CN102151501B - Preparation method of organic-inorganic nano composite separation membrane and uses - Google Patents
Preparation method of organic-inorganic nano composite separation membrane and uses Download PDFInfo
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- CN102151501B CN102151501B CN2011100437965A CN201110043796A CN102151501B CN 102151501 B CN102151501 B CN 102151501B CN 2011100437965 A CN2011100437965 A CN 2011100437965A CN 201110043796 A CN201110043796 A CN 201110043796A CN 102151501 B CN102151501 B CN 102151501B
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Abstract
The invention discloses a preparation method of an organic-inorganic nano composite separation membrane, which comprises the following steps of: 1) stirring and mixing nitrate aqueous solution and alkaline solution having the same volume, then placing the mixture for 3 hours to 3 days to generate crystalline inorganic nano-wire flocculent precipitates, ultrasonically treating and filtering, filtering 4 to 5ml of inorganic nano-wire dispersion on a porous alumina substrate with the pore diameter of 200 nanometers to form a mesoporous membrane; 2) mixing 0.01 to 1mg/ml of macromolecular toluene solution with curing agent based on the proportion of 10:1, then diluting the mixture 10 times, 20 times or 40 times; pouring the diluted solution to a filter with the mesoporous membrane therein, sealing the filter, vacuum pumping to 40 to 60kPa to form a layer of homogeneous polymeric membrane on the surface of the nano-wire, and then curing and crosslinking the resultant membrane for 12 to 24 hours in a drying box from 60 to 80 DEG C. The simple method can obtain hydrophilic/hydrophobic composite separation membranes having good adhesion without surface modification. The separation membrane is used for the separation of molecules, proteins, nano particles and the like in aqueous solution.
Description
Technical field
The present invention relates to the preparation method of diffusion barrier, relate in particular to a kind of preparation method of organic-inorganic nano composite separating film.
Background technology
Composite organic-inorganic material in conjunction with the characteristic of separately excellence, has obtained to use very widely in parting material.Usually need special surperficial compatibility functionalization could obtain good composite.And aspect the organic and inorganic composite membrane, just more require adhesive force well dispersed and each other.Usually the composite membrane thickness that obtains all is that this greatly reduces membrane separation efficiency at micron order.And traditional thick film is normally in surface of solids casting, and solvent flashing makes, and thickness is tens to microns up to a hundred.Require membrane separation efficiency high more good more in the industry, the thickness of this low film of will begging to surrender.But reduce mechanical strength and separating effect that thickness will lose film.The present invention utilizes the poplar Laplace's equation to prepare the organic-inorganic nano composite separating film and gets method, and effective film is less than 100 nanometers.Especially can in hydrophilic porous substrate, prepare hydrophobic nano-high molecule film.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of organic-inorganic nano composite separating film is provided.
The preparation method's of organic-inorganic nano composite separating film step is following:
1) under the normal temperature; 0.4～4mM nitrate aqueous solution of equal volume mixes under magnetic agitation with 0.03～1.4 mM aqueous slkali, places then 3 hours～3 days, directly generates the inorganic nanowires flocculent deposit of crystalline state; Ultrasonic then 5～10 minutes; Filter, it is in the Woelm Alumina substrate of 200 nanometers that 4～5 ml inorganic nanowires dispersion liquids are filtered in the aperture, forms the mesoporous film of 200～220 nanometer thickness;
2) be the mixed of 10:1 with high molecular toluene solution of 0.1～10 mg/ml and curing agent according to mass ratio, dilute gross mass again 10 times, 20 times or 40 times; Dilute solution is poured in the filter that above-mentioned nano wire mesoporous film is housed, and sealing vacuumizes through the bottom; Negative pressure is 40～60 kPa, from the lower surface solvent flashing of liquid, forms the layer of even polymeric membrane on the surface of hydrophilic nano wire; The film that obtains solidifies glue again and joins 12～24 hours in the drying box of 60～80 degree; Obtain the organic-inorganic nano composite separating film, the organic-inorganic nano composite separating film is non-porous film or perforated film, and the aperture of perforated film is 0.000001～5 nm.
