CN101698139B - Method for preparing high-performance polyelectrolyte-nano layered silicate composite pervaporation membrane - Google Patents
Method for preparing high-performance polyelectrolyte-nano layered silicate composite pervaporation membrane Download PDFInfo
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- CN101698139B CN101698139B CN2009101532601A CN200910153260A CN101698139B CN 101698139 B CN101698139 B CN 101698139B CN 2009101532601 A CN2009101532601 A CN 2009101532601A CN 200910153260 A CN200910153260 A CN 200910153260A CN 101698139 B CN101698139 B CN 101698139B
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 title abstract description 15
- 238000000034 method Methods 0.000 title abstract description 11
- 238000005373 pervaporation Methods 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000005266 casting Methods 0.000 claims abstract description 34
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 34
- 238000001291 vacuum drying Methods 0.000 claims abstract description 32
- 125000002091 cationic group Chemical group 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 16
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims description 77
- 229910052708 sodium Inorganic materials 0.000 claims description 77
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 72
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 72
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 66
- 238000005342 ion exchange Methods 0.000 claims description 39
- 230000004888 barrier function Effects 0.000 claims description 35
- 238000009792 diffusion process Methods 0.000 claims description 35
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 32
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims description 16
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 16
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229920000193 polymethacrylate Polymers 0.000 claims description 14
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 235000010980 cellulose Nutrition 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- -1 alkyl ammonium halide Chemical class 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001589 annite Inorganic materials 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 3
- 150000004760 silicates Chemical class 0.000 abstract 2
- 238000002604 ultrasonography Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 90
- 150000001875 compounds Chemical class 0.000 description 34
- 238000013019 agitation Methods 0.000 description 26
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 17
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 14
- 230000004907 flux Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 13
- 230000003204 osmotic effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 7
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 230000031709 bromination Effects 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 241000446313 Lamella Species 0.000 description 5
- 229910052615 phyllosilicate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical class [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing a high-performance polyelectrolyte-nano layered silicate composite separation membrane. The method comprises the following steps: after vacuum drying, dissolving the vacuum-dried anionic polyelectrolyte and the vacuum-dried cationic polyelectrolyte in water respectively, and adding hydrochloric acid into the solution; dispersing nano layered silicateinto cationic polyelectrolyte solution under the conditions of stirring and ultrasound; dropping the cationic polyelectrolyte solution dispersed with the nano layered silicate into anionic polyelectrolyte solution under the conditions of stirring and ultrasound to obtain a series of polyelectrolyte-nano layered silicate composites; after vacuum drying, adding the vacuum-dried polyelectrolyte-nanolayered silicate composites and sodium hydroxide into the water, stirring, dissolving, standing and defoaming the mixture to obtain membrane casting liquor; and evenly scraping the polyelectrolyte-nano layered silicate composite membrane casting liquor onto a polyacrylonitrile porous membrane by using a knife, and drying to obtain the polyelectrolyte-nano layered silicate composite separation membrane. The polyelectrolyte-nano layered silicate composite separation membrane has the advantages of cheap and easily-obtained raw materials, simple preparation method and excellent mechanical property and separation property. The invention discloses a method for preparing a high-performance polyelectrolyte-nano layered silicate composite pervaporation membrane.
Description
Technical field
The present invention relates to the preparation and the film separation field of polyelectrolyte nano material, relate in particular to a kind of preparation method of high-performance polyelectrolyte-nano layered silicate composite infiltrating and vaporizing membrane.
Background technology
Inorganic nano material and high-molecular organic material are compound, can improve the mechanical strength of macromolecular material.In numerous high molecular nanometer hybrid materials, stratified material and macromolecule are compound to be one of focus of this area research.Imvite, kaolin, talcum, attapulgite, sepiolite, annite, sericite, vermiculite, potassic feldspar all are the members in the phyllosilicate extended familys.Their crystal structure comprises the lamella that is made up of two silicon-oxy tetrahedrons and alumina or magnesia octahedron.The about 1nm of sheet bed thickness, length and width 30nm does not wait the phyllosilicate that some is special even bigger to several microns.These lamellas are stacked together regularly.Have part coordination displacement in the lamella, cause lamella electronegative, lamella institute is electronegative to come balance by the positive son of the metal in the sheet lamellar spacing.The most frequently used phyllosilicate is to have the imvite that different chemical is formed, and it has moderate ion exchange capacity (80-120mequiv/10g) and layer structure.Because peculiar physics, chemical property and the potential application prospect of nano layered silicate receives people's attention day by day.At present, stratified material has all carried out deep research at high performance material and water resource purification usefulness, and has obtained remarkable progress.Macromolecular material and nano layered silicate carry out compound, can improve mechanical property and barrier property of material etc.Therefore, nano layered silicate-polymer compound film is the new direction of film separation field research.
