Summary of the invention
the problem that invention will solve
The object of the invention is to, a kind of high-selectivity composite nanofiltration membrane and preparation method thereof is provided.The present invention is by utilize interfacial polymerization method to be formed on porous support layer function desalination layer that one deck has high selectivity, and by the active site access active group on film surface or/and coating one deck nano particle carries out finishing, while the higher water flux of guarantee and salt rejection rate, improve the antifouling property of film, extend the service life of membrane component.
for the scheme of dealing with problems
In order to achieve the above object, the invention provides following technical scheme: a kind of high-selectivity composite nanofiltration membrane, comprise nonwoven layer and high-molecular porous supporting layer, be characterized in: on porous support layer, have the polyamide surface layer that one deck polyamine and/or polyhydric alcohol amine and polynary acyl chloride reaction are made.
Described porous support layer is one or more the mixture in polysulfone porous supporting layer, polyether sulfone porous support layer, polyacrylonitrile porous support layer, polyethylene porous supporting layer, polypropylene porous support layer, sulfonated polyether sulfone porous support layer, Kynoar porous support layer, polyvinylpyrrolidone.
The preparation method of above-mentioned high-selectivity composite nanofiltration membrane comprises the following steps:
(1) solution A of porous support layer with the compound containing at least two reactive aminos is contacted;
(2) remove the unnecessary solution in top layer, this supporting layer is contacted with the B solution containing at least two multi-functional chloride compounds of reactive acid chloride group, form polyamide surface layer;
(3) after the volatilization of top layer solvent, with the compound containing at least two active groups or/and the C solution containing nano particle contacts, finishing coat is formed;
(4) after post processing, oven dry, composite nanometer filtering film is obtained.
The compound of two active reactive groups (or being called reactive group, active group) is had at least to be at least one in aromatic series, aliphatic, alicyclic polyfunctional amine, polyhydric alcohol amine, polyalcohol, epoxy, nano particle contained by solution A or C solution.
Described aromatic series polyfunctional amine is o-phenylenediamine, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 1,3,5-tri-amido benzene, 1,2,4-tri-amido benzene, 3,5-diaminobenzoic acids, 2, at least one in 4-diaminotoluene, 2,4-diamino anisoles, amidol, xylylene diamine; Described aliphatic polyfunctional amine is at least one in ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-aminoethyl) amine, diethylenetriamine, N-(2-ethoxy) ethylenediamine, hexamethylene diamine; Described alicyclic polyfunctional amine is 1,3-diamines butylcyclohexane, 1,2-diamines butylcyclohexane, Isosorbide-5-Nitrae-DACH, piperazine, 1, at least one in 3 a pair of piperidyl propane, 4 one aminomethylpiperazine; Described polyhydric alcohol amine is at least one in monoethanolamine, diethanol amine, hexylene glycol amine, diglycolamine; Described epoxy compounds is at least one in terephthalic acid (TPA) diglycidyl ether, terephthalic acid diglycidyl ester, diaminourea dimethylbenzene epoxy resin, para-aminophenol epoxy resin, cyanuric acid three-glycidyl amine, isocyanuric acid three-glycidyl ester, ethylene glycol diglycidylether, propylene glycol glycidyl ether; Described nano particle mainly contains at least one in nano silicon, nano zine oxide, Nano Silver, nano calcium oxide.
Two multi-functional chloride compounds of reactive acid chloride group are had at least to be one or more in aromatic series, aliphatic, alicyclic multifunctional chloride compounds contained by aforementioned B solution.
The multifunctional chloride compounds of described aromatic series is at least one in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride; The multifunctional chloride compounds of described aliphatic is at least one in fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, the last of the ten Heavenly stems three acyl chlorides; Described alicyclic multifunctional chloride compounds is at least one in oxolane diacid chloride, oxolane four acyl chlorides, cyclopropane three acyl chlorides, cyclobutane diacid chloride, cyclobutane four acyl chlorides, pentamethylene diacid chloride, pentamethylene three acyl chlorides, pentamethylene four acyl chlorides, cyclohexane diacid chloride, cyclohexane three acyl chlorides, cyclohexane four acyl chlorides.
The time that porous support layer contacts with solution A is 5s ~ 300s, and the time contacted with B solution is 5s ~ 300s, and the time contacted with C solution is 5s ~ 300s.
Be respectively the surfactant of 0.1% ~ 5% containing weight percent concentration in aforementioned solution A, C solution, at least one compound at least one compound in the isopropyl alcohol of 0.1% ~ 10%, '-biphenyl diphenol, DMSO and the triethylamine of 0.1% ~ 3%, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, potassium hydroxide.