Described nitrate is Mn nitrate, copper nitrate or cadmium nitrate.Described aqueous slkali is monoethanolamine, NaOH or potassium hydroxide.Described macromolecule is dimethyl silicone polymer, Merlon, polyethylene, polyvinyl chloride, polyacrylonitrile, polyamide or epoxy resin.
The organic-inorganic nano composite separating film is used for concentrating alcohol, divided gas flow, the molecule in the separation solution, protein or nano particle.
The beneficial effect that the present invention compared with prior art has:
1) utilizes the principle of Young-Laplace equation, directly hydrophobic macromolecule is formed the effective separating layer of one deck macromolecule on hydrophilic nano wire mesoporous film surface;
2) this method need not finishing and just can prepare hydrophilic and hydrophobic composite diffusion barrier;
3) can comparatively fast prepare very thin fractionated polymer absciss layer from the bottom interface vacuum volatilization;
4) but the effective aperture of simple modulation diffusion barrier.
Description of drawings
Fig. 1 is the surperficial SEM photo of the composite compact film that makes of 10 times of dilutions;
Fig. 2 is the section SEM photo of the composite compact film that makes of 10 times of dilutions;
Fig. 3 is the surperficial SEM photo of the composite compact film that makes of 20 times of dilutions;
Fig. 4 is the section SEM photo of the composite compact film that makes of 20 times of dilutions;
Fig. 5 is the surperficial SEM photo of the composite compact film that makes of 40 times of dilutions;
Fig. 6 is the section SEM photo of the composite compact film that makes of 40 times of dilutions.
The specific embodiment
Further specify the present invention below in conjunction with instance.
Embodiment 1
Under the normal temperature magnetic agitation, with 10 ml, 0.8 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 0.4 mM Mn nitrate (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow mixing speed, and reaction vessel is sealed.After one day; Can obtain the brown flocculent deposit, the β that more than makes-MnOOH nano wire precipitates through ultrasonic dispersion 5 minutes, gets this dispersion liquid of 4 ml; Through the method for filtering; Go up the thick β-mesoporous filtering layer of MnOOH nano wire of formation one deck 220 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Then equal-volume silicon rubber 1 mg/ ml toluene solution and the solution of curing agent 0.1mg/ ml toluene are mixed, leave in the container of sealing, the maintenance weight ratio is 10:1.This mixture is used as one (PDMS) mother liquor.2 ml; The mother liquor of 10 times of dilutions is poured a surface that the thick β of 220 nm-MnOOH nano wire film is housed into, seals filter tunnel then, keeps the 60kPa negative pressure; Through the method for vacuum solution bottom interface volatilization, form one deck PDMS layer on porous nano line film surface.Because the Young-Laplace principle, under this negative pressure, PDMS solution can not be deep into nano wire inside, just in its superficial layer film forming.After 24 hours curing of 70 degree, obtain fine and close PDMS/ β-MnOOH nano wire composite membrane.This layer is fine and close that film can be concentrated to 34% through the infiltration evaporating method with 10% alcohol water blend, and flow velocity is 0.7kg/m
2Hbar.Under 4 atmospheric pressure, this fine and close film is 26.5 to the separation factor of carbon dioxide and nitrogen, and the rate of departure of carbon dioxide is 4676 L/ m
2
Embodiment 2
Under the normal temperature magnetic agitation, with 10 ml, 0.8 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 0.4 mM Mn nitrate (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow mixing speed, and reaction vessel is sealed.After one day; Can obtain the brown flocculent deposit, the β that more than makes-MnOOH nano wire precipitates through ultrasonic dispersion 10 minutes, gets this dispersion liquid of 4 ml; Through the method for filtering; Go up the thick β-mesoporous filtering layer of MnOOH nano wire of formation one deck 220 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Then equal-volume silicon rubber 1 mg/ ml toluene solution and the solution of curing agent 0.1mg/ ml toluene are mixed, leave in the container of sealing, the maintenance weight ratio is 10:1.This mixture is used as one (PDMS) mother liquor.2 ml; The mother liquor of 20 times of dilutions is poured a surface that the thick β of 220 nm-MnOOH nano wire film is housed into, seals filter tunnel then, keeps the 60kPa negative pressure; Through the method for vacuum solution bottom interface volatilization, form one deck PDMS layer on porous nano line film surface.Because the Young-Laplace principle, under this negative pressure, PDMS solution can not be deep into nano wire inside, just in its superficial layer film forming.After 24 hours curing of 60 degree, the film that obtains has the hole about 2 nanometers, can separate the big cromoci of 2.5 nanometers, and rejection is 94%, is 85% to the rejection of the gold nano grain of 2 nanometers, and flow velocity is 1150 L/m
2H bar.
