CN103084081A - 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 the membrane separation technique field, 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 characteristics: molecular cut off is suitable for removing the dissolved constituent of about 1nm left and right between 200～1000Da; Operating pressure is low, and is lower than the desired pressure of counter-infiltration, therefore also referred to as " low-pressure reverse osmosis membrane "; Has ion selectivity, a very large feature of NF membrane is that membrane body is with electric charge, pass through electrostatic interaction, can remove divalence and multivalent ion in the aqueous solution, to the rejection of divalence and multivalent ion more than 90 ﹪, less than 80 ﹪, therefore can realize the separation of different valence state ion to the rejection of monovalent ion.Because NF membrane has above characteristics, the industry-by-industries such as environmental protection, water resource, food, medicine and chemical industry therefore have been widely used in.
The preparation method of NF membrane can be divided into two kinds of phase inversion and composite algorithms.Phase inversion prepares that NF membrane is simple to operate, easy row, but it is most important to choose suitable membrane material, the more difficult film that directly makes the small-bore of traditional macromolecule member material.Composite algorithm prepares NF membrane and mainly comprised for 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 that selection and basement membrane are complementary, but complex liquid and basement membrane are physisorptions, and complex liquid can run off when cleaning, and loses the function of nanofiltration.Interfacial polymerization is with two kinds of monomers that reactivity is very high, at two mutual exclusive polymerization reaction take places at the interface, thereby forms thin layer on how empty supporter.The interface polycondensation that utilizes this method Chinese patent (CN102423643A) to utilize the sericin aqueous solution and contain between the organic solution of aromatic polycarboxylic acyl chlorides prepares a kind of high flux anion composite nanometer filtering film; Chinese patent (CN1636626A) makes nanofiltration film by the interfacial polymerization of terminated polyamidoamines and polyphenyl three formyl chloride organic solutions, 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 is chosen and prepares basement membrane, and distribution coefficient and the diffusion velocity of regulation and control two class reactants, and optimize boundary condition make the conditional request such as top layer porousness rationalization all harsher.The coating that Chinese patent (CN101766962A) utilizes the process more complicated and heat cross-linking solidification method are combined to prepare the NF membrane of 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 ﹪.Compare with the preparation method of above various NF membrane, to have preparation technology simple due to the uv photo initiated grafting method, reacts the characteristics such as controlled, and can only change the surface nature of film, can not change the character of basement membrane, the hydrophily NF membrane of this method preparation still has good stability in water.Wherein Chinese patent (CN102247771A) has prepared a kind of nanofiltration membrane with negative electric charge with the vinyl monomer that contains hydroxyl or carboxyl as monomer adopts the method for ultraviolet irradiation substep grafting to contain sulfonic vinyl monomer respectively, and 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 to make the both sexes NF membrane take the polyether-ether-ketone milipore filter as basement membrane, and this film is to bivalent cation (MgCl
2) and dianion (Na
2SO
4) salting liquid all has higher rejection all more than 90 ﹪, but the flux ratio of this film is lower, and flux only has 3.2～9.6L/m under 0.4MPa
2h。
Analyze by the preparation method to above various NF membrane, discovery utilizes the ultraviolet irradiation Graft Method to prepare NF membrane becomes a kind of masking technique with potential using value, utilizes the large flux polysulphone super-filter membrane of modification to prepare large flux NF membrane less than report as basement membrane by the ultraviolet irradiation Graft Method.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of large flux both sexes NF membrane for the deficiencies in the prior art.
The present invention utilizes milipore filter to be basement membrane, adopts the ultraviolet irradiation Graft Method to prepare large flux both sexes NF membrane.