Described surfactant is at least one compound in lauryl sodium sulfate, neopelex, 1-METHYLPYRROLIDONE, dodecyl sodium sulfate, dioctyl succinate disulfonate acid.
The compound method of aforementioned solution A or C solution is: aromatic series, aliphatic, alicyclic polyfunctional amine and/or polyhydric alcohol amine, one or more in epoxide are dissolved in the water, its total concentration by weight is in aqueous 0.1% ~ 5%, treat polyfunctional amine and/or polyhydric alcohol amine, after epoxide is dissolved in water completely, the surfactant that percentage by weight is 0.1% ~ 5% is added again in the aqueous solution, the isopropyl alcohol of 0.1% ~ 10%, '-biphenyl diphenol, at least one compound in DMSO and the triethylamine of 0.1% ~ 3%, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, at least one compound in potassium hydroxide, after stirring and dissolving and get final product.Namely in the present invention, solution A is identical with the compound method of C solution, but the reactive amine based compound contained by C solution can be identical with the reactive amine based compound contained by solution A, also can be different; Equally, although the weight percent concentration of reactive amine based compound is all in the scope of 0.1% ~ 5% in solution A and C solution, both concentration can be identical, also can be different.
The compound method of aforementioned B solution is: get one or more in aromatic series, aliphatic, alicyclic multifunctional chloride compounds, the ratio being 0.05% ~ 5% according to gross mass percentage is dissolved in one or more compounds in aliphatic hydrocarbon containing 4 ~ 12 carbon atoms, cycloalphatic hydrocarbon, aromatic hydrocarbon, after stirring and dissolving and get final product.
Post processing described in step (4), furnace drying method for: be 1.0% ~ 15% by formed polyamide surface layer film weight concentration, temperature be that the acid solution of 40 ~ 90 DEG C soaks 1 ~ 60 minute, then unnecessary acid is washed off with clear water, soak 1 ~ 30 minute with the glycerite that weight concentration is 10% again, finally this film being placed on temperature is keep 5 minutes in the baking oven of 30 ~ 120 DEG C, forms finished product composite nanometer filtering film.
the effect of invention
Polyamide surface layer composite nanometer filtering film obtained by the present invention, under the test condition of the 2000ppmNaCl aqueous solution, 75psi operating pressure, temperature 25 DEG C, pH value 6.5 ~ 7.5, NaCl removal efficiency is 40 ~ 95%, and water flux is at 10 ~ 40GFD; At 2000ppm MgSO
4under aqueous solution test condition, MgSO
4removal efficiency is more than 95%, and water flux is at 15 ~ 40GFD.
Compared with prior art, the present invention forms polyamide surface layer by utilizing interfacial polymerization on porous support layer, adds the thickness on NF membrane top layer, makes film surface more smooth, more hydrolysis, resistance to oxidation and scratch resistant, also improve the anti-fouling performance of film; And film surface can electronegative or positive charge, thus makes this composite nanometer filtering film have the function desalination layer of high selectivity; In addition, the present invention prepares the method for composite nanometer filtering film and simple to operate, and while the higher water flux of guarantee and salt rejection rate, extends the service life of membrane component.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail, but not as limitation of the present invention.
Embodiment 1: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A: 18g Piperazine anhydrous (weight concentration 1.8%), 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%) are dissolved in 976g water, to be dissolved completely after, stirring and dissolving completely after obtain solution A.
(2) preparation of B solution: get 26.7g pyromellitic trimethylsilyl chloride and be dissolved in 1573.3g n-hexane and be made into the solution that weight concentration is 1.67%, to be dissolved completely after obtain B solution.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely weight concentration be 6%, temperature is soak 10 minutes in the sulfuric acid solution of 80 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with the glycerite of 10% again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 2: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A, B solution is with embodiment 1.
(2) preparation of C solution: with the preparation of solution A.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization is dry, is immersed in 20s in C solution forms finishing coat, afterwards weight concentration be 6%, temperature be in the sulfuric acid solution of 80 DEG C soak 10 minutes, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with the glycerite of 10% again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 3: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A, B solution is with embodiment 1.
(2) preparation of C solution: get 5g m-phenylene diamine (MPD) (weight concentration 0.5%), 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%) to be dissolved in 989g water stirring and dissolving completely after obtain C solution.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization is dry, is immersed in 20s in C solution forms finishing coat, afterwards weight concentration be 6%, temperature be in the sulfuric acid solution of 80 DEG C soak 10 minutes, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 4: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A: get 12g Piperazine anhydrous and 6g m-phenylene diamine (MPD) (amine total concentration by weight is 1.8%) respectively, 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%) be dissolved in 976g water, stirring and dissolving completely after obtain solution A.
