane tube (membrane layer porosity 43%);
(4) Soaking the alumina micro-filtration membrane tube in sodium hydroxide solution with the concentration of 0.1mol/L at 80 ℃ for 12 hours, and then washing the tube cleanly with RO water to obtain a pretreated alumina micro-filtration membrane tube;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 95% to be acidic by using a nitric acid aqueous solution with the concentration of 0.1mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 12 to the concentration of 5mol/L to obtain a polyethylene oxide siloxane solution;
(6) And (3) immersing the pretreated alumina micro-filtration membrane tube obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 12 hours, and curing for 1 hour at 110 ℃ to obtain the heat-stability modified spherical alumina ceramic micro-filtration membrane with the membrane tube water contact angle of 5 degrees.
The membrane flux of the thermal stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment is 730LHM after the skim milk is filtered for 30min at the temperature of 0.1MPa and 25 ℃, and the bacterial retention rate is 99%. After the heat-stability modified spherical alumina ceramic microfiltration membrane prepared in the embodiment 1 is subjected to oven heat treatment at 120 ℃ for 12 hours, skim milk is filtered for 30 minutes under the conditions of 0.1MPa and 25 ℃ and then the membrane flux is 720LHM, and the bacterial retention rate is 99%.
Comparative example 1
(1) Placing non-spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion, the content of non-spherical alumina is 10wt percent, and the content of nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the coating liquid, the content of hydroxyethyl cellulose is 3wt%, the content of polyvinyl alcohol is 2wt%, and the content of an organosilicon defoamer KH550 is 0.01wt%;
(3) The coating liquid is coated on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, then the temperature is raised to 120 ℃ at a speed of 3 ℃/min at room temperature, then the heat is preserved and dried for 5 hours, and then the temperature is raised to 1300 ℃ at a speed of 3 ℃/min, and the heat is preserved and sintered for 3 hours, thus obtaining the comparative membrane 1 (the porosity of the membrane layer is 35%).
The comparative film 1 prepared in this comparative example was used to filter skim milk for 1min at 0.1MPa and 25℃to cause clogging of the film.
Comparative example 2
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding polyethylene glycol and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the film coating liquid, the content of polyethylene glycol is 2wt%, the content of polyvinyl alcohol is 3wt%, and the content of organosilicon defoamer KH550 is 0.01wt%;
(3) The coating liquid is coated on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, then the temperature is raised to 120 ℃ at a speed of 3 ℃/min at room temperature, then the heat is preserved and dried for 5 hours, the temperature is raised to 1300 ℃ at a speed of 3 ℃/min, and the heat is preserved and sintered for 3 hours, thus obtaining the comparative membrane 2 (the porosity of the membrane layer is 33%).
The flux of the membrane layer of the comparative membrane 2 after filtering the skim milk for 30min under the conditions of 0.1MPa and 25 ℃ is 200-300LHM, and the bacterial retention rate is 99%.
Comparative example 3
(1) Placing spherical alumina with the particle size of 2 mu m and nano zirconia (with the particle size of 20 nm) into RO water, and shearing and dispersing for 15min to obtain spherical alumina dispersion liquid; in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano zirconia is 1wt percent;
(2) Adding hydroxyethyl cellulose and polyvinyl alcohol into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoamer KH550 to obtain a coating liquid; in the film coating liquid, the content of polyethylene glycol is 2wt%, the content of polyvinyl alcohol is 2wt%, and the content of organosilicon defoamer KH550 is 0.01wt%;
(3) The coating liquid is coated on a tubular porous ceramic membrane support with an average pore diameter of 10-20 mu m, then the temperature is raised to 120 ℃ at a speed of 3 ℃/min at room temperature, then the heat is preserved and dried for 5 hours, the temperature is raised to 1300 ℃ at a speed of 3 ℃/min, and the heat is preserved and sintered for 3 hours, thus obtaining the comparative membrane 3 (the porosity of the membrane layer is 42%).
