CN103084081B - Preparation method of large-flux amphiprotic nano-filtration membrane - Google Patents
Preparation method of large-flux amphiprotic nano-filtration membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a large-flux amphiprotic nano-filtration membrane. A preparation method of the conventional nano-filtration membrane mainly comprises a phase transferring method and a compounding method, and the membrane with the very large flux is difficult to obtain. The method comprises the following steps of: washing the nano-filtration membrane by utilizing ethanol and de-ionized water; then immersing the washed nano-filtration membrane in an olefins cation monomer solution and irradiating under a 100-600W ultraviolet lamp for 3-120 minutes to obtain a cation nano-filtration membrane; washing the cation nano-filtration membrane by using the de-ionized water and then immersing the cation nano-filtration membrane into an amphiprotic olefins monomer solution; irradiating under the 100-600W ultraviolet lamp for 2-40 minutes to obtain the amphiprotic nano-filtration membrane; and finally, washing the amphiprotic nano-filtration membrane by using the de-ionized water. The amphiprotic nano-filtration membrane prepared by using the method disclosed by the invention has the water flux of 55-200L/m<2>h under 0.5MPa and the reject rates of the amphiprotic nano-filtration membrane to sodium chloride, MgCl2 and MgSO4 are respectively 40-85%, 80-97% and 60-63%. The method disclosed by the invention has a simple and reliable preparation process and is applied to industrialization.
Description
Technical field
The invention belongs to technical field of membrane separation, relate to a kind of preparation method of large flux both sexes NF membrane.
Background technology
NF membrane is the pressure drive membrane of a kind of performance between ultrafiltration and counter-infiltration.NF membrane has following feature: molecular cut off, between 200 ~ 1000Da, is suitable for the dissolved constituent removing about about 1nm; Operating pressure is low, lower than the pressure required by counter-infiltration, therefore also referred to as " low-pressure reverse osmosis membrane "; There is ion selectivity, the feature that of NF membrane is very large is that membrane body is with electric charge, pass through electrostatic interaction, the divalence in the aqueous solution and multivalent ion can be removed, to the rejection of divalence and multivalent ion at 90 more than ﹪, 80 ﹪ are less than to the rejection of monovalent ion, therefore can realize the separation of different valence state ion.Because NF membrane has above feature, therefore the industry-by-industries such as environmental protection, water resource, food, medicine and chemical industry are widely used in.
The preparation method of NF membrane can be divided into phase inversion and composite algorithm two kinds.It is simple to operate, easy that phase inversion prepares NF membrane, but it is most important to choose suitable membrane material, the film of the more difficult directly obtained small-bore of traditional macromolecule member material.Composite algorithm is prepared NF membrane and is mainly comprised two steps: the first step is the preparation of micropore basal membrane; Second step is the preparation on ultra-thin top layer, and main method has coating process, interfacial polymerization, heat, light, crosslinking with radiation solidification method, Plasma Polymerization etc.Wherein, the key of coating process is the complex liquid selecting to match with basement membrane, but complex liquid and basement membrane are physisorptions, and when cleaning, complex liquid can run off, and loses the function of nanofiltration.Interfacial polymerization is with the very high monomer of two kinds of reactivities, at two mutual exclusive interface polymerization reaction take places, thus forms thin layer on how empty supporter.This method Chinese patent (CN102423643A) is utilized to utilize the interface polycondensation between the sericin aqueous solution and the organic solution containing aromatic polycarboxylic acyl chlorides to prepare a kind of high throughput anion composite nanometer filtering film; Chinese patent (CN1636626A) obtains nanofiltration film by the interfacial polymerization of terminated polyamidoamines and polyphenyl three formyl chloride organic solution, this film under 0.6MPa water flux at 38.3 ~ 56.8L/m