The concrete steps of the inventive method are:
Step (1). milipore filter with ethanol washing 1～10 time, then with deionized water washing 5～20 times, is removed the film surface impurity;
The material of described milipore filter is one or more of polysulfones (PSF), polyether-ketone (PEK), polyether sulfone (PES);
As preferably, milipore filter is with ethanol washing 4～7 times;
As preferably, milipore filter is with deionized water washing 10～15 times;
Step (2). the milipore filter after washing is soaked in olefines cation mono liquid solution, the liquid surface distance of the film upper surface of milipore filter and olefines cation mono liquid solution is 1～5mm, under 100～600W uviol lamp, irradiation is 3～120 minutes, the film upper surface of milipore filter and the distance of uviol lamp are 5～40cm, obtain the cation NF membrane;
Described olefines cation mono liquid solution is that mass fraction is the aqueous solution or methanol solution or the ethanolic solution of 1～65 ﹪ olefines cationic monomer;
Described olefines cationic monomer is the alkene that contains quaternary ammonium salt or tertiary amine groups;
Described uviol lamp is that wavelength is the high-pressure sodium lamp of 290～400nm, reacts in 10～30 ℃ of lower air;
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 that obtains after ultra-violet radiation is washed 5～10 times with deionized water, except the remaining olefines cationic monomer in striping surface, then the cation NF membrane after washing is soaked in both sexes olefin monomer solution, the liquid surface distance of the film upper surface of cation NF membrane and both sexes olefin monomer solution is 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 the both sexes NF membrane;
Described both sexes olefin monomer solution is that mass fraction is the aqueous solution or methanol solution or the ethanolic solution of 1～30 ﹪ both sexes olefin monomer;
Described both sexes olefin monomer is the alkene that contains amphiprotic group; In the both sexes olefin monomer, negative group is one or both of sulfonic group, carboxyl, and positive group is one or both of quaternary ammonium salt, tertiary amine groups;
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 that obtains is washed 10～20 times with deionized water, except the remaining both sexes olefin monomer in striping surface.
Described film upper surface is used for controlling radiation intensity to the distance of uviol lamp and the power of uviol lamp.
The performance of the both sexes NF membrane that the present invention is prepared is controlled by changing exposure time, monomer concentration and radiation intensity.Control the charge species on NF membrane surface by the kind that changes grafted monomers, the character of both sexes NF membrane is changed in the larger context, obtain high-valence cationic and high price anion are had the both sexes charged nanofiltration membrane of very high rejection.
The both sexes NF membrane water flux under 0.5MPa for preparing by the inventive method 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.
The specific embodiment
Below in conjunction with embodiment, the present invention is done further analysis.
Embodiment 1.
Step (1). polysulphone super-filter membrane with ethanol washing 1 time, then with deionized water washing 8 times, is removed the film surface impurity;
Step (2). the polysulphone super-filter membrane after washing is soaked in the aqueous solution that mass fraction is 1 ﹪ 4-vinylpridine, the film upper surface of polysulphone super-filter membrane and mass fraction are that the aqueous solution liquid surface distance of 1 ﹪ 4-vinylpridine is 1mm, under the 100W uviol lamp, irradiation is 120 minutes, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 5cm, obtain the cation NF membrane;
Step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 5 times with deionized water, except the remaining 4-vinylpridine in striping surface, then the cation NF membrane after washing is soaked in the aqueous solution that mass fraction is 1 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the aqueous solution liquid surface distance of 1 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 1mm, irradiation 40min under the 100W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 5cm, obtain the both sexes NF membrane;
Step (4). the both sexes NF membrane that obtains is washed 10 times with deionized water, except the remaining 2-vinylpyridine propyl sulfonic acid salt in striping surface.
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). the polyether-ketone milipore filter with ethanol washing 2 times, then with deionized water washing 10 times, is removed the film surface impurity;
Step (2). the polyether-ketone milipore filter after washing is soaked in the aqueous solution that mass fraction is 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums, the film upper surface of polyether-ketone milipore filter and mass fraction are that the aqueous solution liquid surface distance of 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums is 1.5mm, under the 150W uviol lamp, irradiation is 110 minutes, the film upper surface of polyether-ketone milipore filter and the distance of uviol lamp are 8cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 6 times with deionized water, except the remaining 3-methacryl amido oxypropyl trimethyl ammonium in striping surface, then the cation NF membrane after washing is soaked in the aqueous solution that mass fraction is the 5 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the aqueous solution liquid surface distance of the 5 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt is 1.5mm, irradiation 38min under the 150W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 8cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 11 times with deionized water, except the surperficial remaining meta-vinyl of striping-ortho-, meta-or p-picoline propyl sulfonic acid salt.