The flux of the membrane layer of the comparative membrane 3 after filtering the skim milk for 30min under the conditions of 0.1MPa and 25 ℃ is 400LHM, and the bacterial retention rate is 99%.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (5)
1. A preparation method of a heat stability modified spherical alumina ceramic microfiltration membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) Placing spherical alumina with the particle size of 1-2 mu m and a nano sintering aid into RO water, and shearing and dispersing to obtain spherical alumina dispersion liquid; the nano sintering aid is nano zirconia; in the spherical alumina dispersion liquid, the content of the spherical alumina is 9-11wt percent, and the content of the nano sintering auxiliary agent is 1-3wt percent;
(2) Adding a thickening agent and a pore-forming agent into the spherical alumina dispersion liquid obtained in the step (1), fully mixing, and then adding an organosilicon defoaming agent KH550 to obtain a coating liquid; the thickening agent is hydroxyethyl cellulose, and the pore-forming agent is polyvinyl alcohol; in the film coating liquid, the content of the thickening agent is 2-5wt%, the content of the pore-forming agent is 1-3wt%, and the content of the organosilicon defoamer KH550 is 0.008-0.012wt%;
(3) Coating the coating liquid on a tubular porous ceramic membrane support body, and drying and sintering to obtain an alumina microfiltration membrane;
(4) Soaking the alumina microfiltration membrane in 0.08-0.12mol/L sodium hydroxide solution at 79-81 ℃ for 10-13h, and then washing with RO water to obtain a pretreated alumina microfiltration membrane;
(5) Adjusting the pH of an ethanol aqueous solution with the concentration of 94-96% to be acidic by using a nitric acid aqueous solution with the concentration of 0.08-0.12mol/L, and then adding polyethylene oxide siloxane with the polymerization degree of 6-12 to the concentration of 1-5mol/L to obtain a polyethylene oxide siloxane solution;
(6) Soaking the pretreated alumina microfiltration membrane obtained in the step (4) in the polyethylene oxide siloxane solution obtained in the step (5) for 10-13h, and curing at 105-115 ℃ for 0.8-1.2h to obtain the heat stability modified spherical alumina ceramic microfiltration membrane.
2. The method of manufacturing according to claim 1, wherein: the drying in the step (3) is as follows: heating to 80-120deg.C at a speed of 1-3deg.C/min at room temperature, and drying at a constant temperature for 2-5h.
3. The method of manufacturing as claimed in claim 2, wherein: the sintering in the step (3) is as follows: heating to 1300-1500 ℃ from the temperature of heat preservation and drying at the speed of 1-5 ℃/min, heat preservation and sintering for 2-5h, and naturally cooling.
4. A method of preparation as claimed in claim 3, wherein: the drying in the step (3) is as follows: heating to 120 ℃ at the speed of 3 ℃/min at room temperature, and then preserving heat and drying for 5 hours; the sintering in the step (3) is as follows: heating to 1300-1400 ℃ from the temperature of heat preservation and drying at the speed of 3 ℃/min, and naturally cooling after heat preservation and sintering for 3 h.