Infiltration evaporation (Pervaporation is called for short PV) is proposed in 1917 by Kober, is a kind of important film separation process.PV be a kind ofly utilize that each component in the liquid mixture is dissolved in dense film, the difference of diffusion and the membrane process that makes it to separate.PV begins to realize industrialization the nineties.Compare with separating technologies such as traditional rectifying, absorption, extractions, it has separative efficiency height, simple, easy to operate, the low power consumption and other advantages of equipment.PV more shows its special advantages in the separating of the high mixed system of nearly boiling point mixture, azeotropic mixture and temperature sensitivity.
Organics dehydration is prevalent in the chemical field, like systems such as ethanol dehydration, isopropanol dehydration and butanols dehydrations.Many water-soluble or hydrophilic macromolecules are used to the PV film research of organics dehydration, like PVA1, P4VP and PAM etc.Method through modification makes PVAL have charge, and blend has then improved the performance of PVAL film.
Polyelectrolyte (natural or synthetic) is one type of hydrophilic or water-soluble high-molecular material that contains dissociable construction unit, and it is of a great variety and be widely used in organics dehydration.Since single polyelectrolyte good water solubility, the poor stability of film; Improved the stability of film to a certain extent through cross-linking reaction, but membrane permeability can reduce.According to domestic and foreign literature, be used for organics dehydration just-preparation method of negative compound polyelectrolyte film has three kinds: (1) self-assembling method, promptly two of opposite charges kinds of polyelectrolyte are through the self-assembled multilayer films of self assembly layer by layer (LbL) method preparation; (2) blending method is promptly under acid condition, through the blend film of two kinds of weak polyelectrolytes of Prepared by Solution Mixing Method; (3) are coated with the method for scraping twice layer by layer, and its preparation technology is, scrape a kind of polyelectrolyte casting solution supporting on the counterdie earlier, treat the polyelectrolyte casting solution of its little dried back second kind of oppositely charged on its surperficial blade coating, or it is immersed in second kind of polyelectrolyte solution.At two-layer compound thing film at the interface, positive and negative polyelectrolyte has also improved its mechanical mechanics property because electrostatic interaction has formed the ionomer structure, thereby improved the separating property of two-layer compound thing film.It is crosslinked that polyelectrolyte complex compound has produced certain physical through big molecular anion and the effect of cation Coulomb force, be difficult for little molecule counter ion leakage takes place, so separating property is stable.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of high-performance polyelectrolyte-nano layered silicate composite infiltrating and vaporizing membrane is provided.
The preparation method of polyelectrolyte-nano layered silicate composite diffusion barrier comprises the steps:
1) with the cationic polyelectrolyte of 1.0～10.0 mass parts at 50～80 ℃ of following vacuum drying 6～10h, cationic polyelectrolyte is: shitosan, PAH, poly dimethyl allyl-ammonium, polymine, polymethyl acyl-oxygen ethyl-trimethyl salmiac, polyvinylpyridine alkyl ammonium halide or cationic cellulose;
2) get the above-mentioned dried cationic polyelectrolyte of 0.5～5.0 mass parts and be dissolved in 100～2000 mass parts water, add 0.04～0.5 mass parts hydrochloric acid;
3) with the anionic polyelectrolyte of 0.6～8.0 mass parts at 50～80 ℃ of following vacuum drying 6～10h, anionic polyelectrolyte is: sodium carboxymethylcellulose, Sodium Polyacrylate, sodium alginate, sodium polymethacrylate or polyphosphate sodium;
4) get the above-mentioned dried anionic polyelectrolyte of 0.2～2.0 mass parts and be dissolved in 100～2000 mass parts water, add 0.04～0.5 mass parts hydrochloric acid;
5) under 50～100W is ultrasonic, be scattered in 0.02～0.5 mass parts nano layered silicate in the cationic polyelectrolyte solution; The cationic polyelectrolyte drips of solution that will include nano layered silicate adds in the anionic polyelectrolyte solution, obtains polyelectrolyte-nano layered silicate composite;
6) with polyelectrolyte-nano layered silicate composite with absolute ethanol washing after, at 60～80 ℃ of down dry 6～10h;
7) NaOH with 0.2～1.0 mass parts polyelectrolyte-nano layered silicate composite and 0.03～0.2 mass parts joins in 10～50 mass parts water; Obtain casting solution after the dissolving; This casting solution is assorted through filtering; Evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtain the diffusion barrier that cortex is polyelectrolyte-nano layered silicate composite.