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 with ethanol washing 3 times, then with deionized water washing 9 times, is removed the film surface impurity;
Step (2). the poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the aqueous solution that mass fraction is 30 ﹪ diallyldimethylammonium chlorides, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the aqueous solution liquid surface distance of 30 ﹪ diallyldimethylammonium chlorides is 2mm, under the 180W uviol lamp, irradiation is 90 minutes, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 10cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 7 times with deionized water, except the remaining diallyldimethylammonium chloride in striping surface, then the cation NF membrane after washing is soaked in the aqueous solution that mass fraction is 10 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the aqueous solution liquid surface distance of 10 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt is 2mm, irradiation 35min under the 180W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 10cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 12 times with deionized water, except the remaining acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 4 times, then with deionized water washing 5 times, is removed the film surface impurity;
Step (2). the polysulfones after washing/polyether-ketone milipore filter is soaked in the aqueous solution that mass fraction is 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the film upper surface of polysulfones/polyether-ketone milipore filter and mass fraction are that the aqueous solution liquid surface distance of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is 2.5mm, under the 200W uviol lamp, irradiation is 80 minutes, the film upper surface of polysulfones/polyether-ketone milipore filter and the distance of uviol lamp are 12cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 8 times with deionized water, except the remaining MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride in striping surface, then it is in the aqueous solution of 20 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt that the cation NF membrane after washing is soaked mass fraction, the film upper surface of cation NF membrane and mass fraction are that the aqueous solution liquid surface distance of 20 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt is 2mm, irradiation 32min under the 200W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 12cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 13 times with deionized water, except the remaining 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 5 times, then with deionized water washing 6 times, is removed the film surface impurity;
Step (2). the polysulfones/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the aqueous solution that mass fraction is 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the aqueous solution liquid surface distance of 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium is 3mm, under the 250W uviol lamp, irradiation is 70 minutes, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 15cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 9 times with deionized water, except the surperficial remaining 3-acrylamido of striping-3-methyl butyl trimethyl ammonium, then the cation NF membrane after washing is soaked in the aqueous solution that mass fraction is 30 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the aqueous solution liquid surface distance of 30 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt is 3mm, irradiation 28min under the 250W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 15cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 14 times with deionized water, except the remaining 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 6 times, then with deionized water washing 7 times, is removed the film surface impurity;
Step (2). the polyether-ketone/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the methanol solution that mass fraction is 1 ﹪ 4-vinylpridine, the film upper surface of polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the methanol solution liquid surface distance of 1 ﹪ 4-vinylpridine is 3.5mm, under the 280W uviol lamp, irradiation is 65 minutes, the film upper surface of milipore filter and the distance of uviol lamp are 20cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 10 times with deionized water, except the remaining 4-vinylpridine in striping surface, then the cation NF membrane after washing is soaked in the methanol solution that mass fraction is 1 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the methanol solution liquid surface distance of 1 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt is 3.5mm, irradiation 30min under the 280W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 20cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 15 times with deionized water, except the remaining 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 7 times, then with deionized water washing 11 times, is removed the film surface impurity;
Step (2). the polysulfones/polyether-ketone after washing/poly (ether-sulfone) ultrafiltration membrane is soaked in the methanol solution that mass fraction is 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the methanol solution liquid surface distance of 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums is 4mm, under the 300W uviol lamp, irradiation is 60 minutes, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 18cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 5 times with deionized water, except the remaining 3-methacryl amido oxypropyl trimethyl ammonium in striping surface, then the cation NF membrane after washing is soaked in the methanol solution that mass fraction is 5 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the methanol solution liquid surface distance of 5 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 4.5mm, irradiation 25min under the 300W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 18cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 16 times with deionized water, except the remaining 2-vinylpyridine propyl sulfonic acid salt in striping surface.
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 with ethanol washing 8 times, then with deionized water washing 12 times, is removed the film surface impurity;
Step (2). the polysulphone super-filter membrane after washing is soaked in the methanol solution that mass fraction is 20 ﹪ diallyldimethylammonium chlorides, the film upper surface of polysulphone super-filter membrane and mass fraction are that the methanol solution liquid surface distance of 20 ﹪ diallyldimethylammonium chlorides is 5mm, under the 350W uviol lamp, irradiation is 50 minutes, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 22cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 6 times with deionized water, except the remaining diallyldimethylammonium chloride in striping surface, then the cation NF membrane after washing is soaked in the methanol solution that mass fraction is the 8 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the methanol solution liquid surface distance of the 8 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt is 5mm, irradiation 22min under the 350W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 22cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 17 times with deionized water, except the surperficial remaining meta-vinyl of striping-ortho-, meta-or p-picoline propyl sulfonic acid salt.
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). the polyether-ketone milipore filter with ethanol washing 9 times, then with deionized water washing 14 times, is removed the film surface impurity;
Step (2). the polyether-ketone milipore filter after washing is soaked in the methanol solution that mass fraction is 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the film upper surface of polyether-ketone milipore filter and mass fraction are that the methanol solution liquid surface distance of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is 2.5mm, under the 380W uviol lamp, irradiation is 40 minutes, the film upper surface of polyether-ketone milipore filter and the distance of uviol lamp are 25cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 7 times with deionized water, except the remaining MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride in striping surface, then the cation NF membrane after washing is soaked in the methanol solution that mass fraction is 20 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the methanol solution liquid surface distance of 20 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt is 2.5mm, irradiation 20min under the 380W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 25cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 18 times with deionized water, except the remaining acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt in striping surface.
