CN101934201A - High-selectivity composite nanofiltration membrane and preparation method thereof - Google Patents
High-selectivity composite nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-selectivity composite nanofiltration membrane and a preparation method thereof. The high-selectivity composite nanofiltration membrane comprises a nonwoven layer and a polymer porous supporting layer; and the porous supporting layer is provided with one or two polyamide surface layers prepared by reacting polyamine and/or amine polyalcohol with chlorine polyacyl. Compared with the prior art, by forming one or two polyamide surface layers on the porous supporting layer through an interfacial polymerization method, the nanofiltration membrane has increased thickness of a surface layer, has more smooth, hydrolysis-resistant, oxidation-resistant and scratch-resistant surface, and improves pollution resistance; and the surface of the membrane can carry negative or positive charges, so that the composite nanofiltration membrane has a high-selectively functional desalting layer; besides, the method for preparing the composite nanofiltration membrane is simple to operate, high water flux and desalination rate are ensured under low pressure, and the service life of the membrane component is prolonged.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering film and preparation method thereof, particularly a kind of composite nanometer filtering film and interfacial polymerization preparation method thereof with high selectivity function desalination layer.
Background technology
Diffusion barrier is a kind of energy-efficient parting material, is with a wide range of applications.NF membrane comes across late 1970s the earliest, is to develop one of film kind faster in recent years in the world, has now become the research focus in the diffusion barrier field.NF membrane is the pressure drive membrane of a kind of separating property between reverse osmosis membrane and milipore filter, its pore diameter range is about several nanometers, lower to monovalent salt and relative molecular weight less than 150 organic molecule rejection, and higher to multivalent salts and relative molecular weight in the rejection of the organic molecule more than 300.Composite nanometer filtering film depends primarily on electrostatic interaction between ion and the film to the cutoff performance of salt.Because its unique separating property and lower operating pressure, NF membrane the separation in fields such as water treatment, dyestuff, biochemical industry, food, environmental protection and concentrated aspect be used widely.
The method for preparing NF membrane has multiple: L-S phase inversion, blending method, lotus electrochemical process and composite algorithm etc.
Composite algorithm is that adopting at most at present also is the most effective method for preparing NF membrane, and this method is the ultrathin functional layer that compound one deck has nano aperture on the porous basement membrane, and basement membrane is as supporting layer, and decision film characteristics and separating property is ultrathin functional layer.The advantage of composite membrane is can choose different materials to produce basement membrane and composite membrane, makes their performance reach optimization respectively.Since the eighties, the commodity NF membrane series of exploitation mainly contains NF, NTR, UTC, ATF, MPT, SU, Desal-5 and A-15 film etc. in succession in the world from eighties of last century.China's NF membrane research starts from eighties of last century beginning of the nineties, units such as Tsing-Hua University, Fudan University, Dalian University of Technology, Beijing University of Chemical Technology, National Bureau of Oceanography's water treatment centers have all carried out number of research projects, obtained certain progress, but great majority still are in laboratory stage.Present commercial NF membrane mainly is a rolling, mainly adopts the method for interfacial polymerization to form the complex function layer.The membrane material of NF membrane is substantially the same with the membrane material of counter-infiltration.The membrane material of commercialization NF membrane mainly contains following several at present: cellulose acetate (CA), SPSF (SPS), sulfonated polyether sulfone (SPES), polyamide (PA), polysulfones (PSU), Kynoar (PVDF) and polyvinyl alcohol (PVA) etc.
Usually, the key step that adopts interfacial polymerization to prepare composite membrane comprises:
1) support membrane is immersed aqueous phase solution (being generally the aqueous solution of polynary amine) a period of time;
2) drain the globule on support membrane surface, and immerse organic solution (being generally the organic solution of polynary acyl chlorides) a period of time;
3) through obtaining NF membrane after post processing, the oven dry.
Adopt the NF membrane surface of method for preparing generally all electronegative, removal efficiency to monovalent ion can be very not high, and the electronegative NF membrane in this film surface is also easier to be contaminated, cause flux sharply decay at short notice, can increase the cleaning frequency of membrane component, increase cost, also can reduce the life-span of membrane component simultaneously.
Summary of the invention
The objective of the invention is to, a kind of high selectivity composite nanometer filtering film and preparation method thereof is provided.The present invention forms one deck or double-deck function desalination layer with high selectivity by the method for utilizing interfacial polymerization and surface-coated on porous support layer, and when guaranteeing higher water flux and salt rejection rate, has prolonged the service life of membrane component.