Phyllosilicate in described polyelectrolyte-nano layered silicate composite is imvite, kaolin, talcum, attapulgite, sepiolite, annite, sericite, vermiculite or potassic feldspar, is preferably calcium-base montmorillonite, sodium-based montmorillonite, magnesium base montmorillonite, Sodium base montmorillonite; The ion exchange capacity of said imvite (CEC) is 80～120mmol/100g.The content of the cationic polyelectrolyte in described polyelectrolyte-nano layered silicate composite is 10～30%.The content of the nano layered silicate in described polyelectrolyte-nano layered silicate composite is 0.1～15%.The alkyl of described polyvinylpyridine alkyl ammonium halide is methyl, ethyl, propyl group or butyl, and halogen is bromine or chlorine.
Polyelectrolyte of the present invention-nano layered silicate composite raw material are cheap and easy to get, and the preparation method is simple for its composite separating membrane, and has good structural behaviour, in separation of organic substances/water mixed system, shown high permeability and selectivity.
The present invention combines the advantage of compound polyelectrolyte high score from performance and nano layered silicate material; The composition of having prepared polyelectrolyte and phyllosilicate is controlled; The structure homogeneous of film has high score from the factor and flux, and good stable property and excellent mechanical property infiltrating and vaporizing membrane.
The specific embodiment
Embodiment 1
10.0 mass parts sodium carboxymethylcelluloses at 80 ℃ of following vacuum drying 6h, are dissolved in the dried sodium carboxymethylcellulose of 2 mass parts in the 2000 mass parts water under the 300rpm magnetic agitation speed, are made into carboxymethylcellulose sodium solution, add 0.5 mass parts hydrochloric acid.4 mass parts shitosans at 50 ℃ of following vacuum drying 6h, are dissolved in the dried shitosan of 2 mass parts in the 200 mass parts water under the 300rpm magnetic agitation speed, are made into chitosan solution, add 0.5 mass parts hydrochloric acid.With 0.5 mass parts ion exchange capacity is that the calcium-base montmorillonite of 120mmol/100g is scattered in the chitosan solution under 50W is ultrasonic; The chitosan solution that will include ion exchange capacity under the 800rpm mixing speed and be the calcium-base montmorillonite of 120mmol/100g is added dropwise in the carboxymethylcellulose sodium solution; Obtaining shitosan/sodium carboxymethylcellulose-ion exchange capacity is the calcium-base montmorillonite nano-complex of 120mmol/100g; After washing with alcohol, 80 ℃ of following dry 6h.1 mass parts shitosan/sodium carboxymethylcellulose-calcium-base montmorillonite nano-complex and 0.2 mass parts NaOH are joined in the 50 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-calcium-base montmorillonite nano-complex.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1633.5g/m
2H, the concentration that sees through water in the liquid is 99.41wt%.
Embodiment 2
With 1.0 mass parts sodium carboxymethylcelluloses at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried sodium carboxymethylcellulose of 0.25 mass parts is dissolved in the 100 mass parts water; Be made into carboxymethylcellulose sodium solution, add 0.04 mass parts hydrochloric acid.0.4 mass parts shitosan at 80 ℃ of following vacuum drying 6h, is dissolved in the dried shitosan of 0.2 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, is made into chitosan solution, add 0.04 mass parts hydrochloric acid.With 0.02 mass parts ion exchange capacity is that the sodium-based montmorillonite of 80mmol/100g is scattered in the chitosan solution under 100W is ultrasonic; The chitosan solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 80mmol/100g is added dropwise in the carboxymethylcellulose sodium solution; Obtaining shitosan/sodium carboxymethylcellulose-ion exchange capacity is the sodium-based montmorillonite nanometer compound of 80mmol/100g; After washing with alcohol, 60 ℃ of following dry 10h.0.2 mass parts shitosan/sodium carboxymethylcellulose-sodium-based montmorillonite nanometer compound and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1544.9g/m
2H, the concentration that sees through water in the liquid is 99.39wt%.
