CN102553460A - Method for preparing pollution-resistant low-pressure reverse osmosis membrane - Google Patents
Method for preparing pollution-resistant low-pressure reverse osmosis membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing a pollution-resistant low-pressure reverse osmosis membrane and belongs to the technical field of the separation of reverse osmosis membranes for water treatment. The method comprises the following steps of: preparing a polyamide membrane on a polysulfone porous membrane by using an aqueous solution of polyamine and an organic solution of polyacyl chloride through interfacial polycondensation, and coating and cross-linking a layer of polyvinyl alcohol-grafted zwitterionic copolymer membrane on the surface of the polyamide membrane. The method for preparing the pollution-resistant low-pressure reverse osmosis membrane is reasonably designed; a polyvinyl alcohol-grafted zwitterionic copolymer is coated and cross-linked on the polyamide membrane which is prepared on the polysulfone porous membrane by using the aqueous solution of polyamine and the organic solution of polyacyl chloride through interfacial polycondensation, so that the hydrophilcity of the surface of the membrane is improved, and the adhesiveness of organic matter is reduced; and the reverse osmosis membrane has good pollution resistance during long-time running. The membrane has high backwashing resistance and stability; and the salt rejection rate of the membrane on a NaCl aqueous solution at the concentration of 3.5g.L<-1> can reach over 97.0 percent at the temperature of 25 DEG C and under the pressure of 1.5MPa.
Description
Technical field
The invention belongs to water treatment reverse osmosis membrane separation technical field, be specifically related to a kind of anti-pollution low pressure reverse osmosis film and preparation method thereof.
Background technology
Reverse osmosis membrane is a kind of film of processing, having the semi permeability ability with special material and processing method.It can make some component selective permeations of the aqueous solution under the impressed pressure effect, thereby reaches the purpose of desalination, purification or concentrating and separating.1978, scholars such as U.S. J.E.Cadotte were obtaining important breakthrough aspect reverse osmosis composite membrane technology of preparing and the functional material research; U.S. Filmtec company had released the FT-30 reverse osmosis composite membrane in 1980; Realized the commercialization of reverse osmosis composite membrane technology; Make the reverse osmosis composite membrane technology obtain epoch-making progress, Filmtec company has succeeded in developing conventional reverse osmosis composite membrane again in succession afterwards, desalinization is used.
In the history of reverse osmosis membrane development, cellulose acetate and aromatic polyamide are typical excellent membrane materials, and the research and development of asymmetric membrane and composite membrane are two examples of innovation.Polyamide reverse osmose membrane successful Application desalinization at present, drinking water treatment and waste water recycling etc.The advantage of aromatic polyamide class composite membrane is that salt rejection rate is high, and flux is big, uses the pH wide ranges, anti-biodegradation, and it is low etc. that operating pressure requires, and shortcoming is a resistance to oxidation not, and performance sharply decays after the oxidation, resistive connection dirt and pollution capacity difference etc.Be widely used in the preparation of pure water and ultra-pure water, aspects such as water for industrial use processing.Around the stain resistance that improves polyamide reverse osmose membrane, film company has all carried out relevant research (CN200410068155.5) with research unit.
Use hydrophilic macromolecule,, can prepare reverse osmosis membrane (CN1345626A) at the polysulfones porous film surface through crosslinked like acrylic acid and copolymer thereof.Polyvinyl alcohol has good film forming as a kind of hydrophilic macromolecule.As with polyvinyl alcohol as filmogen, directly be coated on the surface of polysulphone super-filter membrane, crosslinking curing becomes composite nanometer filtering film (J Colloid Interface Sci. 2009,338,121 – 127).Chinese patent CN1213985A discloses and has used polyvinyl alcohol polyamide coated film in " counter-infiltration compound and carry out the method for reverse-osmosis treated water with it ", has improved the stain resistance of film.But since polyvinyl alcohol do not have crosslinked, anti-backwash ability and less stable.In recent years, the stain resistance research about amphoteric ion copolymer is very extensive.Research shows that the material that contains the amphion functional group has good water permeability and resistance tocrocking.Utilize the good filming property and the zwitterionic stain resistance of polyvinyl alcohol; Preparation contains the polyvinyl alcohol of amphion group; With it as applying agent; Can the characteristics of amphion hydrophily and resistance tocrocking be combined with polyamide interfacial polymerization system film characteristics easily and fast, prepare a kind of novel anti-pollution reverse osmosis membrane.