Technical scheme of the present invention: a kind of high selectivity composite nanometer filtering film, comprise nonwoven layer and high-molecular porous supporting layer, be characterized in: one deck or the double-deck polyamide surface layer made from polyamine and/or polyhydric alcohol amine and polynary acyl chloride reaction are arranged on porous support layer.
Described porous support layer is one or more the mixture in polysulfones porous support layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, Kynoar porous support layer, the polyvinylpyrrolidone.
Whole or (1) during the preparation method of above-mentioned high selectivity composite nanometer filtering film may further comprise the steps, (2) and (4):
(1) porous support layer is contacted with the A solution of the compound that contains two reactive amino at least;
(2) remove the top layer excessive solution, this supporting layer is contacted with the B solution that contains two multi-functional chloride compounds of reactive acid chloride group at least, form polyamide surface layer;
(3) treat the top layer solvent evaporates after, contact with the C solution of the compound that contains at least two reactive amino, form second layer polyamide surface layer;
(4) after post processing, oven dry, obtain composite nanometer filtering film.
The contained compound that has two reactive amino at least is one or more in aromatic series, aliphatic, alicyclic polyfunctional amine, the polyhydric alcohol amine in aforementioned A solution or the C solution.
Described aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2, at least a in 4-diamino anisole, amidol, the xyxylene diamines; Described aliphatic polyfunctional amine is at least a in ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-aminoethyl) amine, diethylenetriamine, N-(2-ethoxy) ethylenediamine, the hexamethylene diamine; Described alicyclic polyfunctional amine is 1,3-DACH, 1,2-DACH, 1,4-DACH, piperazine, 1, at least a in the two piperidyl propane of 3-, the 4-amino methyl piperazine; Described polyhydric alcohol amine is at least a in monoethanolamine, diethanol amine, hexylene glycol amine, the diglycolamine.
It is contained in the aforementioned B solution that to have two multi-functional chloride compounds of reactive acid chloride group at least be in aromatic series, aliphatic, the alicyclic multifunctional chloride compounds one or more.
The multifunctional chloride compounds of described aromatic series is at least a in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, the pyromellitic trimethylsilyl chloride; The multifunctional chloride compounds of described aliphatic is at least a in fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, adipyl chlorine, sebacoyl chloride, the last of the ten Heavenly stems three acyl chlorides; Described alicyclic multifunctional chloride compounds is at least a in 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, oxolane diacid chloride, oxolane four acyl chlorides.
The time that porous support layer contacts with A solution is 5s～300s, and the time that contacts with B solution is 5s～300s, and the time that contacts with C solution is 5s～300s.
Respectively contain weight percent concentration in aforementioned A solution, the C solution and be 0.1%～5% surfactant, at least a compound at least a compound among 0.1%～10% isopropyl alcohol, '-biphenyl diphenol, the DMSO and 0.1%～3% triethylamine, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, the potassium hydroxide.
The compound method of aforementioned A solution or C solution is: get aromatic series, aliphatic, in alicyclic polyfunctional amine and/or the polyhydric alcohol amine one or more are dissolved in the water, its total concentration by weight in the aqueous solution is 0.1%～5%, after treating that polyfunctional amine and/or polyhydric alcohol amine are dissolved in water fully, in the aqueous solution, add percentage by weight again and be 0.1%～5% surfactant, 0.1%～10% isopropyl alcohol, '-biphenyl diphenol, at least a compound among the DMSO and 0.1%～3% triethylamine, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, at least a compound in the potassium hydroxide, after the stirring and dissolving promptly.Be that A solution is identical with the compound method of C solution among the present invention, but the contained reactive amino compound of C solution can be identical with the contained reactive amino compound of A solution, also can be different; Equally, though the weight percent concentration of reactive amino compound is all in 0.1%～5% scope in A solution and the C solution, both concentration can be identical, also can be different.
Described surfactant is at least a compound in lauryl sodium sulfate, neopelex, N-methyl pyrrolidone, the dodecyl sodium sulfate.
The compound method of aforementioned B solution is: get in aromatic series, aliphatic, the alicyclic multifunctional chloride compounds one or more, according to gross mass percentage is that 0.05%～5% ratio is dissolved in one or more compounds in the aliphatic hydrocarbon that contains 4～12 carbon atoms, cycloalphatic hydrocarbon, the aromatic hydrocarbon, after the stirring and dissolving promptly.