Embodiment 3
5.0 mass parts sodium carboxymethylcelluloses at 70 ℃ of following vacuum drying 6h, are dissolved in the dried sodium carboxymethylcellulose of 2 mass parts in the 1000 mass parts water under the 300rpm magnetic agitation speed, are made into carboxymethylcellulose sodium solution, add 0.5 mass parts hydrochloric acid.With 4 mass parts polyvinylpyridine butyl ammonium bromides at 60 ℃ of following vacuum drying 8h; Under the 300rpm magnetic agitation speed the dried polyvinylpyridine butyl of 2 mass parts ammonium bromide is dissolved in the 1000 mass parts water; Be made into polyvinylpyridine butyl bromination ammonium salt solution, add 0.5 mass parts hydrochloric acid.With 0.5 mass parts ion exchange capacity is that the sodium-based montmorillonite of 90mmol/100g is scattered under 100W is ultrasonic in the polyvinylpyridine butyl bromination ammonium salt solution; The polyvinylpyridine butyl bromination ammonium salt solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 90mmol/100g is added dropwise in the carboxymethylcellulose sodium solution; Obtain the sodium-based montmorillonite nanometer compound that polyvinylpyridine butyl ammonium bromide/sodium carboxymethylcellulose-ion exchange capacity is 90mmol/100g; After washing with alcohol, 60 ℃ of following dry 10h.0.5 mass parts polyvinylpyridine butyl ammonium bromide/sodium carboxymethylcellulose-sodium-based montmorillonite nanometer compound and 0.1 mass parts NaOH are joined in the 25 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1933.5g/m
2H, the concentration that sees through water in the liquid is 99.29wt%.
Embodiment 4
1.0 mass parts Sodium Polyacrylates at 50 ℃ of following vacuum drying 8h, are dissolved in the dried Sodium Polyacrylate of 0.25 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, are made into sodium polyacrylate solution, add 0.04 mass parts hydrochloric acid.0.4 mass parts PAH at 60 ℃ of following vacuum drying 10h, is dissolved in the dried PAH of 0.2 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, is made into PAH solution, add 0.04 mass parts hydrochloric acid.With 0.03 mass parts ion exchange capacity is that the calcium-base montmorillonite of 100mmol/100g is scattered in the PAH solution under 50W is ultrasonic; The PAH drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the calcium-base montmorillonite of 100mmol/100g adds in the sodium polyacrylate solution; Obtaining PAH/Sodium Polyacrylate-ion exchange capacity is the calcium-base montmorillonite nano-complex of 100mmol/100g; After washing with alcohol, 60 ℃ of following dry 8h.0.2 mass parts PAH/Sodium Polyacrylate-calcium-base montmorillonite nano-complex and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-calcium-base montmorillonite nano-complex.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1762.7g/m
2H, the concentration that sees through water in the liquid is 99.33wt%.
Embodiment 5
10.0 mass parts sodium carboxymethylcelluloses at 80 ℃ of following vacuum drying 6h, are dissolved in the dried sodium carboxymethylcellulose of 2 mass parts in the 2000 mass parts water under the 300rpm magnetic agitation speed, are made into carboxymethylcellulose sodium solution, add 0.5 mass parts hydrochloric acid.With 4 mass parts poly dimethyl allyl-ammoniums at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried poly dimethyl allyl-ammonium of 2 mass parts is dissolved in the 2000 mass parts water; Be made into poly dimethyl allyl-ammonium solution, add 0.5 mass parts hydrochloric acid.With 0.5 mass parts ion exchange capacity is that the magnesium base montmorillonite of 110mmol/100g is scattered under 80W is ultrasonic in the poly dimethyl allyl-ammonium solution; The poly dimethyl allyl-ammonium drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the magnesium base montmorillonite of 110mmol/100g adds in the carboxymethylcellulose sodium solution; Obtaining poly dimethyl allyl-ammonium/sodium carboxymethylcellulose-ion exchange capacity is the magnesium based montmorillonite nanometer compound of 110mmol/100g; After washing with alcohol, 70 ℃ of following dry 8h.0.5 mass parts poly dimethyl allyl-ammonium/sodium carboxymethylcellulose-magnesium based montmorillonite nanometer compound and 0.1 mass parts NaOH are joined in the 25 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-magnesium based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 2699.7g/m
2H, the concentration that sees through water in the liquid is 99.58wt%.
