CN103360080A - Improved method for preparing ceramic nanofiltration membrane by sol-gel method - Google Patents
Improved method for preparing ceramic nanofiltration membrane by sol-gel method Download PDFInfo
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- CN103360080A CN103360080A CN2013103030998A CN201310303099A CN103360080A CN 103360080 A CN103360080 A CN 103360080A CN 2013103030998 A CN2013103030998 A CN 2013103030998A CN 201310303099 A CN201310303099 A CN 201310303099A CN 103360080 A CN103360080 A CN 103360080A
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 29
- 238000003980 solgel method Methods 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 238000003618 dip coating Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000001354 calcination Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 229920002307 Dextran Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- -1 γ-(methacryloxypropyl) propyl Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BYRRPYMBVHTVKO-UHFFFAOYSA-N [Na].[Ti] Chemical compound [Na].[Ti] BYRRPYMBVHTVKO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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Abstract
The invention relates to an improved method for preparing a ceramic nanofiltration membrane by a sol-gel method, which is characterized in that nano particles with a certain particle size are added into a sol to prepare a coating liquid, the prepared coating liquid is used for coating a porous support body, and a wet membrane is dried in the air and is directly roasted to obtain the nanofiltration membrane. The method adopts 3-50 nm nano particles to modify the macroporous defects on the surface of the support body, can achieve the aim of toughening gel, increases the strength of the support body, effectively avoids the problem of cracking of a membrane layer in the drying process, and can prepare a ceramic membrane with a complete membrane layer, no crack, no defect and a 1-10 nm pore diameter on a sheet-type, single-tube or multi-channel support body with a pore diameter of 50-200 nm. The ceramic nanofiltration membrane prepared by the method has the advantages of narrow pore size distribution, simple process and good repeatability, and is suitable for large-scale production of the ceramic nanofiltration membrane.
Description
Technical field
The present invention relates to a kind of preparation method of nanofiltration membrane, relate in particular to the method that a kind of improved sol-gel method prepares nanofiltration membrane; The sol-gel method that the method is based on the nano-particle toughening technical development prepares the method for nanofiltration membrane, is suitable for the mass-producing preparation of high-performance ceramic nanofiltration membrane.
Background technology
Nanofiltration is the sepn process that grows up phase late 1980s, is a kind of take the Aspect of some new membrane processes of pressure as driving between reverse osmosis and ultrafiltration.Nanofiltration membrane because have that chemically stable is good, the antibiont ability is strong, physical strength is large, the nontoxic characteristics such as high temperature resistant, be widely used in the fields such as biology, food, chemical industry and environment.
The preparation method of inorganic ceramic film mainly contains solid particles sintering process and sol-gel method.Wherein the solid particles sintering process is relatively effective means of a kind of generally acknowledged preparation microfiltration membrane.By wet chemistry method being prepared the coupling of powder method and solid particles sintering process, the method can be used for the ultra-filtration membrane preparation preferably, but the method is not suitable for the preparation of the less nanofiltration membrane in aperture among the CN1443597A.Sol-gel method is because technique is simple, and process is easily controlled, and can big area prepare film at the substrate of different shapes, differing materials, is widely used in the preparation of ceramic super-filtering film and nanofiltration membrane.But the method is difficult to the microscopic properties such as the pore size distribution, porosity of controlling diaphragm material, and is more obvious for these problems of the high-precision small aperture ceramic film of preparation.Mention among the CN101265113A with the improved sol-gel method of template, thereby can realize the control of mould material microtexture is reached the purpose that membrane pore size is controlled.
Commercial nanofiltration membrane kind is very limited at present, and scale is also less.The principal element that limits its scale operation has the qualitative otherness of supporter to cause difference on the nanofiltration membrane performance, and rete easily ftractures simultaneously, has reduced the separation performance of film.Therefore, how to the supporter repair process, make complete rete without cracking then extremely important.Propose among the CN101564652A to adopt a kind of particle-filled method, ceramic supporting body is filled pre-treatment, reach the purpose of modifying supporting body surface and inner aperture, thereby improve quality of forming film.Propose among the CN10126512A to reduce the anchor of supporting body surface, thereby reduced the impact of supporter on film preparation by have the supporter of larger aperture with the organic solution pre-treatment.These methods all need in advance nanofiltration membrane supporting body to be soaked, and surface cleaning and drying, technique are comparatively complicated.