5. The method of manufacturing according to claim 1, wherein: in the spherical alumina dispersion liquid, the content of the spherical alumina is 10wt percent, and the content of the nano sintering aid is 1wt percent; in the film coating liquid, the content of the thickener is 2-5wt%, the content of the pore-forming agent is 2wt%, and the content of the organic silicon defoamer is 0.01wt%.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686920A (en) * | 2005-04-05 | 2005-10-26 | 南京工业大学 | Method for preparing micro filtration membrane made from ceramics |
| WO2006079208A1 (en) * | 2005-01-26 | 2006-08-03 | Global Synfrac Inc. | Lightweight proppant and method of making same |
| CN102350226A (en) * | 2011-08-30 | 2012-02-15 | 南京工业大学 | Preparation method for organic and inorganic hollow fiber composite membrane |
| CN102380321A (en) * | 2011-09-07 | 2012-03-21 | 三达膜科技（厦门）有限公司 | Method for preparing coating of alumina ceramic membrane |
| CN102408250A (en) * | 2011-07-25 | 2012-04-11 | 三达膜科技（厦门）有限公司 | Ceramic membrane support and preparation method thereof |
| CN105561803A (en) * | 2015-12-29 | 2016-05-11 | 合肥创想能源环境科技有限公司 | Preparation method of high-flux and high-precision ceramic ultrafiltration membrane for oil removal and iron removal of high-temperature condensed water |
| CN106474947A (en) * | 2016-12-14 | 2017-03-08 | 中国科学技术大学 | A kind of preparation method of surface hydrophobicity porous ceramic film |
| CN109351205A (en) * | 2018-09-19 | 2019-02-19 | 广州中国科学院先进技术研究所 | A kind of silicon-oxygen-carbon ceramic hollow-fibre membrane and preparation method thereof |
| CN110270230A (en) * | 2018-03-16 | 2019-09-24 | 翁志龙 | A kind of preparation method of zirconia ceramic ultrafiltration film |
| CN110652875A (en) * | 2019-09-20 | 2020-01-07 | 三达膜科技（厦门）有限公司 | Preparation method of wear-resistant ceramic microfiltration membrane |
| CN110922204A (en) * | 2019-12-08 | 2020-03-27 | 浙江理工大学 | Preparation method of low-temperature sintered alumina ceramic membrane |
| CN112156656A (en) * | 2020-09-11 | 2021-01-01 | 武汉理工大学 | Mullite whisker ceramic filter membrane with high permeability and high filtering precision and preparation method thereof |
-
2021
- 2021-05-21 CN CN202110562022.7A patent/CN115364677B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006079208A1 (en) * | 2005-01-26 | 2006-08-03 | Global Synfrac Inc. | Lightweight proppant and method of making same |
| CN1686920A (en) * | 2005-04-05 | 2005-10-26 | 南京工业大学 | Method for preparing micro filtration membrane made from ceramics |
| CN102408250A (en) * | 2011-07-25 | 2012-04-11 | 三达膜科技（厦门）有限公司 | Ceramic membrane support and preparation method thereof |
| CN102350226A (en) * | 2011-08-30 | 2012-02-15 | 南京工业大学 | Preparation method for organic and inorganic hollow fiber composite membrane |
| CN102380321A (en) * | 2011-09-07 | 2012-03-21 | 三达膜科技（厦门）有限公司 | Method for preparing coating of alumina ceramic membrane |
| CN105561803A (en) * | 2015-12-29 | 2016-05-11 | 合肥创想能源环境科技有限公司 | Preparation method of high-flux and high-precision ceramic ultrafiltration membrane for oil removal and iron removal of high-temperature condensed water |
| CN106474947A (en) * | 2016-12-14 | 2017-03-08 | 中国科学技术大学 | A kind of preparation method of surface hydrophobicity porous ceramic film |
| CN110270230A (en) * | 2018-03-16 | 2019-09-24 | 翁志龙 | A kind of preparation method of zirconia ceramic ultrafiltration film |
| CN109351205A (en) * | 2018-09-19 | 2019-02-19 | 广州中国科学院先进技术研究所 | A kind of silicon-oxygen-carbon ceramic hollow-fibre membrane and preparation method thereof |
| CN110652875A (en) * | 2019-09-20 | 2020-01-07 | 三达膜科技（厦门）有限公司 | Preparation method of wear-resistant ceramic microfiltration membrane |
| CN110922204A (en) * | 2019-12-08 | 2020-03-27 | 浙江理工大学 | Preparation method of low-temperature sintered alumina ceramic membrane |
| CN112156656A (en) * | 2020-09-11 | 2021-01-01 | 武汉理工大学 | Mullite whisker ceramic filter membrane with high permeability and high filtering precision and preparation method thereof |
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