2between h, to the rejection of 1000mg/L sodium chloride between 41.8 ~ 53.8 ﹪; But this method choosing and preparing basement membrane, regulates and controls distribution coefficient and the diffusion velocity of two class reactants, and optimize boundary condition, make the conditional requests such as top layer porousness rationalization all harsher.Chinese patent (CN101766962A) utilizes the coating of process more complicated to be combined with heat cross-linking solidification method the NF membrane preparing lotus positive electricity, and this film water flux under 0.6MPa is 12 ~ 18L/m
2h, is generally 75 ~ 95 ﹪ to the rejection of bivalent cation, to the rejection of monovalent cation lower than 65 ﹪.Compared with the preparation method of above various NF membrane, due to uv photo initiated grafting method, to have preparation technology simple, reacts the feature such as controlled, and can only change the surface nature of film, can not change the character of basement membrane, hydrophily NF membrane prepared by this method still has good stability in water.Wherein Chinese patent (CN102247771A) respectively with containing sulfonic vinyl monomer and the vinyl monomer containing hydroxyl or carboxyl for monomer adopts the method for ultraviolet irradiation substep grafting to prepare a kind of nanofiltration membrane with negative electric charge, this film flux under 0.4MPa is 28.3 ~ 36.6L/m
2h is 94.8 ~ 97.9 ﹪ to the rejection of sodium sulphate, is 60.2 ~ 65.3 ﹪ to the rejection of sodium chloride, but lower to the salting liquid rejection of high-valence cationic; Chinese patent (CN101934204A) utilizes ultraviolet irradiation to divide step grafting method with polyether-ether-ketone milipore filter for basement membrane obtains both sexes NF membrane, and this film is to bivalent cation (MgCl
2) and dianion (Na
2sO
4) salting liquid all has higher rejection all at 90 more than ﹪, but the flux ratio of this film is lower, and under 0.4MPa, flux only has 3.2 ~ 9.6L/m
2h.
By analyzing the preparation method of above various NF membrane, find that utilizing ultraviolet irradiation Graft Method to prepare NF membrane becomes a kind of masking technique with potential using value, utilize the large flux polysulphone super-filter membrane of modification to prepare large flux NF membrane as basement membrane then do not report by ultraviolet irradiation Graft Method.
Summary of the invention
Object of the present invention, for the deficiencies in the prior art, provides a kind of preparation method of large flux both sexes NF membrane.
The present invention utilizes milipore filter for basement membrane, adopts ultraviolet irradiation Graft Method to prepare large flux both sexes NF membrane.
The concrete steps of the inventive method are:
Step (1). by milipore filter ethanol washing 1 ~ 10 time, then spend deionized water 5 ~ 20 times, remove film surface impurity;
The material of described milipore filter be polysulfones (PSF), polyether-ketone (PEK), polyether sulfone (PES) one or more;
As preferably, milipore filter ethanol washing 4 ~ 7 times;
As preferably, milipore filter spends deionized water 10 ~ 15 times;
Step (2). the milipore filter after washing is soaked in olefines cation mono liquid solution, the film upper surface of milipore filter and the liquid surface distance of olefines cation mono liquid solution are 1 ~ 5mm, irradiation 3 ~ 120 minutes under 100 ~ 600W uviol lamp, the film upper surface of milipore filter and the distance of uviol lamp are 5 ~ 40cm, obtain cation NF membrane;
The aqueous solution of described olefines cation mono liquid solution to be mass fraction be 1 ~ 65 ﹪ olefines cationic monomer or methanol solution or ethanolic solution;
Described olefines cationic monomer is the alkene containing quaternary ammonium salt or tertiary amine groups;
The high-pressure sodium lamp of described uviol lamp to be wavelength be 290 ~ 400nm, reacts in air at 10 ~ 30 DEG C;
As preferably, in olefines cation mono liquid solution, the mass content of olefines cationic monomer is 5 ~ 50 ﹪;
As preferably, the power of uviol lamp is 300 ~ 500W, and the ultraviolet irradiation time is 5 ~ 30min, and the film upper surface of milipore filter and the distance of uviol lamp are 10 ~ 30cm;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 5 ~ 10 times, except the olefines cationic monomer of striping surface residual, then the cation NF membrane after washing is soaked in both sexes olefin monomer solution, the film upper surface of cation NF membrane and the liquid surface distance of both sexes olefin monomer solution are 1 ~ 5mm, irradiation 2 ~ 40min under 100 ~ 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 5 ~ 40cm, obtain both sexes NF membrane;
