CN103657433A - Forward-osmosis organic-inorganic composite membrane and preparation method thereof - Google Patents
Forward-osmosis organic-inorganic composite membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000009292 forward osmosis Methods 0.000 title abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000005266 casting Methods 0.000 claims description 28
- 239000012466 permeate Substances 0.000 claims description 19
- 229920002301 Cellulose acetate Polymers 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- -1 poly (aryl ether sulfone ketone Chemical class 0.000 claims description 5
- 229920002492 poly(sulfones) Polymers 0.000 claims description 5
- 238000001764 infiltration Methods 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229920005601 base polymer Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229920002496 poly(ether sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 230000000813 microbial Effects 0.000 abstract description 24
- 230000004907 flux Effects 0.000 abstract description 22
- 230000000844 anti-bacterial Effects 0.000 abstract description 2
- 230000002035 prolonged Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 19
- 230000000845 anti-microbial Effects 0.000 description 11
- 238000011109 contamination Methods 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 9
- 244000005700 microbiome Species 0.000 description 9
- 230000003115 biocidal Effects 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 230000000149 penetrating Effects 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940018564 M-PHENYLENEDIAMINE Drugs 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N Triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920003288 polysulfone Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-M 2-methylpropanimidate Chemical compound CC(C)C([O-])=N WFKAJVHLWXSISD-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N Trimethylsilyl chloride Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000003409 anti-rejection Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-M triacetate(1-) Chemical compound CC(=O)CC(=O)CC([O-])=O ILJSQTXMGCGYMG-UHFFFAOYSA-M 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention discloses a forward-osmosis organic-inorganic composite membrane. The forward-osmosis organic-inorganic composite membrane comprises at least one bottom membrane layer, wherein the at least one bottom membrane layer contains polymers and nano particles dispersed in the at least one bottom membrane layer; and the water flux of the forward-osmosis organic-inorganic composite membrane is larger than 12L*m<-2>*h<-1>. The invention further discloses a preparation method of the forward-osmosis organic-inorganic composite membrane. The forward-osmosis organic-inorganic composite membrane has the larger contact area with water and has the better hydrophilicity, so that the water flux of the forward-osmosis organic-inorganic composite membrane is increased to a greater degree. Besides, the antibacterial property of the forward-osmosis membrane can be improved remarkably, so that the defect that traditional forward-osmosis organic-inorganic composite membranes are prone to microbial pollution in water treatment environments is overcome, the service life of the forward-osmosis membrane is prolonged, and the membrane is a new forward-osmosis organic-inorganic composite membrane with the wide application potential.
Description
Technical field
The present invention relates to membrane separation technique field, be specially and just permeate organic and inorganic composite membrane and preparation method thereof.
Background technology
Film separation process is a kind of energy-efficient water treatment procedure, and membrane for water treatment is the core of embrane method water treatment procedure, and the quality of its performance is determining that can embrane method water treatment procedure large-scale application.Forward osmosis membrane separation process is a kind of new membrane isolation technics growing up in the last few years, compares with traditional pressure-driven type membrane process, and positive process of osmosis does not need impressed pressure, energy consumption is less, process is lower to the pollution level of film, and the rate of recovery of process is higher, and environmental effect is friendly.Forward osmosis membrane is the core of positive process of osmosis, and the quality of its performance is determining that can positive process of osmosis obtain large-scale application.In diffusion barrier market, reverse osmosis membrane accounts for 85% of film market at present, the preparation process development of reverse osmosis membrane is comparatively ripe, commodity reverse osmosis membrane can reach very high flux, and it is less to the research of the forward osmosis membrane for positive process of osmosis at present, in Patents WO2006110497A2, the material selection cellulose acetate class of forward osmosis membrane, make to be subject in its application process the restriction of Treatment Solution pH condition, and its membrane flux is lower.
The principal element that restricts membrane flux in positive process of osmosis is the interior concentration polarization phenomenon occurring in process in porous support layer, therefore its existence makes forward osmosis membrane flux far below theoretical membrane flux, will improve the interior concentration polarization phenomenon in the flux reduction process as far as possible of forward osmosis membrane.At present a lot of research institutions just carry out research and probe in the preparation of involutory forward osmosis membrane in the world, but generally, are just permeating that to have the flux of film to improve be not very large.Therefore develop high flux, high performance forward osmosis membrane aligns process of osmosis and has great importance.