Implementing the 9 both sexes NF membrane that prepare water flux under 0.5MPa 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 with ethanol washing 10 times, then with deionized water washing 15 times, is removed the film surface impurity;
Step (2). the poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the methanol solution that mass fraction is 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the methanol solution liquid surface distance of 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium is 3.5mm, under the 400W uviol lamp, irradiation is 30 minutes, the film upper surface of poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 30cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 8 times with deionized water, except the surperficial remaining 3-acrylamido of striping-3-methyl butyl trimethyl ammonium, then the cation NF membrane after washing is soaked in the methanol solution that mass fraction is 30 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the methanol solution liquid surface distance of 30 ﹪ 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt is 3.5mm, irradiation 18min under the 400W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 30cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 19 times with deionized water, except the remaining 2-Methacrylamide ethyl diethyl ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 5 times, then with deionized water washing 16 times, is removed the film surface impurity;
Step (2). the polysulfones after washing/polyether-ketone milipore filter is soaked in the ethanolic solution that mass fraction is 1 ﹪ 4-vinylpridine, the film upper surface of polysulfones/polyether-ketone milipore filter and mass fraction are that the ethanolic solution liquid surface distance of 1 ﹪ 4-vinylpridine is 4.5mm, under the 450W uviol lamp, irradiation is 100 minutes, the film upper surface of polysulfones/polyether-ketone milipore filter and the distance of uviol lamp are 32cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 5～10 times with deionized water, except the remaining 4-vinylpridine in striping surface, then the cation NF membrane after washing is soaked in the ethanolic solution that mass fraction is 1 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the ethanolic solution liquid surface distance of 1 ﹪ 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt is 4.5mm, irradiation 10min under the 450W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 32cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 20 times with deionized water, except the remaining 2-methylacryoyloxyethyl Dimethyl Ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 7 times, then with deionized water washing 18 times, is removed the film surface impurity;
Step (2). the polysulfones/poly (ether-sulfone) ultrafiltration membrane after washing is soaked in the ethanolic solution that mass fraction is 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and mass fraction are that the ethanolic solution liquid surface distance of 5 ﹪ 3-methacryl amido oxypropyl trimethyl ammoniums is 4mm, under the 500W uviol lamp, irradiation is 10 minutes, the film upper surface of polysulfones/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 35cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 9 times with deionized water, except the remaining 3-methacryl amido oxypropyl trimethyl ammonium in striping surface, then the cation NF membrane after washing is soaked in the ethanolic solution that mass fraction is 5 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the ethanolic solution liquid surface distance of 5 ﹪ 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt is 4mm, irradiation 15min under the 500W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 35cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 20 times with deionized water, except the remaining 2-methylacryoyloxyethyl diethyl ammonium propyl sulfonic acid salt in striping surface.
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 with ethanol washing 9 times, then with deionized water washing 20 times, is removed the film surface impurity;
Step (2). the milipore filter after washing is soaked in the ethanolic solution that mass fraction is 40 ﹪ diallyldimethylammonium chlorides, the film upper surface of milipore filter and mass fraction are that the ethanolic solution liquid surface distance of 40 ﹪ diallyldimethylammonium chlorides is 5mm, under the 550W uviol lamp, irradiation is 3 minutes, the film upper surface of milipore filter and the distance of uviol lamp are 38cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 10 times with deionized water, except the remaining diallyldimethylammonium chloride in striping surface, then the cation NF membrane after washing is soaked in the ethanolic solution that mass fraction is 15 ﹪ 2-vinylpyridine propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the ethanolic solution liquid surface distance of 15 ﹪ 2-vinylpyridine propyl sulfonic acid salt is 5mm, irradiation 5min under the 550W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 38cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 15 times with deionized water, except the remaining 2-vinylpyridine propyl sulfonic acid salt in striping surface.
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 with ethanol washing 8 times, then with deionized water washing 19 times, is removed the film surface impurity;
Step (2). the polysulfones/polyether-ketone after washing/poly (ether-sulfone) ultrafiltration membrane is soaked in the ethanolic solution of 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the ethanolic solution liquid surface distance of the film upper surface of milipore filter and 50 ﹪ MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is 3.5mm, under the 600W uviol lamp, irradiation is 3 minutes, the film upper surface of polysulfones/polyether-ketone/poly (ether-sulfone) ultrafiltration membrane and the distance of uviol lamp are 40cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 8 times with deionized water, except the remaining MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride in striping surface, then the cation NF membrane after washing is soaked in the ethanolic solution that mass fraction is the 20 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the ethanolic solution liquid surface distance of the 20 meta-vinyl of ﹪-ortho-, meta-or p-picoline propyl sulfonic acid salt is 2mm, irradiation 2min under the 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 40cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 18 times with deionized water, except the surperficial remaining meta-vinyl of striping-ortho-, meta-or p-picoline propyl sulfonic acid salt.