The aqueous solution of described both sexes olefin monomer solution to be mass fraction be 1 ~ 30 ﹪ both sexes olefin monomer or methanol solution or ethanolic solution;
Described both sexes olefin monomer is the alkene containing amphiprotic group; In both sexes olefin monomer negative group be sulfonic group, carboxyl one or both, positive group be quaternary ammonium salt, tertiary amine groups one or both;
As preferably, in both sexes olefin monomer solution, the mass content of both sexes olefin monomer is 5 ~ 20 ﹪;
As preferably, the power of uviol lamp is 300 ~ 500W, and the ultraviolet irradiation time is 10 ~ 30min, and the film upper surface of cation NF membrane and the distance of uviol lamp are 10 ~ 30cm;
Step (4). the both sexes NF membrane obtained is spent deionized water 10 ~ 20 times, except the both sexes olefin monomer of striping surface residual.
Described film upper surface is used to control radiation intensity to the power of the Distance geometry uviol lamp of uviol lamp.
The performance of the both sexes NF membrane prepared by the present invention controls by changing exposure time, monomer concentration and radiation intensity.Controlled the charge species on NF membrane surface by the kind changing grafted monomers, the character of both sexes NF membrane is changed in the larger context, obtains both sexes charged nanofiltration membrane high-valence cationic and high-valence anion being had to very high rejection.
The both sexes NF membrane prepared by the inventive method water flux under 0.5MPa is 55 ~ 200L/m
2h is 40 ~ 85 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 80 ~ 97 ﹪, to MgSO
4rejection be 60 ~ 93 ﹪.
The inventive method preparation technology is simple and reliable, is applicable to suitability for industrialized production.
Detailed description of the invention
For further analysis to the present invention below in conjunction with embodiment.
Embodiment 1.
Step (1). polysulphone super-filter membrane ethanol is washed 1 time, then spends deionized water 8 times, remove film surface impurity;
Step (2). it is in the aqueous solution of 1 ﹪ 4-vinylpridine that the polysulphone super-filter membrane after washing is soaked in mass fraction, the film upper surface of polysulphone super-filter membrane and mass fraction are the aqueous liquid surface distance of 1 ﹪ 4-vinylpridine is 1mm, irradiation 120 minutes under 100W uviol lamp, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 5cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 5 times, except the 4-vinylpridine of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the aqueous solution of 1 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the aqueous liquid surface distance of 1 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 1mm, irradiation 40min under 100W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 5cm, obtain both sexes NF membrane;
Step (4). the both sexes NF membrane obtained is spent deionized water 10 times, except the 2-vinylpyridine propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 1 prepares water flux under 0.5MPa is 200L/m
2h is 40 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 80 ﹪, to MgSO
4rejection be 60 ﹪.
Embodiment 2.
Step (1). polyether-ketone milipore filter ethanol is washed 2 times, then spends deionized water 10 times, remove film surface impurity;
Step (2). it is in the aqueous solution of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums that the polyether-ketone milipore filter after washing is soaked in mass fraction, the film upper surface of polyether-ketone milipore filter and mass fraction are the aqueous liquid surface distance of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums is 1.5mm, irradiation 110 minutes under 150W uviol lamp, the film upper surface of polyether-ketone milipore filter and the distance of uviol lamp are 8cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 6 times, except the 3-methacryiamidopropyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the aqueous solution of the m-vinyl of 5 ﹪-o-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the aqueous liquid surface distance of the m-vinyl of 5 ﹪-o-picoline propyl sulfonic acid salt is 1.5mm, irradiation 38min under 150W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 8cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 11 times, except the m-vinyl-o-picoline propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 2 prepares water flux under 0.5MPa is 180L/m
2h is 48.7 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 82.1 ﹪, to MgSO
4rejection be 63.2 ﹪.