Because membrane for water treatment is applied in water body environment, microorganism in water body of long duration is easily attached to the surface of film, fenestra is damaged, thereby changed the original performance of film.Therefore, preparation has the membrane for water treatment of high anti-microbial property the application in water treatment procedure also has great importance for film.That especially for new development, gets up all has the forward osmosis membrane of extensive use potentiality at multiple fields, it is than traditional pressure-driven type film, in application process, the both sides of film all contact with solution phase, thereby increased the tendency that film is subject to microbial contamination, so antibacterial film is also very important for positive process of osmosis.
Summary of the invention
Technical problem solved by the invention is to provide a kind of organic and inorganic composite membrane and preparation method thereof that just permeating, this is just permeating organic and inorganic composite membrane not only can significantly improve the permeation flux of film, retained high rejection, and anti-microbial property also can significantly be increased, in order to solve the problem proposing in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
Just permeating organic and inorganic composite membrane, comprising at least one bottom membrane, described bottom membrane comprises polymer and is scattered in the nano particle in described bottom membrane; The described water flux that just permeates organic and inorganic composite membrane is greater than 12Lm
-2h
-1.
In described bottom membrane, the 0.05-5wt% of the gross weight that the content of nano particle is bottom membrane, preferred version is 0.1-2wt%.
Described nano particle is TiO
2one or more in nano particle, metal nanoparticle, the zeolite molecular sieve that is loaded with metal ion, NaA type zeolite molecular sieve, the particle diameter of nano particle is 0.1-4 μ m, preferably, is 0.5-2 μ m.
Polymer in described bottom membrane comprises (a) group polymer or the polymer of (b) organizing, wherein (a) group polymer is one or more in polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile, and (b) polymer of group is cellulose acetate base polymer.
The mass ratio of described polymer and nano particle is 10-22: 0.04-20, and preferred version is 10-18: 0.1-2.
The described organic and inorganic composite membrane that just permeates also comprises for the supporting layer of support base rete and/or is positioned at the active layer on bottom membrane.
Described active layer is compound by interface polymerization reaction and bottom membrane.
Described supporting layer is nonwoven, polyester screen, brown paper or its combination.
Described metal nanoparticle is Nano silver grain, copper nano-particle, zinc nano particle, Fe nanometer particles or its combination.
Described nano particle is porous material.
The preparation method who is just permeating organic and inorganic composite membrane, comprises the following steps:
(1) provide a casting solution, described casting solution contains polymer, nano particle and solvent;
(2) described casting solution is coated on base material, then standing in air, until solvent evaporates wherein forms dense layer surface, the film of the dense layer surface of formation is placed on to gel in coagulation bath, after inversion of phases, obtain needed bottom membrane, by the bottom membrane washed with de-ionized water obtaining, thereby remove remaining organic solvent;
(3) gained bottom membrane is both for just permeating organic and inorganic composite membrane; Or when described base material is used as supporting layer, obtain the just infiltration organic and inorganic composite membrane containing supporting layer and polymer film.
In described casting solution, the content of polymer is the 10-22wt% of casting solution gross weight, and in described casting solution, the content of nano particle is the 0.04-20wt% of casting solution gross weight.
The thickness of described bottom membrane is 80-200 μ m, is preferably 80-180 μ m, more preferably 100-150 μ m.
Described in step (1), casting solution is to prepare by following placement:
(1) polymer is dissolved in to solvent (preferably dissolve adding under thermal agitation, stir under 60 ℃ of conditions 6-9 hour), forms polymer solution;
(2) nano particle is added in described polymer solution, form casting solution.
The coagulation bath using in described phase inversion comprises the mixed solution of deionized water or deionized water and solvent for use.
Described solvent is dioxane, 1-METHYLPYRROLIDONE, DMA, triethyl phosphate or its combination.
The method of just permeating, comprises the following steps: right to use requires the just infiltration organic and inorganic composite membrane described in 1 just to permeate.
The present invention compares with conventional art, has the following advantages:
Provided by the inventionly just permeate organic and inorganic composite membrane and water has larger contact area, and thering is good hydrophily, improving largely the water flux that is just permeating organic and inorganic composite membrane.In addition, the anti-microbial property of forward osmosis membrane obviously improves, and has solved tradition and has just permeated organic and inorganic composite membrane and in water treatment environment, be subject to the defect of microbial contamination, having extended the service life of forward osmosis membrane, is a kind of novel organic and inorganic composite membrane that just permeating with extensive use potentiality.
The specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Just permeating organic and inorganic composite membrane and preparation method thereof:
Adopt cellulose acetate as polymer, 12g cellulose acetate and 0.4gAg nano particle (particle diameter is 1.5 μ m) are added to 87.6g1, in 4-dioxane solvent, stirring and dissolving forms the casting solution of the Ag nano particle that content is 0.4wt%, gel-forming film in coagulation bath, by prepared film washed with de-ionized water, removes remaining organic solvent, make and just permeate organic and inorganic composite membrane, be kept in deionized water standby.
After tested, the flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 20Lm
-2h
-1, rejection is more than 99%.
The prepared organic and inorganic composite membrane that just permeates carries out microbial contamination experiment with the film of plus nano particle not under identical condition.On film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, discovery has added film surface attachment that the film of nano particle do not add without microbial adhesion a large amount of microorganism, has shown to add the film of nano particle to have obvious antibiotic property.Antibiotic rate is greater than 90%.
Embodiment 2
Just permeating organic and inorganic composite membrane and preparation method thereof:
Take 16g polysulfone polymer, be dissolved in the mixed solvent that 84g is comprised of DMA and PEG400 (the two ratio is 76: 8), be made into polymer concentration and be 18% polysulfones solution.In the polysulfones solution preparing, add 2g to there is the silver-colored NaA type zeolite molecular sieve nano particle (particle diameter is 1.5 μ m) that carries of hexahedral shape, at ultrasonic middle dispersion 30min, be made into the casting solution that carries silver-colored NaA type zeolite molecular sieve nano particle that contains 2wt%, casting solution is coated on low-density nonwoven fabric supporting layer, adopt certain thickness scraper to carry out knifing, put into coagulation bath gel film forming, adopt m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride to carry out interface polymerization reaction (reacting 3min at 110 ℃) on the film forming, thereby make, just permeate organic and inorganic composite membrane.
After tested, the water flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 18Lm
-2h
-1, rejection is more than 99%.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find that its surface is without microbial adhesion, show that this film has obvious anti-microbial property.Antibiotic rate is greater than 90%.
Embodiment 3
Just permeating organic and inorganic composite membrane and preparation method thereof:
Take 18g polysulfone polymer, the TiO2 nano particle that 0.6g is spherical (particle diameter is 2 μ m), be dissolved in 82g by N, in the mixed solvent that N-dimethylacetylamide and PEG400 form (the two ratio is 72: 10), being made into polysulfones concentration is the casting solution that 18wt%, TiO2 nano particle concentration are 0.6wt%.Casting solution is coated on low-density nonwoven fabric supporting layer, adopts certain thickness scraper to carry out knifing, put into coagulation bath gel film forming, obtain and just permeate organic and inorganic composite membrane, be kept in deionized water standby.
After tested, the water flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 22Lm
-2h
-1, rejection is more than 99%.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find that its surface is without microbial adhesion, show that this film has obvious anti-microbial property.Antibiotic rate is greater than 90%.
Embodiment 4
Just permeating organic and inorganic composite membrane and preparation method thereof:
Take 8g Triafol T polymer, be dissolved in the mixed solvent that 84g is comprised of triethyl phosphate and PEG400 (the two ratio is 72: 8), being made into concentration is the triacetate fiber cellulose solution of 8wt%.In the solution preparing, add 1g to have the zeolite molecular sieve nano particle (particle diameter is 1.5 μ m) that carries iron ion of tetrahedron shape, at ultrasonic middle dispersion 30min, obtaining nano particle concentration is 1% casting solution.Casting solution is coated on low-density nonwoven fabric supporting layer, adopts certain thickness scraper to carry out knifing, put into coagulation bath gel film forming, obtain and just permeate organic and inorganic composite membrane, be kept in deionized water standby.
After tested, the water flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 25Lm
-2h
-1, rejection is more than 99%.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find that its surface is without microbial adhesion, show that this film has obvious anti-microbial property.Antibiotic rate is greater than 90%.