Embodiment 6
1.0 mass parts sodium polymethacrylates at 70 ℃ of following vacuum drying 8h, are dissolved in the dried sodium polymethacrylate of 0.25 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, are made into sodium polymethacrylate solution, add 0.05 mass parts hydrochloric acid.With 0.4 mass parts polyvinylpyridine ammonio methacrylate at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried polyvinylpyridine ammonio methacrylate of 0.2 mass parts is dissolved in the 100 mass parts water; Be made into polyvinylpyridine ammonio methacrylate solution, add 0.05 mass parts hydrochloric acid.With 0.02 mass parts ion exchange capacity is that the calcium-base montmorillonite of 110mmol/100g is scattered under 90W is ultrasonic in the polyvinylpyridine ammonio methacrylate solution; The polyvinylpyridine ammonio methacrylate drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the calcium-base montmorillonite of 110mmol/100g adds in the sodium polymethacrylate solution; Obtain the Sodium based montmorillonite nanometer compound of polyvinylpyridine ammonio methacrylate/sodium polymethacrylate-110mmol/100g; After washing with alcohol, 60 ℃ of following dry 10h.0.2 mass parts polyvinylpyridine ammonio methacrylate/polymethylacrylic acid-calcium-base montmorillonite nano-complex and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-calcium-base montmorillonite nano-complex.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1892.9g/m
2H, the concentration that sees through water in the liquid is 99.24wt%.
Embodiment 7
10.0 mass parts sodium carboxymethylcelluloses at 50 ℃ of following vacuum drying 10h, are dissolved in the dried sodium carboxymethylcellulose of 2 mass parts in the 1000 mass parts water under the 300rpm magnetic agitation speed, are made into carboxymethylcellulose sodium solution, add 0.5 mass parts hydrochloric acid.4 mass parts cationic celluloses at 50 ℃ of following vacuum drying 10h, are dissolved in the dried cationic cellulose of 2 mass parts in the 1000 mass parts water under the 300rpm magnetic agitation speed, are made into the cationic fiber cellulose solution, add 0.5 mass parts hydrochloric acid.With 0.5 mass parts ion exchange capacity is that the sodium-based montmorillonite of 100mmol/100g is scattered in the cationic fiber cellulose solution under 60W is ultrasonic; The cationic cellulose drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 100mmol/100g adds in the carboxymethylcellulose sodium solution; Obtaining cationic cellulose/sodium carboxymethylcellulose-ion exchange capacity is the sodium-based montmorillonite nanometer compound of 100mmol/100g; After washing with alcohol, 70 ℃ of following dry 8h.1 mass parts cationic cellulose/sodium carboxymethylcellulose-sodium-based montmorillonite nanometer compound and 0.2 mass parts NaOH are joined in the 50 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 2293.6g/m
2H, the concentration that sees through water in the liquid is 99.35wt%.
Embodiment 8
1.0 mass parts sodium polymethacrylates at 70 ℃ of following vacuum drying 6h, are dissolved in the dried sodium polymethacrylate of 0.5 mass parts in the 300 mass parts water under the 300rpm magnetic agitation speed, are made into sodium polymethacrylate solution, add 0.12 mass parts hydrochloric acid.With 1 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiac at 70 ℃ of following vacuum drying 6h; Under the 300rpm magnetic agitation speed the dried polymethyl acyl-oxygen of 0.5 mass parts ethyl-trimethyl salmiac is dissolved in the 300 mass parts water; Be made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution, add 0.12 mass parts hydrochloric acid.With 0.04 mass parts ion exchange capacity is that the sodium-based montmorillonite of 110mmol/100g is scattered under 80W is ultrasonic in the polymethyl acyl-oxygen ethyl-trimethyl salmiac solution; The polymethyl acyl-oxygen ethyl-trimethyl salmiac drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 110mmol/100g adds in the sodium polymethacrylate solution; Obtain the sodium-based montmorillonite nanometer compound that polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium polymethacrylate-ion exchange capacity is 100mmol/100g; After washing with alcohol, 70 ℃ of following dry 7h.0.3 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium polymethacrylate-sodium-based montmorillonite nanometer compound and 0.04 mass parts NaOH are joined in the 15 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 2855.8g/m
2H, the concentration that sees through water in the liquid is 99.59wt%.