Embodiment 3.
Step (1). poly (ether-sulfone) ultrafiltration membrane ethanol is washed 3 times, then spends deionized water 9 times, remove film surface impurity;
Step (2). it is in the aqueous solution of 30 ﹪ diallyldimethylammonium chlorides that the poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and mass fraction are the aqueous liquid surface distance of 30 ﹪ diallyldimethylammonium chlorides is 2mm, irradiation 90 minutes under 180W uviol lamp, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 10cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 7 times, except the diallyldimethylammonium chloride of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the aqueous solution of 10 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the aqueous liquid surface distance of 10 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt is 2mm, irradiation 35min under 180W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 10cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 12 times, except the acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 3 prepares water flux under 0.5MPa is 100L/m
2h is 65.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 85.9 ﹪, to MgSO
4rejection be 72.7 ﹪.
Embodiment 4.
Step (1). polysulfones/polyether-ketone milipore filter ethanol is washed 4 times, then spends deionized water 5 times, remove film surface impurity;
Step (2). it is in the aqueous solution of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides that the polysulfones/polyether-ketone milipore filter after washing is soaked in mass fraction, the film upper surface of polysulfones/polyether-ketone milipore filter and mass fraction are the aqueous liquid surface distance of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is 2.5mm, irradiation 80 minutes under 200W uviol lamp, the film upper surface of polysulfones/polyether-ketone milipore filter and the distance of uviol lamp are 12cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 8 times, except the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of striping surface residual, then the cation NF membrane after washing being soaked mass fraction is in the aqueous solution of 20 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the aqueous liquid surface distance of 20 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt is 2mm, irradiation 32min under 200W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 12cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 13 times, except the 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 4 prepares water flux under 0.5MPa is 72L/m
2h is 78.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 89.5 ﹪, to MgSO
4rejection be 82.3 ﹪.
Embodiment 5.
Step (1). polysulfones/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 5 times, then spends deionized water 6 times, remove film surface impurity;
Step (2). it is in the aqueous solution of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums that the polysulfones/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and mass fraction are the aqueous liquid surface distance of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums is 3mm, irradiation 70 minutes under 250W uviol lamp, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 15cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 9 times, except the 3-acrylamido-3-methyl butyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the aqueous solution of 30 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the aqueous liquid surface distance of 30 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt is 3mm, irradiation 28min under 250W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 15cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 14 times, except the 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 5 prepares water flux under 0.5MPa is 65L/m
2h is 80.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 91.4 ﹪, to MgSO
4rejection be 87.2 ﹪.
Embodiment 6.
Step (1). polyether-ketone/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 6 times, then spends deionized water 7 times, remove film surface impurity;
Step (2). it is in the methanol solution of 1 ﹪ 4-vinylpridine that the polyether-ketone/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and mass fraction are the methanol solution liquid surface distance of 1 ﹪ 4-vinylpridine is 3.5mm, irradiation 65 minutes under 280W uviol lamp, the film upper surface of milipore filter and the distance of uviol lamp are 20cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 10 times, except the 4-vinylpridine of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the methanol solution of 1 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the methanol solution liquid surface distance of 1 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt is 3.5mm, irradiation 30min under 280W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 20cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 15 times, except the 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 6 prepares water flux under 0.5MPa is 195L/m
2h is 40.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 80.9 ﹪, to MgSO
4rejection be 61.2 ﹪.
Embodiment 7.
Step (1). polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 7 times, then spends deionized water 11 times, remove film surface impurity;
Step (2). it is in the methanol solution of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums that the polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and mass fraction are the methanol solution liquid surface distance of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums is 4mm, irradiation 60 minutes under 300W uviol lamp, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 18cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 5 times, except the 3-methacryiamidopropyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the methanol solution of 5 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the methanol solution liquid surface distance of 5 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 4.5mm, irradiation 25min under 300W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 18cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 16 times, except the 2-vinylpyridine propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 7 prepares water flux under 0.5MPa is 140L/m
2h is 50.4 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 83.2 ﹪, to MgSO
4rejection be 65.3 ﹪.