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 with ethanol washing 6 times, then with deionized water washing 17 times, is removed the film surface impurity;
Step (2). the polysulphone super-filter membrane after washing is soaked in the ethanolic solution that mass fraction is 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium, the film upper surface of polysulphone super-filter membrane and mass fraction are that the ethanolic solution liquid surface distance of 65 ﹪ 3-acrylamidos-3-methyl butyl trimethyl ammonium is 5mm, under the 600W uviol lamp, irradiation is 5 minutes, the film upper surface of polysulphone super-filter membrane and the distance of uviol lamp are 30cm, obtain the cation NF membrane;
step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 8 times with deionized water, except the surperficial remaining 3-acrylamido of striping-3-methyl butyl trimethyl ammonium, then the cation NF membrane after washing is soaked in the ethanolic solution that mass fraction is 30 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt, the film upper surface of cation NF membrane and mass fraction are that the ethanolic solution liquid surface distance of 30 ﹪ acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt is 5mm, irradiation 30min under the 600W uviol lamp, the film upper surface of cation NF membrane and the distance of uviol lamp are 30cm, obtain the both sexes NF membrane,
Step (4). the both sexes NF membrane that obtains is washed 15 times with deionized water, except the remaining acrylamido ethyl Dimethyl Ammonium propyl sulfonic acid salt in striping surface.
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, and reaction, carry out in air under 10～30 ℃; The film upper surface is used for controlling radiation intensity to the distance of uviol lamp and the power of uviol lamp.
The strainability of the prepared both sexes NF membrane of the present invention is estimated in instrument at film and is estimated.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 (10)
1. the preparation method of a large flux both sexes NF membrane is characterized in that the method comprises the following steps:
Step (1). milipore filter with ethanol washing 1～10 time, then with deionized water washing 5～20 times, is removed the film surface impurity;
Step (2). the milipore filter after washing is soaked in olefines cation mono liquid solution, the liquid surface distance of the film upper surface of milipore filter and olefines cation mono liquid solution is 1～5mm, under 100～600W uviol lamp, irradiation is 3～120 minutes, the film upper surface of milipore filter and the distance of uviol lamp are 5～40cm, obtain the cation NF membrane;
Step (3). the cation NF membrane that obtains after ultra-violet radiation is washed 5～10 times with deionized water, except the remaining olefines cationic monomer in striping surface, then the cation NF membrane after washing is soaked in both sexes olefin monomer solution, the liquid surface distance of the film upper surface of cation NF membrane and both sexes olefin monomer solution is 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 the both sexes NF membrane;
Step (4). the both sexes NF membrane that obtains is washed 10～20 times with deionized water, except the remaining both sexes olefines ion monomer in striping surface.
2. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, the material that it is characterized in that the milipore filter described in step (1) are one or more of polysulfones, polyether-ketone, polyether sulfone.
3. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, is characterized in that the olefines cation mono liquid solution described in step (2) is that mass fraction is the aqueous solution or methanol solution or the ethanolic solution of 1～65 ﹪ olefines cationic monomer;
Described olefines cationic monomer is the alkene that contains quaternary ammonium salt or tertiary amine groups.
4. 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) is that wavelength is the high-pressure sodium lamp of 290～400nm, reacts in 10～30 ℃ of lower air.
5. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, is characterized in that the both sexes olefin monomer solution described in step (3) is that mass fraction is the aqueous solution or methanol solution or the ethanolic solution of 1～30 ﹪ both sexes olefin monomer;
Described both sexes olefin monomer is the alkene that contains amphiprotic group; In the both sexes olefin monomer, negative group is one or both of sulfonic group, carboxyl, and positive group is one or both of quaternary ammonium salt, tertiary amine groups.
6. 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 is with ethanol washing 4～7 times, then with deionized water washing 10～15 times.
7. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, the power that it is characterized in that 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.
8. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 1, the power that it is characterized in that 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.
9. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 3, the mass content that it is characterized in that olefines cationic monomer in olefines cation mono liquid solution is 5～50 ﹪.
10. the preparation method of a kind of large flux both sexes NF membrane as claimed in claim 5, the mass content that it is characterized in that both sexes olefin monomer in both sexes olefin monomer solution is 5～20 ﹪.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106179002A (en) * | 2016-08-09 | 2016-12-07 | 中北大学 | A kind of polysulfones side chain graft poly-tertiary amine micro-filtration membrane |
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