Summary of the invention
Problem to prior art exists the objective of the invention is to design the technical scheme that a kind of anti-pollution low pressure reverse osmosis film and preparation method thereof is provided.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film; It is characterized in that on the polysulfones perforated membrane, utilizing the organic solution of the polyamine aqueous solution and polynary acyl chlorides to prepare PA membrane, then at PA membrane surface-coated and crosslinked layer of polyethylene alcohol grafting amphoteric ion copolymer film through interfacial polycondensation.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film is characterized in that comprising following steps:
1) adds in the polyvinyl alcohol water solution of 50 grams per liters that to account for the polyvinyl alcohol water solution gross mass be 20～35% zwitterionic monomer, under nitrogen protection, add that to account for the polyvinyl alcohol water solution gross mass be 0.25～1.0% oxidation-reduction initiator; Reacted 3～5 hours down at 55 ℃; Product is through acetone precipitation, washing, in 60～80 ℃ of dryings 3 hours, pulverizes; Obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
2) earlier the polysulfones perforated membrane is immersed in the polyamine aqueous solution, flooded 0.5～1 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the oil-phase solution that contains polynary acyl chlorides monomer, reacted 0.5～1 minute, through interfacial polymerization; Then in 40～60
oSolidified in the C baking oven 20～40 minutes; Soak with deionized water at last, subsequent use;
3) it is 0.2～0.5wt/v% aqueous solution that the polyvinyl alcohol graft copolymerized amphoteric ion copolymer that earlier step 1) is obtained is configured to mass concentration; Polyaldehyde is joined in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer; Regulator solution pH value to 2～5; Again with step 2) PA membrane that obtains takes out after in the above-mentioned polyvinyl alcohol graft copolymerized amphoteric ion copolymer aqueous solution, flooding 1～2 minute, then 45～60
oCrosslinking curing is 3～6 hours in the baking oven of C temperature, obtains anti-pollution low pressure reverse osmosis film.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film, the degree of hydrolysis that it is characterized in that the vinylacetate in the polyvinyl alcohol molecule described in the step 1) is 88～99%.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film; It is characterized in that the zwitterionic monomer described in the step 1) is N, a kind of in N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium or N-(3-sulfopropyl) 4-vinylpridine.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film; It is characterized in that the oxidant in the oxidation-reduction initiator described in the step 1) is ammonium persulfate or potassium peroxydisulfate; Reducing agent in the described oxidation-reduction initiator is a sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.0～2.0.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film is characterized in that step 2) described in the polyamine monomer be a kind of in o-phenylenediamine or the m-phenylene diamine (MPD); The polyamine monomer concentration is 1.0～5.0wt/v% in the aqueous phase solution.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film is characterized in that step 2) described in polynary acyl chlorides monomer be a kind of in pyromellitic trimethylsilyl chloride or the Polychlorinated biphenyls acyl chlorides; The concentration of polynary acyl chlorides monomer is 0.1～0.5wt/v% in the organic phase solution.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film is characterized in that step 2) described in the oil-phase solution of polynary acyl chlorides monomer in oil phase be a kind of in n-hexane or the cyclohexane.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film; It is characterized in that the polyaldehyde described in the step 3) is a kind of in MDA or the glutaraldehyde, the concentration of polyaldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1～0.3wt/v%.
The preparation method of described a kind of anti-pollution low pressure reverse osmosis film is characterized in that using in the described step 3) sulphur acid for adjusting pH value.
The preparation method of above-mentioned a kind of anti-pollution low pressure reverse osmosis film; Reasonable in design; On the polysulfones perforated membrane, utilize the organic solution of the polyamine aqueous solution and polynary acyl chlorides to prepare coating cross-linking polyvinyl alcohol grafting amphoteric ion copolymer on the PA membrane, improved the hydrophily on film surface, reduced the organic matter tack through interfacial polycondensation; This kind reverse osmosis membrane shows good stain resistance in long-time running.This film has very strong anti-backwash ability and stability, and this film is at 25 ℃, under the 1.5MPa pressure, for 3.5g.L
-1The salt rejection of the NaCl aqueous solution can reach more than 97.0%.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1
At the degree of hydrolysis that 50 grams per liters are housed (degree of hydrolysis that refers to vinylacetate in the polyvinyl alcohol molecule) is in the agitated reactor of 99% polyvinyl alcohol water solution; Adding mass percent (refer to N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium accounts for the mass percent of polyvinyl alcohol water solution gross mass) concentration is 20% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.0) of 0.25%, reacts 5 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 1wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the hexane solution that concentration is 0.1wt/v trimesoyl chloride monomer, reacted 0.5 minute; In 40 ℃ of baking ovens, solidified 40 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde is joined in the aqueous solution that mass concentration is 0.2% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1wt/v; Adding sulfuric acid regulation solution pH value is 2; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution (aqueous solution that contains the polyvinyl alcohol graft copolymerized amphoteric ion copolymer of glutaraldehyde), 45
oCrosslinking curing is 6 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 97.8%, and water flux is 32.5L.m
-2.h
-1
Embodiment 2
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 88% polyvinyl alcohol water solution, adds mass percent concentration and be 35% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 1%, reacts 3 hours down at 55 ℃, and product is through acetone precipitation, washing; In 80 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 5wt/v, flooded 1 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the hexane solution that concentration is 0.5wt/v trimesoyl chloride monomer, reacted 1 minute; In 60 ℃ of baking ovens, solidified 20 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.5% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.3wt/v; Adding sulfuric acid regulation solution pH value is 5; Again PA membrane is flooded taking-up in 2 minutes in above-mentioned aqueous copolymers solution, 60