In addition, in the film preparation process, the control that colloidal sol turns the gel drying process also is to affect the complete important factor without cracking of rete.For fear of the cracking situation of rete, by as dry under the constant-temperature constant-humidity environment, stage drying and prolong time of drying, the method such as dry under the super critical condition, thus drying process accurately controlled the cracking that prevents rete.Preparing SiO with people such as flags
2-TiO
2In the process of composite membrane, the employing classification is dry and dry under 65%RH relative humidity condition, and (Chen Fangfang is with .SiO such as flags to have obtained complete rete without ftractureing
2-TiO
2The preparation and characterization of composite membrane. ceramic journal .2010 (31): 576-579).These methods cause increasing substantially of facility investment expense and productive expense owing to need to the humiture of production process be carried out accurate control.Therefore, develop that a kind of technique is simple, facility investment is few, the high-performance ceramic Nanofiltration-membrane technique is then very important cheaply.
Summary of the invention
The object of the invention is to provides a kind of improved sol-gel method to prepare the method for nanofiltration membrane in order to improve the deficiencies in the prior art.
Technical scheme of the present invention is: the nanoparticle doped of taking different-grain diameter according to the difference of supporter quality in colloidal sol to its finishing, rely on simultaneously the rigid body particle to the ponding of macropore, can effectively reduce endosmosis, reduce the pretreated process of supporter in the nanofiltration membrane production.The in addition introducing of nanoparticle can improve storage modulus and the out-of-phase modulus of gel, increases rigidity and the toughness of gelatinous material, reaches the purpose toughness reinforcing to gel; And also play simultaneously energy storage, hinder the effect of stress propagation, prevent that rete from ftractureing in drying process.Thereby prepare that rete is complete, zero defect, nanofiltration membrane that separation accuracy is high.
Concrete technical scheme of the present invention is: a kind of improved sol-gel method prepares the method for nanofiltration membrane, it is characterized in that: in colloidal sol, add nanoparticle, utilize dispersed with stirring to make coating liquid, coating liquid is coated on the supporter, with after the wet film oven dry, direct sintering namely obtains nanofiltration membrane again; The nanoparticle that wherein adds is TiO
2, ZrO
2, Al
2O
3Or SiO
2Nano particle.
Preferred described colloidal sol is the colloidal sol that contains one or more elements in titanium, aluminium, zirconium or the element silicon, and wherein the total content of these elements in colloidal sol is 0.1～2molL
-1The median size of colloidal sol is 1～20nm; The Average Particle Diameters of the nanoparticle that adds is 3～50nm, and greater than the particle diameter of colloidal sol; The concentration of nanoparticle in coating liquid of adding is 0.01～1g/L.
The preferred described nanoparticle of the present invention is SiO
2, TiO
2, Al
2O
3, ZrO
2Nano particle in order to improve the dispersion of particle in colloidal sol, also can be selected the nano particle of this particle through surface hydrophilic or oleophylic modification; The particle diameter of this particle should be greater than the particle diameter of sol particle, since nano particle in colloidal sol difficulty reach fully decentralized degree, therefore the particle diameter of nano particle only needs the particle diameter greater than sol particle, and nano particle just can to form certain particle diameter poor with the colloidal sol particle diameter in colloidal sol.
Described supporter is that the mean pore size of surface tissue is the porous material of 50～200nm, is preferably ceramic membrane, carbon film, stainless steel membrane or titanium aluminum alloy film with one deck structure or multilayered structure; Supporter is chip, single tube or the multi-channel membrane of vesicular structure.
The temperature of preferred wet film oven dry is 20～120 ℃; Sintering temperature is 200～1200 ℃, and heat-up rate is 0.5～5 ℃/min, and roasting time is at 1～24h.
Above-mentioned coating method is that dip coating is filmed or rotational method is filmed.Adopt dip coating to film for pipe porous material, adopt spin-coating method to film for dull and stereotyped porous material.As required, 1～2 time be can repeat and membrane process and oven dry calcining are coated with.
The prepared ceramic membrane of the present invention can be TiO
2, ZrO
2, SiO
2, Al
2O
3And the nanofiltration membrane of mixture.
Beneficial effect:
1: nanoparticle directly added form preparation liquid in the colloidal sol, need not to adopt the rigid body particle that nanofiltration membrane supporting body is carried out pre-treatment.
2: select the rigidity nanoparticle doped of macroparticle, when filming, can reduce endosmosis.
3: the nano-particles filled of macroparticle can be modified supporting body surface and pore size distribution on supporter, can adopt the method for gradient distribution successively supporter to be modified simultaneously, thereby can obtain high-throughput, the narrow nanofiltration membrane of pore size distribution.