Embodiment 8.
Step (1). polysulphone super-filter membrane ethanol is washed 8 times, then spends deionized water 12 times, remove film surface impurity;
Step (2). it is in the methanol solution of 20 ﹪ diallyldimethylammonium chlorides that the polysulphone super-filter membrane after washing is soaked in mass fraction, the film upper surface of polysulphone super-filter membrane and mass fraction are the methanol solution liquid surface distance of 20 ﹪ diallyldimethylammonium chlorides is 5mm, irradiation 50 minutes under 350W uviol lamp, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 22cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 6 times, except the diallyldimethylammonium chloride of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the methanol solution of the m-vinyl of 8 ﹪-o-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the methanol solution liquid surface distance of the m-vinyl of 8 ﹪-o-picoline propyl sulfonic acid salt is 5mm, irradiation 22min under 350W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 22cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 17 times, except the m-vinyl-o-picoline propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 8 prepares water flux under 0.5MPa is 85L/m
2h is 67.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 86.4 ﹪, to MgSO
4rejection be 74.5 ﹪.
Embodiment 9.
Step (1). polyether-ketone milipore filter ethanol is washed 9 times, then spends deionized water 14 times, remove film surface impurity;
Step (2). it is in the methanol solution of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides that the polyether-ketone milipore filter after washing is soaked in mass fraction, the film upper surface of polyether-ketone milipore filter and mass fraction are the methanol solution liquid surface distance of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is 2.5mm, irradiation 40 minutes under 380W uviol lamp, the film upper surface of polyether-ketone milipore filter and the distance of uviol lamp are 25cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 7 times, except the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the methanol solution of 20 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the methanol solution liquid surface distance of 20 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt is 2.5mm, irradiation 20min under 380W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 25cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 18 times, except the acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt of striping surface residual.
Implementing the 9 both sexes NF membrane water fluxes under 0.5MPa prepared is 62L/m
2h is 81.2 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 92.5 ﹪, to MgSO
4rejection be 89.4 ﹪.
Embodiment 10.
Step (1). poly (ether-sulfone) ultrafiltration membrane ethanol is washed 10 times, then spends deionized water 15 times, remove film surface impurity;
Step (2). it is in the methanol solution of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums that the poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and mass fraction are the methanol solution liquid surface distance of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums is 3.5mm, irradiation 30 minutes under 400W uviol lamp, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 30cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 8 times, except the 3-acrylamido-3-methyl butyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the methanol solution of 30 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the methanol solution liquid surface distance of 30 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt is 3.5mm, irradiation 18min under 400W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 30cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 19 times, except the 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 10 prepares water flux under 0.5MPa is 55L/m
2h is 85 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 97 ﹪, to MgSO
4rejection be 93 ﹪.
Embodiment 11.
Step (1). polysulfones/polyether-ketone milipore filter ethanol is washed 5 times, then spends deionized water 16 times, remove film surface impurity;
Step (2). it is in the ethanolic solution of 1 ﹪ 4-vinylpridine that the polysulfones/polyether-ketone milipore filter after washing is soaked in mass fraction, the film upper surface of polysulfones/polyether-ketone milipore filter and mass fraction are the ethanolic solution liquid surface distance of 1 ﹪ 4-vinylpridine is 4.5mm, irradiation 100 minutes under 450W uviol lamp, the film upper surface of polysulfones/polyether-ketone milipore filter and the distance of uviol lamp are 32cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 5 ~ 10 times, except the 4-vinylpridine of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the ethanolic solution of 1 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the ethanolic solution liquid surface distance of 1 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt is 4.5mm, irradiation 10min under 450W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 32cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 20 times, except the 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 11 prepares water flux under 0.5MPa is 193L/m
2h is 41.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 81.7 ﹪, to MgSO
4rejection be 61.5 ﹪.