Embodiment 3
Under the normal temperature magnetic agitation, with 10 ml, 0.8 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 0.4 mM Mn nitrate (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow mixing speed, and reaction vessel is sealed.After two days; Can obtain the brown flocculent deposit, the β that more than makes-MnOOH nano wire precipitates through ultrasonic dispersion 5 minutes, gets this dispersion liquid of 4 ml; Through the method for filtering; Go up the thick β-mesoporous filtering layer of MnOOH nano wire of formation one deck 220 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Then equal-volume silicon rubber 1 mg/ ml toluene solution and the solution of curing agent 0.1mg/ ml toluene are mixed, leave in the container of sealing, the maintenance weight ratio is 10:1.This mixture is used as one (PDMS) mother liquor.2 ml; The mother liquor of 40 times of dilutions is poured a surface that the thick β of 220 nm-MnOOH nano wire film is housed into, seals filter tunnel then, keeps the 60kPa negative pressure; Through the method for vacuum solution bottom interface volatilization, form one deck PDMS layer on porous nano line film surface.Because the Young-Laplace principle, under this negative pressure, PDMS solution can not be deep into nano wire inside, just in its superficial layer film forming.After 12 hours curing of 80 degree, the film that obtains has the hole about 5 nanometers, can separate the nanogold particle of 5 nm, and rejection is 93%, and flow velocity is 2200 L/m
2H bar.
Embodiment 4
With 10 ml, 1.4 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 4 mM copper nitrates (Cu (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing three days, obtain Kocide SD nano wire solution.The filtration of 5 ml copper nano-wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the Merlon toluene solution of 2 ml 0.01mg/ ml into a surface that the thick Kocide SD nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 60kPa negative pressure.Solution forms one deck PC thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, PC solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Embodiment 5
With 10 ml, 0.03 mM potassium hydroxide aqueous solution adds 4 mM cadmium nitrate Cd (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing one day, obtain cadmium hydroxide nano wire solution.The filtration of 5 ml cadmium nano wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the polyethylene toluene solution of 2 ml 0.01mg/ ml into a surface that the thick cadmium hydroxide nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 40kPa negative pressure.Solution forms the layer of polyethylene thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, polyethylene solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Embodiment 6
With 10 ml, 0.03 mM sodium hydrate aqueous solution adds 4 mM cadmium nitrate Cd (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing 3 hours, obtain cadmium hydroxide nano wire solution.The filtration of 4 ml cadmium nano wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the polyvinyl chloride toluene solution of 2 ml 0.01mg/ ml into a surface that the thick cadmium hydroxide nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 40kPa negative pressure.Solution forms one deck polyvinyl chloride thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, polyvinyl chloride solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Embodiment 7
With 10 ml, 1.4 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 4 mM copper nitrates (Cu (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing three days, obtain Kocide SD nano wire solution.The filtration of 5 ml copper nano-wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the polyacrylonitrile toluene solution of 2 ml 0.01mg/ ml into a surface that the thick Kocide SD nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 60kPa negative pressure.Solution forms one deck polyacrylonitrile thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, polyacrylonitrile solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Embodiment 8
With 10 ml, 1.4 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 4 mM copper nitrates (Cu (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing three days, obtain Kocide SD nano wire solution.The filtration of 5 ml copper nano-wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the polyamide toluene solution of 2 ml 0.01mg/ ml into a surface that the thick Kocide SD nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 60kPa negative pressure.Solution forms one deck polyamide thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, polyamide solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Embodiment 9
With 10 ml, 1.4 mM monoethanolamine (NH
2CH
2CH
2OH) aqueous solution adds 4 mM copper nitrates (Cu (NO) fast
3) in the aqueous solution, stir after 1 minute, with reaction vessel sealing three days, obtain Kocide SD nano wire solution.The filtration of 5 ml copper nano-wire solution is gone up the thick mesoporous filtering layer of nano wire of formation one deck 200 nm at multiaperture pellumina (2.5 cm, aperture 200 nm, voidage 25-50%).Pour the epoxy resin toluene solution of 2 ml 0.01mg/ ml into a surface that the thick Kocide SD nano wire film of 200 nm is housed then, sealing is filtered, and keeps the 60kPa negative pressure.Solution forms one deck epoxy resin thin layer on porous nano line film surface after the volatilization of vacuum bottom interface.Because the Young-Laplace principle, under this negative pressure, epoxy resin solution can not be deep into nano wire inside, just in its superficial layer film forming.This film can be used for divided gas flow.