4: nanoparticle doped can improve storage modulus and the out-of-phase modulus of gel in colloidal sol, increases rigidity and the toughness of gelatinous material, reaches the purpose toughness reinforcing to gel; Play simultaneously energy storage, hinder the effect of stress propagation and avoid rete in drying process, to ftracture.Therefore, improved the stable and repeated of process of producing product.
Description of drawings
Fig. 1 is the surperficial Electronic Speculum figure of embodiment 1 roasting caudacoria.
Fig. 2 is the section Electronic Speculum figure of embodiment 1 roasting caudacoria.
Fig. 3 is respectively embodiment 2,6, and 7 prepared ceramic membranes are to the retention curve figure of dextran, and X-coordinate is the molecular weight of dextran among the figure, and ordinate zou is the rejection of corresponding molecular weight dextran; Wherein 3A is embodiment 2, and 3B is embodiment 6, and 3C is embodiment 7.
Fig. 4 is the graph of a relation that adds particle front and back storage modulus and temperature of embodiment 3 gelatinous materials.
Fig. 5 is the graph of a relation that adds particle front and back out-of-phase modulus and temperature of embodiment 3 gelatinous materials.
Embodiment
Embodiment 1
Be 8nm in the colloidal sol median size, titanium content is 1molL
-1Acidic sol in to add median size be the TiO of 21nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.5g/L.(surface tissue is the Al of 100nm at porous chip supporter with the coating liquid that makes
2O
3Ceramic membrane) upward film with spin-coating method, dry in 40 ℃ of baking ovens after drying, heat up with 1 ℃/min, getting the aperture at 400 ℃ of lower calcining 4h is that 7nm, porosity are 40% titanium dioxide ceramic film.Fig. 1 is the surperficial Electronic Speculum figure of embodiment 1 calcining caudacoria; Fig. 2 is the section Electronic Speculum figure of embodiment 1 calcining caudacoria; The even film layer that as can be seen from the figure makes by this method there is not slight crack, almost oozes phenomenon without Inner when filming.
Embodiment 2
Be 2nm in the colloidal sol median size, titanium content is 1molL
-1Alkaline colloidal sol in to add median size be the TiO of 25nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.2g/L.(surface tissue is the Al of 100nm at porous chip supporter with the coating liquid that makes
2O
3Ceramic membrane) upward films with the dip-coating embrane method, in 70 ℃ of baking ovens, dry after drying, heat up with 1 ℃/min, at 300 ℃ of lower calcining 3h, get the ceramic membrane of aperture 8nm.And then be 0.2molL at titanium content
-1The TiO that adds 10nm in the titanium colloidal sol
2Nanoparticle (0.05g/L) obtains stable coating liquid and repeats the dried coating film sintering to obtain the aperture be that 2.1nm, porosity are 50% titanium dioxide nanofiltration membrane.Fig. 3 A is that the rear ceramic membrane of embodiment 2 calcinings is to the retention curve of dextran; As can be seen from the figure the dextran molecular weight cut-off of prepared film is 2200Da, and corresponding aperture is 2.1nm.
Embodiment 3
Be 3nm in the colloidal sol median size, titanium content is 1.5molL
-1Acidic sol in to add median size be the TiO of 5nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.2g/L.With the coating liquid that makes at tubular type ZrO
2(aperture is 50nm to ultra-filtration membrane, single tube 10cm is long) upward film with the dip-coating embrane method, at 65 ℃, dry in the climatic chamber of 70%RH after drying, heat up with 2 ℃/min, getting the aperture at 600 ℃ of lower calcining 3h is that 4.5nm, porosity are 45% titanium dioxide ceramic film.Fig. 4 is the graph of a relation that adds particle front and back storage modulus and temperature of gelatinous material, and Fig. 5 is the graph of a relation that adds particle front and back out-of-phase modulus and temperature of gelatinous material.As can be seen from the figure mix behind the particle, storage modulus and the out-of-phase modulus of gel all improve a lot.
Embodiment 4
Be 5nm in the colloidal sol median size, titanium, silicon total content are 1.5molL
-1Acid complex sol (wherein silicon accounts for 10%) in to add with median size after Silane coupling reagent KH-570 (γ-(methacryloxypropyl) propyl trimethoxy silicane) modification be the TiO of 21nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.2g/L.(surface tissue is the Al of 100nm at porous chip supporter with the coating liquid that makes
2O
3Ceramic membrane) upward film with spin-coating method, dry in 70 ℃ of baking ovens after drying, heat up with 2 ℃/min, 500 ℃ of lower calcining 3h get the ceramic membrane of aperture 8nm.And then in titanium, silicon composite sol, add the TiO of 10nm
2Nanoparticle (0.03g/L) obtains stable coating liquid and repeats the dried coating film sintering to obtain the aperture be that 4nm, porosity are 50% titanium Si composite ceramic film.