Embodiment 9
3.0 mass parts sodium polymethacrylates at 50 ℃ of following vacuum drying 9h, are dissolved in the dried sodium polymethacrylate of 0.25 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, are made into sodium polymethacrylate solution, add 0.05 mass parts hydrochloric acid.With 0.4 mass parts polyvinylpyridine ethyl ammonium bromide at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried polyvinylpyridine ethyl of 0.2 mass parts ammonium bromide is dissolved in the 100 mass parts water; Be made into polyvinylpyridine ethyl bromination ammonium salt solution, add 0.05 mass parts hydrochloric acid.With 0.02 mass parts ion exchange capacity is that the sodium-based montmorillonite of 120mmol/100g is scattered under 90W is ultrasonic in the polyvinylpyridine ethyl bromination ammonium salt solution; The polyvinylpyridine ethyl bromination ammonium salt solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 120mmol/100g is added dropwise in the sodium polymethacrylate solution; Obtain the sodium-based montmorillonite nanometer compound that polyvinylpyridine ethyl ammonium bromide/sodium polymethacrylate-ion exchange capacity is 120mmol/100g; After washing with alcohol, 80 ℃ of following dry 6h.0.2 mass parts polyvinylpyridine ethyl ammonium bromide/sodium polymethacrylate-sodium-based montmorillonite nanometer compound and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 2124.6g/m
2H, the concentration that sees through water in the liquid is 99.37wt%.
Embodiment 10
With 2.0 mass parts sodium carboxymethylcelluloses at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried sodium carboxymethylcellulose of 0.25 mass parts is dissolved in the 300 mass parts water; Be made into carboxymethylcellulose sodium solution, add 0.05 mass parts hydrochloric acid.With 0.4 mass parts polyvinylpyridine alkyl ammomium chloride at 80 ℃ of following vacuum drying 6h; Under the 300rpm magnetic agitation speed the dried polyvinylpyridine alkyl ammomium chloride of 0.2 mass parts is dissolved in the 300 mass parts water; Be made into polyvinylpyridine alkyl ammomium chloride solution, add 0.05 mass parts hydrochloric acid.With 0.02 mass parts ion exchange capacity is that the calcium-base montmorillonite of 90mmol/100g is scattered under 100W is ultrasonic in the polyvinylpyridine alkyl ammomium chloride solution; The polyvinylpyridine alkyl ammomium chloride drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the calcium-base montmorillonite of 90mmol/100g adds in the carboxymethylcellulose sodium solution; Obtaining polyvinylpyridine alkyl ammomium chloride/sodium carboxymethylcellulose-ion exchange capacity is the calcium-base montmorillonite nano-complex of 90mmol/100g; After washing with alcohol, 60 ℃ of following dry 8h.0.3 mass parts polyvinylpyridine alkyl ammomium chloride/sodium carboxymethylcellulose-calcium-base montmorillonite nano-complex and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-calcium-base montmorillonite nano-complex.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1699.7g/m
2H, the concentration that sees through water in the liquid is 99.25wt%.