Post processing described in the step (4), furnace drying method are: with formed polyamide surface layer film weight concentration be 1.0%～15%, temperature is that 40～90 ℃ acid solution soaked 1～60 minute, wash unnecessary acid off with clear water then, be 1%～20% glycerine with weight concentration again or be respectively 1%～20% camphorsulfonic acid and the mixed solution of triethylamine soaked 1～30 minute with weight concentration, at last this film is placed on temperature and is in 30～120 ℃ the baking oven and kept 5 minutes, form the finished product composite nanometer filtering film.
Prepared individual layer of the present invention or double-layer polyamide surface layer composite nanometer filtering film, under the test condition of the 2000ppmNaCl aqueous solution, 75psi operating pressure, 25 ℃ of temperature, pH value 6.5～7.5, the NaCl removal efficiency is 40～95%, and water flux is at 10～40GFD; At 2000ppmMgSO
4Under the 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 one deck or double-layer polyamide surface layer by utilize interfacial polymerization on porous support layer, has increased the thickness on NF membrane top layer, makes the film surface more smooth, more hydrolysis, resistance to oxidation and scratch resistance are hindered, and have also improved the anti-fouling performance of film; And the film surface can electronegative or positive charge, thereby 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 guarantees to have prolonged the service life of membrane component in higher water flux and the salt rejection rate under lower pressure.
Description of drawings:
Fig. 1 is the surface texture sem photograph of the embodiment of the invention 1 obtained composite nanometer filtering film;
Fig. 2 is the section structure sem photograph of the embodiment of the invention 1 obtained composite nanometer filtering film.
The specific embodiment
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 A solution: get the 9g Piperazine anhydrous and be dissolved in that to be made into weight concentration in the 985g water be 0.9% solution, after treating dissolving fully, in this solution, add anhydrous sodium phosphate 3g (weight concentration 0.3%), neopelex 3g (weight concentration 0.3%) again, obtain A solution after stirring and dissolving is complete.
(2) preparation of B solution: get the 26.7g pyromellitic trimethylsilyl chloride and be dissolved in that to be made into weight concentration in the 973.3g ethyl cyclohexane be 2.6% solution, treat to obtain B solution after the dissolving fully.
(3) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat that fully the back is 6% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 5 minutes again, and oven dry obtains composite nanometer filtering film in 80 ℃ of baking ovens at last.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 2: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution, B solution is with embodiment 1.
(2) preparation of C solution: with the preparation of A solution.
(3) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat to be immersed in after solvent evaporates is done 20s formation second layer aramid layer in the C solution, be 6% in weight concentration afterwards, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 5 minutes again, kept 5 minutes in 80 ℃ of baking ovens at last, obtained composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 3: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution, B solution is with embodiment 1.
(2) preparation of C solution: get the 5g m-phenylene diamine (MPD) and be dissolved in that to be made into weight concentration in the 989g water be 0.5% solution, after treating dissolving fully, in this solution, add anhydrous sodium phosphate 3g (weight concentration 0.3%), N-methyl pyrrolidone 3g (weight concentration 0.3%) again, obtain C solution after stirring and dissolving is complete.
(3) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat to be immersed in after solvent evaporates is done 15s formation second layer aramid layer in the C solution, be 6% in weight concentration afterwards, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, soaked 5 minutes with 4% glycerine again, in 80 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 4: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution: get 6g Piperazine anhydrous and 3g m-phenylene diamine (MPD) respectively and be dissolved in the 985g water, after treating dissolving fully, in this solution, add natrium carbonicum calcinatum 3g (weight concentration 0.3%), neopelex 3g (weight concentration 0.3%) again, obtain A solution after stirring and dissolving is complete.
(2) preparation of B solution is with embodiment 1.
(3) porous support layer is immersed in 30s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 20s with B solution then, treat that fully the back is 6% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 5 minutes again, in 50 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 5: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution is with embodiment 1.
(2) preparation of B solution: get 13g pyromellitic trimethylsilyl chloride and 20g m-phthaloyl chloride respectively and be dissolved in the 967g ethyl cyclohexane, obtain B solution after stirring and dissolving is complete.
(3) porous support layer is immersed in 40s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 30s with B solution then, treat that fully the back is 6% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 6% soaked 5 minutes again, in 80 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 6: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution: get the 25g m-phenylene diamine (MPD) and be dissolved in that to be made into weight concentration in the 955g water be 2.5% solution, after treating dissolving fully, in this solution, add anhydrous sodium phosphate 5g (weight concentration 0.5%), N-methyl pyrrolidone 5g (weight concentration 0.5%), isopropyl alcohol 10g (weight concentration 1%) again, obtain A solution after stirring and dissolving is complete.