Embodiment 5
Be 5nm in the colloidal sol median size, the titanium total content is 1.2molL
-1Alkaline complex sol in to add median size be the TiO of 21nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.2g/L.With the coating liquid that makes at tubular type TiO
2Ultra-filtration membrane (aperture is 50nm, and single tube 10cm is long) is upper films with the dip-coating embrane method, dries in 80 ℃ of baking ovens after drying, and heats up with 2 ℃/min, obtains the ceramic membrane of aperture 6nm at 400 ℃ of lower calcining 4h.And then in titanium colloidal sol, add the TiO of 5nm
2Nanoparticle (0.05g/L) obtains stable coating liquid and repeats the dried coating film sintering to obtain the aperture be that 1.5nm, porosity are 45% sodium titanium filter membrane.
Embodiment 6
Be 5nm in the colloidal sol median size, the titanium total content is 0.2molL
-1Acid complex sol in to add with median size after Silane coupling reagent KH-570 (γ-(methacryloxypropyl) propyl trimethoxy silicane) modification be the ZrO of 21nm
2Nanoparticle obtains stable coating liquid.ZrO
2The content of particle is 0.2g/L.With the coating liquid that makes at hyperchannel ZrO
2Ultra-filtration membrane (aperture is 50nm, and 19 path 10 cm are long) is upper films with the dip-coating embrane method, dries in 70 ℃ of baking ovens after drying, and heats up with 1 ℃/min, obtains the titanium zirconium compound film of aperture 8nm at 400 ℃ of lower calcining 4h.And then in titanium colloidal sol, add the ZrO of 5nm
2Nanoparticle (0.02g/L) obtains stable coating liquid and repeats the dried coating film sintering to obtain the aperture be that 4nm, porosity are 45% titanium zirconium compound film.Fig. 3 B is that ceramic membrane is to the retention curve of dextran after embodiment 6 calcinings, and as can be seen from the figure the dextran molecular weight cut-off of prepared film is 17000Da, and corresponding aperture is 6.2nm.
Embodiment 7
Be 3nm in the colloidal sol median size, with ZrOCl
28H
2O is presoma, and zirconium content is 2molL
-1Colloidal sol in to add median size be the TiO of 15nm
2Nanoparticle obtains stable coating liquid, TiO
2The content of particle is 0.5g/L.With the coating liquid that makes at single hose ZrO
2Film on the ultra-filtration membrane (aperture is 50nm, and single tube 10cm is long), in 80 ℃ of baking ovens, dry after drying, heat up with 2 ℃/min, obtain the ceramic membrane of aperture 10nm at 600 ℃ of lower calcining 2h.And then in zirconium colloidal sol, add the TiO of 10nm
2Nanoparticle (0.2g/L) obtains stable coating liquid and repeats the dried coating film sintering to obtain the aperture be that 6.2nm, porosity are 30% zirconium titanium compound film.Fig. 3 C is that ceramic membrane is to the retention curve of dextran after embodiment 7 calcinings, and as can be seen from the figure the dextran molecular weight cut-off of prepared film is 7600Da, and corresponding aperture is 4nm.
Embodiment 8
Be 20nm in the colloidal sol median size, aluminium content is 2molL
-1Colloidal sol in to add median size be the Al of 50nm
2O
3Nanoparticle obtains stable coating liquid.Al
2O
3The content of particle is 0.75g/L.Film with the dip-coating embrane method at porous supporting body (surface tissue is the titanium aluminum alloy film of 200nm) with the coating liquid that makes, dry rear at 100 ℃, dry in the climatic chamber of 60%RH, heat up with 5 ℃/min, getting the aperture at 1100 ℃ of lower calcining 2h is that 10nm, porosity are 30% alumina ceramic membrane.
Embodiment 9
Be 2nm in the colloidal sol median size, silicone content is 1molL
-1Colloidal sol in to add median size be the SiO of 10nm
2Nanoparticle obtains stable coating liquid.SiO
2The content of particle is 0.1g/L.Film with the dip-coating embrane method at porous supporting body (surface tissue is the carbon film of 50nm) with the coating liquid that makes, dry rear at 60 ℃, dry in the climatic chamber of 40%RH, heat up with 0.5 ℃/min, getting the aperture at 200 ℃ of lower calcining 20h is that 1.5nm, porosity are 40% aluminum oxide nanofiltration membrane.
