CN102921300A - Agent and method for surface treatment on nanofiltration membrane - Google Patents
Agent and method for surface treatment on nanofiltration membrane Download PDFInfo
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- CN102921300A CN102921300A CN2012104151641A CN201210415164A CN102921300A CN 102921300 A CN102921300 A CN 102921300A CN 2012104151641 A CN2012104151641 A CN 2012104151641A CN 201210415164 A CN201210415164 A CN 201210415164A CN 102921300 A CN102921300 A CN 102921300A
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- membrane
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- conditioning agent
- surface conditioning
- surface treatment
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004381 surface treatment Methods 0.000 title claims abstract description 17
- 238000001728 nano-filtration Methods 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 230000003750 conditioning effect Effects 0.000 claims description 35
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims description 2
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 claims description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 2
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 claims description 2
- XTJCJAPNPGGFED-UHFFFAOYSA-N 2-hydroxyethylazanium;2-sulfanylacetate Chemical compound [NH3+]CCO.[O-]C(=O)CS XTJCJAPNPGGFED-UHFFFAOYSA-N 0.000 claims description 2
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 2
- NFCPTWDCIHOANE-UHFFFAOYSA-N N(CCO)(CCO)CCO.[Zr].B(F)(F)F Chemical compound N(CCO)(CCO)CCO.[Zr].B(F)(F)F NFCPTWDCIHOANE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001419 myristoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- -1 oleoyl diethanol amine Chemical compound 0.000 claims description 2
- 229960004838 phosphoric acid Drugs 0.000 claims description 2
- 229950001046 piroctone Drugs 0.000 claims description 2
- BTSZTGGZJQFALU-UHFFFAOYSA-N piroctone olamine Chemical compound NCCO.CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O BTSZTGGZJQFALU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229940117957 triethanolamine hydrochloride Drugs 0.000 claims description 2
- 229940117013 triethanolamine oleate Drugs 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 238000010612 desalination reaction Methods 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an agent and a method for surface treatment on a nanofiltration membrane. The agent for surface treatment comprises 0.01 to 10wt% of antibacterial nano-particles, 0.1 to 30wt% of one or more active agents and the balance one or more solvents. A preparation method of the agent comprises the following steps of dispersing the antibacterial nano-particles in the one or more solvents, stirring at a temperature of 20 to 40 DEG C until uniform dispersion, adding the one or more active agents into the mixed solution, and stirring for 1 to 10 hours until dissolution to obtain the agent for surface treatment on a nanofiltration membrane. The method for surface treatment on a nanofiltration membrane comprises the following steps of 1, coating or dipping of the agent for surface treatment on a nanofiltration membrane, 2, air-knife surface drying, and 3, drying in an oven. The agent and the method for surface treatment on a nanofiltration membrane have the advantages that a high desalinization rate is maintained and a nanofiltration membrane treated by the agent and the method has high flux under low pressure so that a nanofiltration membrane product having excellent flux performances and good desalination effects is obtained. The agent has high efficiency, can be operated easily, and has low equipment requirements and strong practicality.
Description
Technical field
The present invention relates to a kind of surface conditioning agent and surface treatment method of NF membrane, belong to water treatment field.
Background technology
NF membrane very easily is subject to organic contamination, and the characteristics such as its surface charge, hydrophobicity, roughness have significant impact to organic adsorption fouling and the obstruction of film.On the one hand, polar organic matter may carry out with hydrogen bond action, dispersion force absorption and hydrophobic effect in the lip-deep absorption of NF membrane; The formation of these adsorption layer of surface active agent makes hydrone will see through film and just must consume higher energy; Exactly because the activation energy of this increase finally causes the decline of aquifer yield.On the other hand, the interaction between hydrophobicity organic matter and water is enriched on the film surface the slow organic matter of these diffusions, and namely the low diffusible organic matter of macromolecule can be concentrated on the film surface; And also being conducive to them, the concentration polarization of macromolecule organic is adsorbed on the film surface; And the water intermediate ion (mainly is Ca
2-) interact with organic matter functional group, also can change hydrophobicity and the diffusivity of these organic molecules, thereby so that nonpolar organic matter, hydrophobicity Adsorption of Organic cause on the NF membrane surface film to pollute.