Claims (2)
1. the preparation method of an organic-inorganic nano composite separating film is characterized in that its step is following:
1) under the normal temperature; 0.4～4mM nitrate aqueous solution of equal volume mixes under magnetic agitation with 0.03～1.4 mM aqueous slkali, places then 3 hours～3 days, directly generates the inorganic nanowires flocculent deposit of crystalline state; Ultrasonic then 5～10 minutes; Filter, it is in the Woelm Alumina substrate of 200 nanometers that 4～5 ml inorganic nanowires dispersion liquids are filtered in the aperture, forms the mesoporous film of 200～220 nanometer thickness;
2) be the mixed of 10:1 with high molecular toluene solution of 0.01～1 mg/ml and curing agent according to mass ratio, dilute gross mass again 10 times, 20 times or 40 times; Dilute solution is poured in the filter that above-mentioned nano wire mesoporous film is housed; Sealing vacuumizes through the bottom, and negative pressure is 40～60 kPa; Lower surface solvent flashing from liquid; Surface at hydrophilic nano wire mesoporous film forms the layer of even polymeric membrane, and the film of acquisition solidifies glue again and joins 12～24 hours in the drying box of 60～80 degree, obtain the organic-inorganic nano composite separating film; The organic-inorganic nano composite separating film is non-porous film or perforated film, and the aperture of perforated film is 0.000001～5 nm;
Described nitrate is Mn nitrate, copper nitrate or cadmium nitrate; Described aqueous slkali is monoethanolamine, NaOH or potassium hydroxide; Described macromolecule is dimethyl silicone polymer, Merlon, polyethylene, polyvinyl chloride, polyacrylonitrile, polyamide or epoxy resin.
2. the purposes of the organic-inorganic nano composite separating film of method preparation according to claim 1 is characterized in that: be used for concentrating alcohol, divided gas flow, the molecule in the separation solution, protein or nano particle.
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| CN102583500B (en) * | 2012-01-12 | 2014-04-09 | 浙江大学 | Method for synthesizing stable CuO nanosheet sol with high specific surface area by means of normal-temperature aqueous solution |
| CN103456832B (en) * | 2012-05-28 | 2016-08-31 | 河南师范大学 | A kind of method of dispersed silicon nano-wire array matte |
| CN102814124B (en) * | 2012-08-13 | 2014-08-13 | 浙江大学 | Method for preparing graphene oxide base porous film by using metal hydroxide nanowires and graphene oxide, and application of graphene oxide base porous film |
| CN103059066B (en) * | 2012-12-06 | 2015-07-29 | 浙江大学 | Hydroxide nano line and organic ligand prepare the method for metal organic framework thin film at normal temperatures fast |
| CN103223299B (en) * | 2013-05-17 | 2015-03-11 | 厦门大学 | Macromolecular negative-charge ultrafiltration membrane and preparation method thereof |
| CN105413479A (en) * | 2015-12-11 | 2016-03-23 | 熊菊莲 | Preparation method of nano separation membrane |
| CN109304099A (en) * | 2018-11-02 | 2019-02-05 | 南京工业大学 | A kind of polymer-metal hydroxide nano line laminated film and preparation method thereof |
| CN109289549A (en) * | 2018-11-07 | 2019-02-01 | 温州莲华环保科技有限公司 | A kind of high temperature resistant organic solvent-resistant high-performance seperation film and preparation method thereof |
| CN111871207B (en) * | 2020-07-17 | 2022-01-25 | 中国海洋大学 | Nanowire reverse osmosis composite membrane and preparation method thereof |
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