Embodiment 12.
Step (1). polysulfones/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 7 times, then spends deionized water 18 times, remove film surface impurity;
Step (2). it is in the ethanolic solution of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums that the polysulfones/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in mass fraction, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and mass fraction are the ethanolic solution liquid surface distance of 5 ﹪ 3-methacryiamidopropyl trimethyl ammoniums is 4mm, irradiation 10 minutes under 500W uviol lamp, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 35cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 9 times, except the 3-methacryiamidopropyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the ethanolic solution of 5 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the ethanolic solution liquid surface distance of 5 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt is 4mm, irradiation 15min under 500W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 35cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 20 times, except the 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 12 prepares water flux under 0.5MPa is 120L/m
2h is 55.3 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 84.5 ﹪, to MgSO
4rejection be 67.2 ﹪.
Embodiment 13.
Step (1). polyether-ketone/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 9 times, then spends deionized water 20 times, remove film surface impurity;
Step (2). it is in the ethanolic solution of 40 ﹪ diallyldimethylammonium chlorides that the milipore filter after washing is soaked in mass fraction, the film upper surface of milipore filter and mass fraction are the ethanolic solution liquid surface distance of 40 ﹪ diallyldimethylammonium chlorides is 5mm, irradiation 3 minutes under 550W uviol lamp, the film upper surface of milipore filter and the distance of uviol lamp are 38cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 10 times, except the diallyldimethylammonium chloride of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the ethanolic solution of 15 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the ethanolic solution liquid surface distance of 15 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 5mm, irradiation 5min under 550W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 38cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 15 times, except the 2-vinylpyridine propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 13 prepares water flux under 0.5MPa is 77L/m
2h is 72.5 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 88.3 ﹪, to MgSO
4rejection be 80.1 ﹪.
Embodiment 14.
Step (1). polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane ethanol is washed 8 times, then spends deionized water 19 times, remove film surface impurity;
Step (2). the polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the ethanolic solution of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the film upper surface of milipore filter and the ethanolic solution liquid surface distance of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides are 3.5mm, irradiation 3 minutes under 600W uviol lamp, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 40cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 8 times, except the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the ethanolic solution of the m-vinyl of 20 ﹪-o-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the ethanolic solution liquid surface distance of the m-vinyl of 20 ﹪-o-picoline propyl sulfonic acid salt is 2mm, irradiation 2min under 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 40cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 18 times, except the m-vinyl-o-picoline propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 14 prepares water flux under 0.5MPa is 68L/m
2h is 80.1 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 90.8 ﹪, to MgSO
4rejection be 85.7 ﹪.
Embodiment 15.
Step (1). polysulphone super-filter membrane ethanol is washed 6 times, then spends deionized water 17 times, remove film surface impurity;
Step (2). it is in the ethanolic solution of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums that the polysulphone super-filter membrane after washing is soaked in mass fraction, the film upper surface of polysulphone super-filter membrane and mass fraction are the ethanolic solution liquid surface distance of 65 ﹪ 3-acrylamido-3-methyl butyl trimethyl ammoniums is 5mm, irradiation 5 minutes under 600W uviol lamp, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 30cm, obtain cation NF membrane;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 8 times, except the 3-acrylamido-3-methyl butyl trimethyl ammonium of striping surface residual, then the cation NF membrane after washing being soaked in mass fraction is in the ethanolic solution of 30 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are the ethanolic solution liquid surface distance of 30 ﹪ acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt is 5mm, irradiation 30min under 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 30cm, obtain both sexes NF membrane,
Step (4). the both sexes NF membrane obtained is spent deionized water 15 times, except the acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt of striping surface residual.
The both sexes NF membrane that embodiment 15 prepares water flux under 0.5MPa is 57L/m
2h is 83.2 ﹪ to the rejection of sodium chloride, to MgCl
2rejection be 94.3 ﹪, to MgSO
4rejection be 91.7 ﹪.