(2) preparation of B solution: get in the mixed solvent that 1g m-phthaloyl chloride and 0.5g pyromellitic trimethylsilyl chloride be dissolved in 6.5g dimethylbenzene and 992g ethyl cyclohexane, stirring and dissolving obtains B solution after fully.
(3) porous support layer is immersed in 60s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 60s with B solution then, treat that fully the back is 6% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 5 minutes again, in 100 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 7: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution, B solution, C solution is with embodiment 2.
(2) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat to be immersed in after solvent evaporates is done 10s formation second layer aramid layer in the C solution, be 2% in weight concentration afterwards, temperature is to soak 30 minutes in 75 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 8% triethylamine and 10% soaked 5 minutes again, kept 5 minutes in 80 ℃ of baking ovens at last, obtained composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 8: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution, B solution, C solution is with embodiment 2.
(2) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat to be immersed in after solvent evaporates is done 60s formation second layer aramid layer in the C solution, be 6% in weight concentration afterwards, temperature is to soak 10 minutes in 80 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 20 minutes again, kept 5 minutes in 80 ℃ of baking ovens at last, obtained composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 9: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution: get the 9g Piperazine anhydrous and be dissolved in that to be made into weight concentration in the 980g water be 0.9% solution, after treating dissolving fully, in this solution, add no water sodium hydroxide 3g (weight concentration 0.3%), neopelex 3g (weight concentration 0.3%), isopropyl alcohol 5g (weight concentration 0.5%) again, obtain A solution after stirring and dissolving is complete.
(2) preparation of B solution is with embodiment 1.
(3) porous support layer is immersed in 10s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 50s with B solution then, treat that fully the back is 10% in weight concentration to solvent evaporates, temperature is to soak 20 minutes in 50 ℃ the citric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 10 minutes again, in 80 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 10: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution is with embodiment 1.
(2) preparation of B solution is with embodiment 1.
(3) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 15s with B solution then, treat that fully the back is 6% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 80 ℃ the sulfuric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, soaked 5 minutes with 8% glycerine again, in 80 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
Embodiment 11: prepare composite nanometer filtering film according to the following steps:
(1) preparation of A solution: get the 9g Piperazine anhydrous and be dissolved in that to be made into weight concentration in the 985g water be 0.9% solution, after treating dissolving fully, in this solution, add anhydrous sodium phosphate 3g (weight concentration 0.3%), neopelex 3g (weight concentration 0.3%) again, obtain A solution after stirring and dissolving is complete.
(2) preparation of B solution: get the 26.7g pyromellitic trimethylsilyl chloride and be dissolved in that to be made into weight concentration in the 973.3g ethyl cyclohexane be 2.6% solution, treat to obtain B solution after the dissolving fully.
(3) porous support layer is immersed in 20s in the A solution, draining to the film surface and the back side does not have the obvious globule; Contact 10s with B solution then, treat that fully the back is 4% in weight concentration to solvent evaporates, temperature is to soak 10 minutes in 70 ℃ the sulfuric acid solution, soaked 5 minutes with pure water again, clean unnecessary acid, camphorsulfonic acid mixed solution with 2% triethylamine and 4% soaked 15 minutes again, in 80 ℃ of baking ovens, kept 5 minutes at last, obtain composite nanometer filtering film.
Get diaphragm in the test of diaphragm monitor station, under the test condition of operating pressure 75psi, 25 ℃ of temperature, pH value 6.5～7.5,2000ppmNaCl aqueous solution NaCl removal efficiency and water flux, 2000ppmMgSO
4Aqueous solution MgSO
4Removal efficiency and water flux see Table 1.
The water flux and the removal efficiency of each embodiment gained NF membrane of table 1
Claims (13)
1. a high selectivity composite nanometer filtering film comprises nonwoven layer and high-molecular porous supporting layer, it is characterized in that: one deck or the double-deck polyamide surface layer made from polyamine and/or polyhydric alcohol amine and polynary acyl chloride reaction are arranged on porous support layer.
2. high selectivity composite nanometer filtering film according to claim 1 is characterized in that: described porous support layer is one or more the mixture in polysulfones porous support layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, Kynoar porous support layer, the polyvinylpyrrolidone.
3. the preparation method of high selectivity composite nanometer filtering film as claimed in claim 1 or 2 is characterized in that: whole or (1) in may further comprise the steps, (2) and (4):
(1) porous support layer is contacted with the A solution of the compound that contains two reactive amino at least; (2) remove the top layer excessive solution, this supporting layer is contacted with the B solution that contains two multi-functional chloride compounds of reactive acid chloride group at least, form polyamide surface layer; (3) treat the top layer solvent evaporates after, contact with the C solution of the compound that contains at least two reactive amino, form second layer polyamide surface layer; (4) after post processing, oven dry, obtain composite nanometer filtering film.
4. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 3, it is characterized in that: the contained compound that has two reactive amino at least is one or more in aromatic series, aliphatic, alicyclic polyfunctional amine, the polyhydric alcohol amine in A solution or the C solution.
5. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 4, it is characterized in that: described aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2, at least a in 4-diamino anisole, amidol, the xyxylene diamines; Described aliphatic polyfunctional amine is at least a in ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-aminoethyl) amine, diethylenetriamine, N-(2-ethoxy) ethylenediamine, the hexamethylene diamine; Described alicyclic polyfunctional amine is 1,3-DACH, 1,2-DACH, 1,4-DACH, piperazine, 1, at least a in the two piperidyl propane of 3-, the 4-amino methyl piperazine; Described polyhydric alcohol amine is at least a in monoethanolamine, diethanol amine, hexylene glycol amine, the diglycolamine.
6. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 3, it is characterized in that: contained in the B solution to have two multi-functional chloride compounds of reactive acid chloride group at least be in aromatic series, aliphatic, the alicyclic multifunctional chloride compounds one or more.
7. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 6, it is characterized in that: the multifunctional chloride compounds of described aromatic series is at least a in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, the pyromellitic trimethylsilyl chloride; The multifunctional chloride compounds of described aliphatic is at least a in fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, adipyl chlorine, sebacoyl chloride, the last of the ten Heavenly stems three acyl chlorides; Described alicyclic multifunctional chloride compounds is at least a in 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, oxolane diacid chloride, oxolane four acyl chlorides.
8. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 3, it is characterized in that: the time that porous support layer contacts with A solution is 5s～300s, and the time that contacts with B solution is 5s～300s, and the time that contacts with C solution is 5s～300s.
9. according to the preparation method of the described high selectivity composite nanometer filtering film of claim 3, it is characterized in that: respectively contain weight percent concentration in A solution, the C solution and be 0.1%～5% surfactant, at least a compound at least a compound among 0.1%～10% isopropyl alcohol, '-biphenyl diphenol, the DMSO and 0.1%～3% triethylamine, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, the potassium hydroxide.
10. according to claim 3,4, the preparation method of 5 or 9 described high selectivity composite nanometer filtering films, it is characterized in that: the compound method of A solution or C solution is: get aromatic series, aliphatic, in alicyclic polyfunctional amine and/or the polyhydric alcohol amine one or more are dissolved in the water, its total concentration by weight in the aqueous solution is 0.1%～5%, after treating that polyfunctional amine and/or polyhydric alcohol amine are dissolved in water fully, in the aqueous solution, add percentage by weight again and be 0.1%～5% surfactant, 0.1%～10% isopropyl alcohol, '-biphenyl diphenol, at least a compound among the DMSO and 0.1%～3% triethylamine, sodium carbonate, sodium acid carbonate, sodium phosphate, NaOH, at least a compound in the potassium hydroxide, after the stirring and dissolving promptly.
11. the preparation method according to the described high selectivity composite nanometer filtering film of claim 10 is characterized in that: described surfactant is at least a compound in lauryl sodium sulfate, neopelex, N-methyl pyrrolidone, the dodecyl sodium sulfate.
12. preparation method according to claim 3,6 or 7 described high selectivity composite nanometer filtering films, it is characterized in that: the compound method of B solution is: get in aromatic series, aliphatic, the alicyclic multifunctional chloride compounds one or more, according to gross mass percentage is that 0.05%～5% ratio is dissolved in one or more compounds in the aliphatic hydrocarbon that contains 4～12 carbon atoms, cycloalphatic hydrocarbon, the aromatic hydrocarbon, after the stirring and dissolving promptly.
13. preparation method according to the described high selectivity composite nanometer filtering film of claim 3, it is characterized in that: the post processing in the step (4), furnace drying method is: with formed polyamide surface layer film weight concentration is 1.0%～15%, temperature is that 40～90 ℃ acid solution soaked 1～60 minute, wash unnecessary acid off with clear water then, be 1%～20% glycerine with weight concentration again or be respectively 1%～20% camphorsulfonic acid and the mixed solution of triethylamine soaked 1～30 minute with weight concentration, at last this film is placed on temperature and is in 30～120 ℃ the baking oven and kept 5 minutes, form the finished product composite nanometer filtering film.
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Application publication date: 20110105 |