Embodiment 11
1.0 mass parts Sodium Polyacrylates at 60 ℃ of following vacuum drying 8h, are dissolved in the dried Sodium Polyacrylate of 0.25 mass parts in the 100 mass parts water under the 300rpm magnetic agitation speed, are made into sodium polyacrylate solution, add 0.04 mass parts hydrochloric acid.With 0.4 mass parts poly dimethyl allyl-ammonium at 50 ℃ of following vacuum drying 10h; Under the 300rpm magnetic agitation speed the dried poly dimethyl allyl-ammonium of 0.2 mass parts is dissolved in the 100 mass parts water; Be made into poly dimethyl allyl-ammonium solution, add 0.04 mass parts hydrochloric acid.0.02 mass parts nano layered silicate is scattered under 100W is ultrasonic in the poly dimethyl allyl-ammonium solution; The poly dimethyl allyl-ammonium drips of solution that will include sub-exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 110mmol/100g adds in the sodium polyacrylate solution; Obtaining poly dimethyl allyl-ammonium/Sodium Polyacrylate-ion exchange capacity is the sodium-based montmorillonite nanometer compound of 110mmol/100g; After washing with alcohol, 60 ℃ of following dry 8h.0.2 mass parts poly dimethyl allyl-ammonium/Sodium Polyacrylate-sodium-based montmorillonite nanometer compound and 0.03 mass parts NaOH are joined in the 10 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1806.5g/m
2H, the concentration that sees through water in the liquid is 99.28wt%.
Embodiment 12
1.0 mass parts sodium alginates at 70 ℃ of following vacuum drying 8h, are dissolved in the dried sodium alginate of 0.2 mass parts in the 200 mass parts water under the 300rpm magnetic agitation speed, are made into sodium alginate soln, add 0.05 mass parts hydrochloric acid.0.4 mass parts polymine at 60 ℃ of following vacuum drying 8h, is dissolved in the dried polymine of 0.2 mass parts in the 200 mass parts water under the 300rpm magnetic agitation speed, is made into the polyethyleneimine: amine aqueous solution, add 0.05 mass parts hydrochloric acid.With 0.02 mass parts ion exchange capacity is that the sodium-based montmorillonite of 100mmol/100g is scattered in the polyethyleneimine: amine aqueous solution under 100W is ultrasonic; The polymine drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the sodium-based montmorillonite of 100mmol/100g adds in the sodium alginate soln; Obtaining polymine/sodium alginate-ion exchange capacity is the sodium-based montmorillonite nanometer compound of 110mmol/100g; After washing with alcohol, 70 ℃ of following dry 8h.0.3 mass parts polymine/sodium alginate-sodium-based montmorillonite nanometer compound and 0.04 mass parts NaOH are joined in the 12 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-sodium-based montmorillonite nanometer compound.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 1544.7g/m
2H, the concentration that sees through water in the liquid is 98.89wt%.
Embodiment 13
5 mass parts sodium carboxymethylcelluloses at 50 ℃ of following vacuum drying 8h, are dissolved in the dried sodium carboxymethylcellulose of 2 mass parts in the 2000 mass parts water under the 300rpm magnetic agitation speed, are made into carboxymethylcellulose sodium solution, add 0.5 mass parts hydrochloric acid.With 4 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiacs at 80 ℃ of following vacuum drying 6h; Under the 300rpm magnetic agitation speed the dried polymethyl acyl-oxygen of 2 mass parts ethyl-trimethyl salmiac is dissolved in the 2000 mass parts water; Be made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution, add 0.5 mass parts hydrochloric acid.With 0.5 mass parts ion exchange capacity is that the calcium-base montmorillonite of 110mmol/100g is scattered under 100W is ultrasonic in the polymethyl acyl-oxygen ethyl-trimethyl salmiac solution; The polymethyl acyl-oxygen ethyl-trimethyl salmiac drips of solution that will include ion exchange capacity under the 800rpm mixing speed and be the calcium-base montmorillonite of 110mmol/100g adds in the carboxymethylcellulose sodium solution; Obtain the calcium-base montmorillonite nano-complex that polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose-ion exchange capacity is 110mmol/100g; After washing with alcohol, 70 ℃ of following dry 8h.1 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose-calcium-base montmorillonite nano-complex and 0.2 mass parts NaOH are joined in the 50 mass parts water, obtain casting solution after the dissolving.This casting solution is assorted through filtering, evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtaining cortex is the diffusion barrier of polyelectrolyte-calcium-base montmorillonite nano-complex.Under 60 ℃ of this diffusion barriers to 90wt% isopropyl alcohol-mixed system osmotic, evaporating and dewatering performance be: permeation flux is 2218.3g/m
2H, the concentration that sees through water in the liquid is 99.48wt%.