The NF membrane separation has two characteristics, i.e. sieve effect and charge effect.Sieve effect refers to that molecular weight holds back tunicle greater than the material of the molecular cut off of film, otherwise then sees through; Charge effect is called again the Donnan effect, refers to ion and the charged electrostatic interaction of film.Mainly be to be sieve effect by steric effect to the filtration of uncharged molecule, utilize the sieve effect can be with the separating substances of different molecular weight; And mainly be by electric charging effect to the filtration with the material of electric charge, NF membrane surface separating layer can be made of polyelectrolyte, the film surface is with certain electric charge, the surface of most of NF membrane is with negative electrical charge, they pass through electrostatic interaction, hinder the infiltration of multivalent ion, this is that NF membrane still has the major reason than the high desalination performance under lower pressure.NF membrane commonly used mostly is charged membrane at present, compares with non-charged nanofiltration membrane, and some specific ions are had preferably removal effect, but the impurity in the easy adsorbed water of charged membrane causes film to pollute, thereby causes film properties to descend.Change an angle, if utilize this characteristic, make film adsorption functional mass, then can by change the film surface nature, such as improving hydrophily, roughness, fill fenestra and improve rejection etc., thereby improve the NF membrane overall performance.
CN1293138C discloses a kind of synthetic polymeric membrane with the surface preparation of surface conditioning agent and synthetic polymeric membrane, be that special ethylene base co-polymer by being contained the nitrogen organic group by side chain and the surface conditioning agent of lubricant carry out certain processing to the synthetic polymeric membrane surface, given the electrostatic prevention of synthetic polymeric membrane excellence, antifog property and excellent sliding.But this scheme is not suitable for high but the problem that membrane flux is lower of NF membrane removal efficiency that solves.
Summary of the invention
The invention provides a kind of surface conditioning agent and surface treatment method of NF membrane, solved the NF membrane removal efficiency high, make the film surface be vulnerable to pollute and make the lower problem of membrane flux.
Technical scheme of the present invention is as described below.
A kind of surface conditioning agent of NF membrane is characterized in that: by antimicrobial nano particle, activating agent and solvent composition; Wherein, the content of antimicrobial nano particle is that the content of 0.01～10wt%, activating agent is 0.1～30wt%, and all the other are solvent;
Described antimicrobial nano particle refers to any or several combination in titanium dioxide, aluminium oxide, silica, zinc oxide, zirconia, imvite and the CNT;
The particle diameter of described antimicrobial nano particle is 1～500nm, is optimized for 10～200nm;
Described solvent refer in water, ethanol, methyl alcohol, isopropyl alcohol, the tert-butyl alcohol and the acetone any or several;
Described activating agent refers to monoethanolamine, diethanol amine, triethanolamine, dimethylethanolamine, phosphoric acid acyl monoethanolamine, N methyldiethanol amine, N, the N-diethyl ethylene diamine, phenolethanolamine, triethanolamine oleate, PVOH amine, the boron trifluoride zirconium triethanolamine complex, the N-aminoethanolamine, Octopirox, N-benzyl ethyl alcohol amine, the monoethanolamine thioglycolate salt, N butyl diethanol amine, tert-butyl group monoethanolamine, coconut oleoyl diethanol amine, triethanolamine hydrochloride, triethanolamine phosphate, myristoyl phosphoric acid acyl monoethanolamine, glycerine, in glycerin ether and the dodecyltriethanolamine sulfate etc. any or several;
The surface conditioning agent of above-mentioned NF membrane, its preparation method are that nano particle is scattered in the solvent, are stirred to be uniformly dispersed under 20～40 ℃, add activating agent, stir 1～10h, obtain surface conditioning agent after the dissolving.
A kind of surface treatment method of NF membrane mainly may further comprise the steps:
(1) surface conditioning agent applies or dipping: above-mentioned surface conditioning agent evenly is coated on the NF membrane surface, perhaps with the NF membrane surface impregnation in surface conditioning agent;
(2) surface drying is processed: adopt the air knife surface drying to process to NF membrane;
(3) drying and processing: place baking oven, at 15-80 ℃ of lower drying and processing 0.1～1h, get final product.
Coating in the described step (1) refers to adopt the mode of blade coating, spraying, and surface conditioning agent evenly is coated on the NF membrane face, and the inorganic agent that is sprayed on the face is 10～200g/m
2, solution keeps 0.1～10min at face after the spraying.