(2) preparation of B solution is with embodiment 1.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely weight concentration be 6%, temperature is soak 10 minutes in the oxalic acid solution of 80 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 5: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A is with embodiment 1.
(2) preparation of B solution: get 13g pyromellitic trimethylsilyl chloride respectively and 25g m-phthaloyl chloride is dissolved in 962g n-hexane, stirring and dissolving completely after obtain B solution.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely weight concentration be 6%, temperature is soak 10 minutes in the citric acid solution of 80 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with the glycerite of 10% again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 6: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A: get 25g m-phenylene diamine (MPD) and be dissolved in 955g water and be made into the solution that weight concentration is 2.5%, to be dissolved completely after, in this solution, add NaOH 5g (weight concentration 0.5%), 1-METHYLPYRROLIDONE 10g (weight concentration 1%), isopropyl alcohol 5g (weight concentration 0.5%) again, after stirring and dissolving is complete, obtain solution A.
(2) preparation of B solution: get 1g m-phthaloyl chloride and 0.5g pyromellitic trimethylsilyl chloride is dissolved in the mixed solvent of 6.5g dimethylbenzene and 992g n-hexane, stirring and dissolving completely after obtain B solution.
(3) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 1Ss is contacted with B solution, after solvent volatilization completely weight concentration be 6%, temperature is soak 10 minutes in the citric acid solution of 80 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with the glycerite of 10% again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 7: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A, B solution, C solution is with embodiment 2.
(2) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization is dry, is immersed in 10s in C solution forms finishing coat, afterwards weight concentration be 6%, temperature be in the sulfuric acid solution of 80 DEG C soak 10 minutes, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 8: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A, B solution, C solution is with embodiment 2.
(2) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization is dry, is immersed in 60s in C solution forms finishing coat, afterwards weight concentration be 6%, temperature be in the sulfuric acid solution of 80 DEG C soak 10 minutes, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 9: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A: get 18g Piperazine anhydrous and be dissolved in 971g water and be made into the solution that weight concentration is 1.8%, to be dissolved completely after, in this solution, add NaOH 3g (weight concentration 0.3%), neopelex 3g (weight concentration 0.3%), isopropyl alcohol 5g (weight concentration 0.5%) again, after stirring and dissolving is complete, obtain solution A.
(2) preparation of B solution is with embodiment 1.
(3) configuration of C solution: get 5g m-phenylene diamine (MPD) (weight concentration 0.5%), 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%), 1g Nano Silver (weight concentration 0.1%) to be dissolved in 988g water stirring and dissolving completely after obtain C solution.
(4) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely, be immersed in 60s in C solution and form finishing coat, afterwards weight concentration be 6%, temperature be in the sulfuric acid solution of 80 DEG C soak 10 minutes, 5 minutes are soaked again with pure water, clean unnecessary acid, then soak 5 minutes with 10% glycerite, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 10: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A is with embodiment 1.
(2) preparation of B solution is with embodiment 1.
(3) configuration of C solution: get 5g m-phenylene diamine (MPD) (weight concentration 0.5%), 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%), 3g isocyanuric acid three-glycidyl ester (weight concentration 0.3%) to be dissolved in 986g water stirring and dissolving completely after obtain C solution.
(4) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely weight concentration be 6%, temperature is soak 10 minutes in the sulfuric acid solution of 80 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
Embodiment 11: prepare composite nanometer filtering film according to the following steps:
(1) preparation of solution A is with embodiment 1.
(2) preparation of B solution is with embodiment 1.
(3) configuration of C solution: get 5g diglycolamine (weight concentration 0.5%), 3g NaOH (weight concentration 0.3%), 3g neopelex (weight concentration 0.3%), 1g nano zine oxide (weight concentration 0.1%) to be dissolved in 988g water stirring and dissolving completely after obtain C solution.
(4) porous support layer is immersed in 20s in solution A, drain to film surface and the back side without the obvious globule; Then 15s is contacted with B solution, after solvent volatilization completely weight concentration be 4%, temperature is soak 5 minutes in the sulfuric acid solution of 60 DEG C, 5 minutes are soaked again with pure water, clean unnecessary acid, soak 5 minutes with 10% glycerite again, finally dry in 80 DEG C of baking ovens and obtain composite nanometer filtering film in 5 minutes.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, temperature 25 DEG C, pH value 6.5 ~ 7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4aqueous solution MgSO
4removal efficiency and water flux are in table 1.
The water flux of table 1 each embodiment gained NF membrane and salt removal efficiency