The wavelength of the uviol lamp that above-described embodiment 1 ~ 15 is used is the high-pressure sodium lamp of 290 ~ 400nm, reacts, carry out in air at 10 ~ 30 DEG C; Film upper surface is used to control radiation intensity to the power of the Distance geometry uviol lamp of uviol lamp.
The strainability of both sexes NF membrane prepared by the present invention is evaluated in instrument at film and is evaluated.Probe temperature is normal temperature, and pressure is 0.5MPa.The strainability of both sexes NF membrane represents (unit: L/m at the water flux of this condition respectively
2h) permeability; With to the 1g/L NaCl aqueous solution, 1g/L MgSO
4the aqueous solution and 1g/L MgCl
2the rejection of the aqueous solution represents that it is selective.
Claims (8)
1. a preparation method for large flux both sexes NF membrane, is characterized in that the method comprises the following steps:
Step (1). by milipore filter ethanol washing 1 ~ 10 time, then spend deionized water 5 ~ 20 times, remove film surface impurity;
Step (2). the milipore filter after washing is soaked in olefines cation mono liquid solution, the film upper surface of milipore filter and the liquid surface distance of olefines cation mono liquid solution are 1 ~ 5mm, irradiation 3 ~ 120 minutes under 100 ~ 600W uviol lamp, the film upper surface of milipore filter and the distance of uviol lamp are 5 ~ 40cm, obtain cation NF membrane;
The aqueous solution of described olefines cation mono liquid solution to be mass fraction be 1 ~ 65 ﹪ olefines cationic monomer or methanol solution or ethanolic solution;
Described olefines cationic monomer is the alkene containing tertiary amine groups;
Step (3). the cation NF membrane obtained after ultra-violet radiation is spent deionized water 5 ~ 10 times, except the olefines cationic monomer of striping surface residual, then the cation NF membrane after washing is soaked in both sexes olefin monomer solution, the film upper surface of cation NF membrane and the liquid surface distance of both sexes olefin monomer solution are 1 ~ 5mm, irradiation 2 ~ 40min under 100 ~ 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 5 ~ 40cm, obtain both sexes NF membrane;
The aqueous solution of described both sexes olefin monomer solution to be mass fraction be 1 ~ 30 ﹪ both sexes olefin monomer or methanol solution or ethanolic solution;
Described both sexes olefin monomer is acrylamidoethyl Dimethyl Ammonium propyl sulfonic acid salt or 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt;
Step (4). the both sexes NF membrane obtained is spent deionized water 10 ~ 20 times, except the both sexes olefines ion monomer of striping surface residual.
2. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, it is characterized in that the material of the milipore filter described in step (1) be polysulfones, polyether-ketone, polyether sulfone one or more.
3. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, is characterized in that the uviol lamp described in step (2) to be wavelength is the high-pressure sodium lamp of 290 ~ 400nm, react at 10 ~ 30 DEG C in air.
4. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, is characterized in that in step (1), milipore filter ethanol washs 4 ~ 7 times, then spends deionized water 10 ~ 15 times.
5. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, it is characterized in that the power of step (2) medium ultraviolet lamp is 300 ~ 500W, the ultraviolet irradiation time is 5 ~ 30min, and the film upper surface of milipore filter and the distance of uviol lamp are 10 ~ 30cm.
6. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, it is characterized in that the power of step (3) medium ultraviolet lamp is 300 ~ 500W, the ultraviolet irradiation time is 10 ~ 30min, and the film upper surface of cation NF membrane and the distance of uviol lamp are 10 ~ 30cm.
7. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 3, is characterized in that the mass content of olefines cationic monomer in olefines cation mono liquid solution is 5 ~ 50 ﹪.
8. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 5, is characterized in that the mass content of both sexes olefin monomer in both sexes olefin monomer solution is 5 ~ 20 ﹪.
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