Embodiment 10
Be 10nm in the colloidal sol median size, titanium, zirconium total content are 0.5molL
-1Complex sol in (wherein zirconium accounts for 8%) to add median size be the TiO of 50nm
2Nanoparticle obtains stable coating liquid.TiO
2The content of particle is 1g/L.Film with the dip-coating embrane method at porous supporting body (surface tissue is the stainless steel membrane of 50nm) with the coating liquid that makes, in 30 ℃ of baking ovens, dry after drying, heat up with 0.5 ℃/min, obtain the ceramic membrane of aperture 18nm at 400 ℃ of lower calcining 6h.And then in titanium, zirconium complex sol, add the TiO of 21nm
2Nanoparticle (0.2g/L) obtains stable coating liquid repetition dried coating film sintering and obtains to such an extent that the aperture is that 10nm, porosity are 40% titanium zirconium composite ceramic film.
Claims (5)
1. an improved sol-gel method prepares the method for nanofiltration membrane, it is characterized in that: in colloidal sol, add nanoparticle, utilize dispersed with stirring to make coating liquid, coating liquid is coated on the supporter, with after the wet film oven dry, direct sintering namely obtains nanofiltration membrane again; The nanoparticle that wherein adds is TiO
2, ZrO
2, Al
2O
3Or SiO
2Nano particle.
2. method according to claim 1 is characterized in that described colloidal sol is the colloidal sol that contains one or more elements in titanium, aluminium, zirconium or the element silicon, and wherein the total content of these elements in colloidal sol is 0.1～2molL
-1The median size of colloidal sol is 1～20nm; The Average Particle Diameters of the nanoparticle that adds is 3～50nm, and greater than the particle diameter of colloidal sol; The concentration of nanoparticle in coating liquid of adding is 0.01～1g/L.
3. method according to claim 1 is characterized in that described supporter is to have ceramic membrane, carbon film, stainless steel membrane or the titanium aluminum alloy film that mean pore size is 50～200nm surface tissue; Supporter is chip, single tube or the multi-channel membrane of vesicular structure.
4. method according to claim 1 is characterized in that the temperature of wet film oven dry is 20～120 ℃; Sintering temperature is 200～1200 ℃, and heat-up rate is 0.5～5 ℃/min, and roasting time is at 1～24h.
5. method according to claim 1 is characterized in that the mode of filming is that dip coating is filmed or rotational method is filmed.
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103551050A (en) * | 2013-10-30 | 2014-02-05 | 华南理工大学 | Inorganic composite ultra-filtration membrane and preparation method thereof |
| CN103739102A (en) * | 2013-12-25 | 2014-04-23 | 江苏久吾高科技股份有限公司 | Ceramic nanofiltration membrane water purifier capable of realizing high-temperature sterilization |
| CN104844244A (en) * | 2015-04-16 | 2015-08-19 | 柳州豪祥特科技有限公司 | Process for preparing tubular ceramic film by rotary method |
| CN105126637A (en) * | 2015-07-28 | 2015-12-09 | 江苏久吾高科技股份有限公司 | Gas-solid separation ceramic film and preparation method thereof |
| CN105693286A (en) * | 2016-02-02 | 2016-06-22 | 武汉梦华洁膜科技有限责任公司 | Inorganic nanofiltration membrane and preparation method thereof |
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| CN112999890A (en) * | 2021-03-03 | 2021-06-22 | 大连理工大学 | Organic-inorganic hybrid SiO of flat plate2Composite membrane and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009095828A (en) * | 2007-09-26 | 2009-05-07 | Toray Ind Inc | Separative membrane supporting body, separative membrane and fluid separation element using separative membrane supporting body |
| CN101612097A (en) * | 2009-07-16 | 2009-12-30 | 东南大学 | Dental machinable diatomite full ceramic restoration material and preparation method thereof |
-
2013
- 2013-07-18 CN CN201310303099.8A patent/CN103360080B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009095828A (en) * | 2007-09-26 | 2009-05-07 | Toray Ind Inc | Separative membrane supporting body, separative membrane and fluid separation element using separative membrane supporting body |
| CN101612097A (en) * | 2009-07-16 | 2009-12-30 | 东南大学 | Dental machinable diatomite full ceramic restoration material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 漆红等: "TiO2纳滤膜的制备及其离子截留性能", 《无机材料学报》 * |
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