Embodiment 5
Just permeating organic and inorganic composite membrane and preparation method thereof:
Adopt cellulose acetate as polymer, 10g cellulose acetate is added in 90g dioxane, add thermal agitation 6-9 hour at 60 ℃ after, dissolve, the cellulose acetate solution that forms 10wt% adds 0.1g Ag nano particle (particle diameter is 1.5 μ m) in this solution, is made into the casting solution of the Ag nano particle that contains 0.1wt% after ultrasonic dispersion, through inversion of phases film forming, by prepared film washed with de-ionized water, remove remaining organic solvent, thereby make forward osmosis membrane.
The water flux of the forward osmosis membrane that after tested, prepared by the present embodiment is 12Lm
-2h
-1.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find its surperficial less microbial adhesion, show that this film has certain anti-microbial property.Antibiotic rate is greater than 90%.
Comparative example 1
Tradition is just being permeated the preparation of organic and inorganic composite membrane:
Adopt cellulose acetate as polymer, 10g cellulose acetate is added in 90g dioxane, add thermal agitation 6-9 hour at 60 ℃ after, dissolve, form the cellulose acetate casting solution of 10wt%, through inversion of phases film forming, by prepared film washed with de-ionized water, remove remaining organic solvent, thereby make, just permeate organic and inorganic composite membrane.
After tested, the water flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 8Lm
-2h
-1.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find that its surperficial Escherichia coli number increases, and shows the not particle modified easy microbial contamination of film of plus nano.
Comparative example 2
Tradition is just being permeated the preparation of organic and inorganic composite membrane:
Adopt cellulose acetate as polymer, 10g cellulose acetate is added in 90g dioxane, add thermal agitation 6-9 hour at 60 ℃ after, dissolve, form the cellulose acetate solution of 10wt%, in this solution, add 0.01g Ag nano particle (particle diameter is 1.5 μ m), after ultrasonic dispersion, be made into the casting solution of the Ag nano particle that contains 0.01wt%, through inversion of phases film forming, by prepared film washed with de-ionized water, remove remaining organic solvent, thereby make, just permeate organic and inorganic composite membrane.
After tested, the water flux that just permeates organic and inorganic composite membrane that prepared by the present embodiment is 7.5Lm
-2h
-1.
Prepared film is carried out to microbial contamination experiment, on film surface, add e. coli microorganisms, after 24h, adopt the microbial adhesion situation on microscopic examination film surface, find that its surperficial Escherichia coli number has certain increase.
The various performance parameters of just permeating organic and inorganic composite membrane of embodiment 1-5 and comparative example 1-2 is in Table 1.
Table 1
As shown in table 1, the anti-microbial property that is just permeating organic and inorganic composite membrane of the present invention obviously improves, and antibiotic rate is all greater than 90%, and the penetrating amount of just permeating composite membrane simultaneously is also significantly improved, up to 25Lm
-2h
-1, and just permeating the high rejection that composite membrane has 99-99.99%, and do not add the penetrating amount of just permeating organic and inorganic composite membrane of nano particle, be only 7-8Lm
-2h
-1, anti-microbial property is poor, and rejection does not reach requirement yet.When nanoparticle content is too low, prepared penetrating amount of just permeating organic and inorganic composite membrane is only also 7-8Lm
-2h
-1, anti-microbial property and rejection effect can not get improving, and show the very few effect that increases water flux but also the anti-microbial property that can not effectively improve film of not only not reached of nanoparticle content.As can be seen here, the organic and inorganic composite membrane that just permeating of the present invention has significantly improved water flux and has had high rejection, having solved traditional forward osmosis membrane simultaneously and in water treatment environment, be subject to the defect of microbial contamination, is a kind of novel forward osmosis membrane with extensive use potentiality.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this description is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of description is only for clarity sake, those skilled in the art should make description as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. just permeating organic and inorganic composite membrane, it is characterized in that, comprising at least one bottom membrane, described bottom membrane comprises polymer and is scattered in the nano particle in described bottom membrane.
2. the organic and inorganic composite membrane that just permeating according to claim 1, is characterized in that, in described bottom membrane, and the 0.05-5wt% of the gross weight that the content of nano particle is bottom membrane.
3. the organic and inorganic composite membrane that just permeating according to claim 1, is characterized in that, described nano particle is TiO
2one or more in nano particle, metal nanoparticle, the zeolite molecular sieve that is loaded with metal ion, NaA type zeolite molecular sieve, the particle diameter of nano particle is 0.1-4 μ m.