Dipping in the described step (1) refers to the NF membrane diaphragm is immersed in 0.1～10min in 10～60 ℃ the surface conditioning agent.
Beneficial effect of the present invention: nano particle in the reagent treatment, such as the introducing of TiO 2 particles, can improve the antibacterial ability of NF membrane in running, and improve to a certain extent the desalting performance of NF membrane; The introducing of activating agent can be by the effect of residual groups on itself and the NF membrane desalination layer and polyamide network the flux of Effective Raise diaphragm; Because the NF membrane salt rejection rate after activating agent is processed has decline to a certain degree, the introducing of nano particle can the equilibrium activity agent for the inhibition of desalting performance; Selected solvent in the surface conditioning agent has promoted the raising of flux.Adopt surface conditioning agent of the present invention and surface treatment method, in the situation that keep than equipment with high desalinization, can make NF membrane under the low pressure condition, possess higher flux, the acquisition desalination is better, and the NF membrane product of flux performance excellence, have efficient, easy-operating characteristics, lower for the requirement of equipment, practicality is very strong.
The specific embodiment
In order to deepen that the present invention is understood, the present invention is described in further detail below in conjunction with embodiment, and this embodiment only is used for explaining the present invention, does not consist of the restriction to protection domain of the present invention.
Embodiment 1
50g titanium dioxide nano-particle (particle diameter 60nm) is scattered in the 4900g deionized water, under 20 ° of C fully dispersed with stirring evenly after, add the 50g monoethanolamine, stir 1h, be mixed with surface conditioning agent.Get 20cm * 20cm specification VNF1 NF membrane and impregnated in the suspension, take out behind the 0.1min, in 80 ° of C baking ovens, heat-treat after removing remained on surface solution with air knife, namely get the NF membrane behind the Nanoparticle Modified behind the processing time 10min.
Embodiment 2
100g aluminium oxide nano particle (particle diameter 500nm) is dissolved in the 4900g ethanol, under 25 ° of C fully dispersed with stirring evenly after, add 50g phosphoric acid acyl monoethanolamine, stir 3h, be mixed with surface conditioning agent.Get 20cm * 20cm specification VNF1 NF membrane and impregnated in the ethylene glycol amine aqueous solution, take out behind the 4min, in 60 ° of C baking ovens, heat-treat after removing remained on surface solution with air knife, namely get the NF membrane of ethylene glycol after amine-modified behind the processing time 30min.
Embodiment 3
50g Nano particles of silicon dioxide (particle diameter 200nm) is scattered in the 4850g methyl alcohol, under 30 ° of C fully dispersed with stirring evenly after, add the 100g dimethylethanolamine and join in the suspension, stir 57h, be mixed with surface conditioning agent.Get 20cm * 20cm specification VNF1 NF membrane and impregnated in the suspension, take out behind the 8min, with in 40 ° of C baking ovens, heat-treating behind the air knife removal remained on surface solution, namely get the NF membrane after surface conditioning agent is modified behind the processing time 40min.
Embodiment 4
50g zinc oxide nano-particle (particle diameter 100nm) is scattered in the 4850g isopropyl alcohol, under 35 ° of C fully dispersed with stirring evenly after, add the 100g triethanolamine in suspension, stir 7h, be mixed with surface conditioning agent.Get 20cm * 20cm specification VNF1 NF membrane and impregnated in the suspension, take out behind the 10min, with in 15 ° of C baking ovens, heat-treating behind the air knife removal remained on surface solution, namely get the NF membrane after surface conditioning agent is modified behind the processing time 60min.
Embodiment 5
50g zirconium oxide nano-particle (particle diameter 10nm) is scattered in the 4950g tert-butyl alcohol, under 40 ° of C fully dispersed with stirring evenly after, add the 50g diethanol amine, stir 10h, be mixed with surface conditioning agent.Get 20cm * 20cm specification VNF1 NF membrane and impregnated in the suspension, take out behind the 6min, in 70 ° of C baking ovens, heat-treat after removing remained on surface solution with air knife, namely get the NF membrane behind the Nanoparticle Modified behind the processing time 20min.