Claims (7)
1. the preparation method of polyelectrolyte-nano layered silicate composite diffusion barrier is characterized in that comprising the steps:
1) with the cationic polyelectrolyte of 0.5～5.0 mass parts at 50～80 ℃ of following vacuum drying 6～10h, cationic polyelectrolyte is: shitosan, PAH, poly dimethyl allyl-ammonium, polymine, polymethyl acyl-oxygen ethyl-trimethyl salmiac, polyvinylpyridine alkyl ammonium halide or cationic cellulose;
2) get the above-mentioned dried cationic polyelectrolyte of 0.4～4.5 mass parts and be dissolved in 100～2000 mass parts water, add 0.04～0.5 mass parts hydrochloric acid;
3) with the anionic polyelectrolyte of 0.4～4.0 mass parts at 50～80 ℃ of following vacuum drying 6～10h, anionic polyelectrolyte is: sodium carboxymethylcellulose, Sodium Polyacrylate, sodium alginate, sodium polymethacrylate or polyphosphate sodium;
4) get the above-mentioned dried anionic polyelectrolyte of 0.2～2.0 mass parts and be dissolved in 100～2000 mass parts water, add 0.04～0.5 mass parts hydrochloric acid;
5) under 50～100W is ultrasonic, be scattered in 0.02～1.0 mass parts nano layered silicate in the cationic polyelectrolyte solution; The cationic polyelectrolyte drips of solution that will include nano layered silicate adds in the anionic polyelectrolyte solution, obtains polyelectrolyte-nano layered silicate composite;
6) with polyelectrolyte-nano layered silicate composite with absolute ethanol washing after, at 60～80 ℃ of down dry 6～10h;
7) NaOH with 0.2～1.0 mass parts polyelectrolyte-nano layered silicate composite and 0.03～0.2 mass parts joins in 10～50 mass parts water; Obtain casting solution after the dissolving; This casting solution is assorted through filtering; Evenly be coated with after the standing and defoaming and scrape on polyacrylonitrile micropore counterdie, obtain the diffusion barrier that cortex is polyelectrolyte-nano layered silicate composite.
2. the preparation method of a kind of polyelectrolyte according to claim 1-nano layered silicate composite diffusion barrier is characterized in that said nano layered silicate is imvite, palygorskite, kaolin, talcum, attapulgite, sepiolite, annite, sericite, vermiculite or potassic feldspar.
3. the preparation method of a kind of polyelectrolyte according to claim 2-nano layered silicate composite diffusion barrier; It is characterized in that said nano layered silicate is imvite, be selected from calcium-base montmorillonite, sodium-based montmorillonite, magnesium base montmorillonite or Sodium base montmorillonite.
4. the preparation method of a kind of polyelectrolyte according to claim 3-nano layered silicate composite diffusion barrier, the ion exchange capacity that it is characterized in that said imvite is 80～120mmol/100g.
5. the preparation method of a kind of polyelectrolyte according to claim 1-nano layered silicate composite diffusion barrier, the content that it is characterized in that the cationic polyelectrolyte in described polyelectrolyte-nano layered silicate composite is 10～30%.
6. the preparation method of a kind of high-performance polyelectrolyte-nano layered silicate composite compounding permeation vaporizing film according to claim 1, the content that it is characterized in that the nano layered silicate in described polyelectrolyte-nano layered silicate composite is 0.1～15%.
7. the preparation method of polyelectrolyte according to claim 1-nano layered silicate composite composite separating film, the alkyl that it is characterized in that described polyvinylpyridine alkyl ammonium halide is methyl, ethyl, propyl group or butyl, halogen is bromine or chlorine.
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| R.S.Veerapur ,etc..Sodium alginate-magnesium aluminum silicate mixed matrix membranes for pervaporation separation of water-isopropanol mixtures.《Separation and Purification Technology》.2008,第59卷(第2期),221,223. |
| R.S.Veerapur,etc..Sodium alginate-magnesium aluminum silicate mixed matrix membranes for pervaporation separation of water-isopropanol mixtures.《Separation and Purification Technology》.2008,第59卷(第2期),221,223. * |
| 许陈云.聚电解质渗透汽化复合膜的新型制备方法及其分离性能的初步研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2008,(第9期),24-25. * |
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