4. the organic and inorganic composite membrane that just permeating according to claim 1, it is characterized in that, polymer in described bottom membrane comprises (a) group polymer or the polymer of (b) organizing, wherein (a) group polymer is one or more in polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile, and (b) polymer of group is cellulose acetate base polymer.
5. the organic and inorganic composite membrane that just permeating according to claim 1, is characterized in that, the mass ratio of described polymer and nano particle is 10-22: 0.04-20.
6. the organic and inorganic composite membrane that just permeating according to claim 1, is characterized in that, also comprises for the supporting layer of support base rete and/or is positioned at the active layer on bottom membrane.
7. just permeating the preparation method of organic and inorganic composite membrane, it is characterized in that, comprising the following steps:
(1) provide a casting solution, described casting solution contains polymer, nano particle and solvent;
(2) described casting solution is coated on base material, then standing in air, until solvent evaporates wherein forms dense layer surface, the film of the dense layer surface of formation is placed on to gel in coagulation bath, after inversion of phases, obtain needed bottom membrane, by the bottom membrane washed with de-ionized water obtaining, thereby remove remaining organic solvent;
(3) gained bottom membrane is both for just permeating organic and inorganic composite membrane; Or when described base material is used as supporting layer, obtain the just infiltration organic and inorganic composite membrane containing supporting layer and polymer film.
8. the described preparation method who is just permeating organic and inorganic composite membrane according to claim 7, it is characterized in that, in casting solution, the content of polymer is the 10-22wt% of casting solution gross weight, and in described casting solution, the content of nano particle is the 0.04-20wt% of casting solution gross weight.
9. the described preparation method who is just permeating organic and inorganic composite membrane according to claim 7, is characterized in that, described in step (1), casting solution is to prepare by following placement:
(1) polymer is dissolved in to solvent, forms polymer solution;
(2) nano particle is added in described polymer solution, form casting solution.
10. the method for just permeating, is characterized in that, comprises the following steps: right to use requires the just infiltration organic and inorganic composite membrane described in 1 just to permeate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785301A (en) * | 2014-02-13 | 2014-05-14 | 中国科学院上海高等研究院 | Cellulose acetate forward osmosis film material and preparation method thereof |
| CN104437139A (en) * | 2014-12-12 | 2015-03-25 | 南京理工大学 | Inorganic-organic hybrid antibacterial ultrafiltration membrane and preparation method thereof |
| CN105645679A (en) * | 2016-01-06 | 2016-06-08 | 南京大学 | Oily wastewater recycling and wastewater treatment system and treatment method thereof |
| CN108314891A (en) * | 2018-03-21 | 2018-07-24 | 安徽江淮汽车集团股份有限公司 | A kind of PEO composite material and preparation methods |
| CN109762462A (en) * | 2019-01-30 | 2019-05-17 | 中国科学院长春应用化学研究所 | A kind of anticorrosive paint with barrier property |
| CN111068524A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Seawater desalination micro-nano membrane material, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785301A (en) * | 2014-02-13 | 2014-05-14 | 中国科学院上海高等研究院 | Cellulose acetate forward osmosis film material and preparation method thereof |
| CN103785301B (en) * | 2014-02-13 | 2016-08-17 | 中国科学院上海高等研究院 | A kind of Cellulose acetate forward osmotic membrane material and preparation method thereof |
| CN104437139A (en) * | 2014-12-12 | 2015-03-25 | 南京理工大学 | Inorganic-organic hybrid antibacterial ultrafiltration membrane and preparation method thereof |
| CN105645679A (en) * | 2016-01-06 | 2016-06-08 | 南京大学 | Oily wastewater recycling and wastewater treatment system and treatment method thereof |
| CN108314891A (en) * | 2018-03-21 | 2018-07-24 | 安徽江淮汽车集团股份有限公司 | A kind of PEO composite material and preparation methods |
| CN111068524A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Seawater desalination micro-nano membrane material, preparation method and application thereof |
| CN111068524B (en) * | 2018-10-18 | 2022-03-22 | 中国科学院宁波材料技术与工程研究所 | Seawater desalination micro-nano membrane material, preparation method and application thereof |
| CN109762462A (en) * | 2019-01-30 | 2019-05-17 | 中国科学院长春应用化学研究所 | A kind of anticorrosive paint with barrier property |
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