Get 6 of Vontron commercialization VNF1 NF membrane, wherein 5 each NF membrane that obtains after the described method of embodiment 1--5 is processed are test product, remaining 1 is reference substance without any surface treatment, in the test of diaphragm monitor station, be 70psi at operating pressure, temperature is 25 ℃, the pH value is under the test condition of 6.5-7.5, obtain 2000ppm NaCl aqueous solution water flux (GFD), and 2000ppm MgSO4 aqueous solution water flux (GFD), the results are shown in Table 1.
The flux of table 1 NF membrane and salt rejection rate
As shown in Table 1, compare with the NF membrane without any processing, adopt surface conditioning agent of the present invention and surface treatment method, can effectively regulate flux and the salt rejection rate of NF membrane.After adopting the embodiment of the invention 1 described method to process NF membrane, the flux of NF membrane descends to some extent, but its salt rejection rate obviously rises; After adopting the embodiment of the invention 2 described methods to process NF membrane, the flux of NF membrane obviously rises, but its salt rejection rate also descends to some extent; After adopting the embodiment of the invention 3 and 4 described methods to process NF membrane, flux and the salt rejection rate of NF membrane all are improved; After adopting the embodiment of the invention 5 described methods to process NF membrane, the flux of NF membrane slightly descends, but salt rejection rate obviously improves.
Claims (9)
1. the surface conditioning agent of a NF membrane is characterized in that: by antimicrobial nano particle, activating agent and solvent composition; Wherein, the content of antimicrobial nano particle is that the content of 0.01～10wt%, activating agent is 0.1～30wt%, and all the other are solvent;
2. the surface conditioning agent of a kind of NF membrane according to claim 1 is characterized in that: described antimicrobial nano particle refers to any or several combination in titanium dioxide, aluminium oxide, silica, zinc oxide, zirconia, imvite and the CNT;
3. the surface conditioning agent of a kind of NF membrane according to claim 2, it is characterized in that: the particle diameter of described antimicrobial nano particle is 1～500nm, is optimized for 10～200nm;
4. the surface conditioning agent of a kind of NF membrane according to claim 1 is characterized in that: described solvent refer in water, ethanol, methyl alcohol, isopropyl alcohol, the tert-butyl alcohol and the acetone any or several;
5. the surface conditioning agent of a kind of NF membrane according to claim 1, it is characterized in that: described activating agent refers to monoethanolamine, diethanol amine, triethanolamine, dimethylethanolamine, phosphoric acid acyl monoethanolamine, N methyldiethanol amine, N, the N-diethyl ethylene diamine, phenolethanolamine, triethanolamine oleate, PVOH amine, the boron trifluoride zirconium triethanolamine complex, the N-aminoethanolamine, Octopirox, N-benzyl ethyl alcohol amine, the monoethanolamine thioglycolate salt, N butyl diethanol amine, tert-butyl group monoethanolamine, coconut oleoyl diethanol amine, triethanolamine hydrochloride, triethanolamine phosphate, myristoyl phosphoric acid acyl monoethanolamine, glycerine, in glycerin ether and the dodecyltriethanolamine sulfate etc. any or several;
6. the surface conditioning agent of a kind of NF membrane according to claim 1, it is characterized in that: its preparation method is that nano particle is scattered in the solvent, is stirred to be uniformly dispersed under 20～40 ℃, adds activating agent, stir 1～10h, obtain surface conditioning agent after the dissolving.
7. the surface treatment method of a NF membrane is characterized in that: mainly may further comprise the steps:
(1) surface conditioning agent applies or dipping: each described surface conditioning agent of claim 1 ~ 6 evenly is coated on the NF membrane surface, perhaps with the NF membrane surface impregnation in surface conditioning agent;
(2) surface drying is processed: adopt the air knife surface drying to process to NF membrane;
(3) drying and processing: place baking oven, at 15-80 ℃ of lower drying and processing 0.1～1h, get final product.
8. the surface treatment method of a kind of NF membrane according to claim 7, it is characterized in that: the coating in the described step (1) refers to adopt the mode of blade coating, spraying, surface conditioning agent evenly is coated on the NF membrane face, and the inorganic agent that is sprayed on the face is 10～200g/m
2, solution keeps 0.1～10min at face after the spraying.
9. the surface treatment method of a kind of NF membrane according to claim 7 is characterized in that: the dipping in the described step (1) refers to the NF membrane diaphragm is immersed in 0.1～10min in 10～60 ℃ the surface conditioning agent.
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