oCrosslinking curing is 3 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 98.2%, and water flux is 27.6L.m
-2.h
-1
Embodiment 3
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 88% polyvinyl alcohol water solution, adds mass percent concentration and be 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the hexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.3% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.2wt/v; Adding sulfuric acid regulation solution pH value is 3; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 98.8%, and water flux is 31.5L.m
-2.h
-1
Embodiment 4
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 95% polyvinyl alcohol water solution; The adding mass percent concentration is 28% N-(3-sulfopropyl) 4-vinylpridine, and under nitrogen protection, the adding mass percent concentration is 0.3% ammonium persulfate-sodium bisulfite (ammonium persulfate and sodium hydrogensulfite mass ratio are 1.0:2.0); Reacted 4 hours down at 55 ℃; Product is through acetone precipitation, washing, in 60 ℃ of dryings 3 hours, pulverizes; Obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 2wt/v, flooded 1 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the cyclohexane solution that concentration is 0.1wt/v Polychlorinated biphenyls acyl chlorides monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.3% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.2wt/v; Adding sulfuric acid regulation solution pH value is 3; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 97.5%, and water flux is 33.4L.m
-2.h
-1
Embodiment 5
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 98% polyvinyl alcohol water solution, adds mass percent concentration and be 25% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.5%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 3wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the hexane solution that concentration is 0.2wt/v Polychlorinated biphenyls acyl chlorides monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.3% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.2wt/v; Adding sulfuric acid regulation solution pH value is 3; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 98.4%, and water flux is 28.5L.m
-2.h
-1
Embodiment 6
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 88% polyvinyl alcohol water solution, adds mass percent concentration and be 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.0) of 1%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the hexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
MDA joined in the aqueous solution of 0.4% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of MDA in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.2wt/v; Adding sulfuric acid regulation solution pH value is 4; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 98.9%, and water flux is 32.5L.m
-2.h
-1
Embodiment 7
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 88% polyvinyl alcohol water solution, adds mass percent concentration and be 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer after, subsequent use;
The polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 2wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.3% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.2wt/v; Adding sulfuric acid regulation solution pH value is 2; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 99.1%, and water flux is 33.7L.m
-2.h
-1
Embodiment 8
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 99% polyvinyl alcohol water solution, adds mass percent concentration and be 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
MDA joined in the aqueous solution of 0.2% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of MDA in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1wt/v; Adding sulfuric acid regulation solution pH value is 2; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 99.4%, and water flux is 31.8L.m
-2.h
-1
Embodiment 9
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 99% polyvinyl alcohol water solution; The adding mass percent concentration is 25% N-(3-sulfopropyl) 4-vinylpridine, and under nitrogen protection, the adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.3%; Reacted 4 hours down at 55 ℃; Product is through acetone precipitation, washing, in 60 ℃ of dryings 3 hours, pulverizes; Obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 1.5wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.15% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1wt/v; Adding sulfuric acid regulation solution pH value is 2; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 99.2%, and water flux is 32.7L.m
-2.h
-1
Embodiment 10
At the degree of hydrolysis that 50 grams per liters are housed is in the agitated reactor of 88% polyvinyl alcohol water solution, adds mass percent concentration and be 25% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium; Under nitrogen protection; The adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.3%, reacts 4 hours down at 55 ℃, and product is through acetone precipitation, washing; In 60 ℃ of dryings 3 hours; Pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
The polysulfones porous support membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, flooded 0.5 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the cyclohexane solution that concentration is 0.25wt/v trimesoyl chloride monomer, reacted 1 minute; In 50 ℃ of baking ovens, solidified 30 minutes then; Soak with deionized water at last, obtain PA membrane, subsequent use;
Glutaraldehyde joined in the aqueous solution of 0.2% polyvinyl alcohol graft copolymerized amphoteric ion copolymer; The concentration of glutaraldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1wt/v; Adding sulfuric acid regulation solution pH value is 2; Again PA membrane is flooded taking-up in 1 minute in above-mentioned aqueous copolymers solution, 50
oCrosslinking curing is 4 hours in the baking oven of C, obtains the anti-pollution reverse osmosis membrane.
This film is at 25 ℃, and under the 1.5MPa pressure, for the NaCl separation of water solution result of 2000ppm be: the salt rejection is 99.6%, and water flux is 30.6L.m
-2.h
-1
Claims (10)
1. the preparation method of an anti-pollution low pressure reverse osmosis film; It is characterized in that on the polysulfones perforated membrane, utilizing the organic solution of the polyamine aqueous solution and polynary acyl chlorides to prepare PA membrane, then at PA membrane surface-coated and crosslinked layer of polyethylene alcohol grafting amphoteric ion copolymer film through interfacial polycondensation.
2. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 1 is characterized in that comprising following steps:
1) adds in the polyvinyl alcohol water solution of 50 grams per liters that to account for the polyvinyl alcohol water solution gross mass be 20～35% zwitterionic monomer, under nitrogen protection, add that to account for the polyvinyl alcohol water solution gross mass be 0.25～1.0% oxidation-reduction initiator; Reacted 3～5 hours down at 55 ℃; Product is through acetone precipitation, washing, in 60～80 ℃ of dryings 3 hours, pulverizes; Obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, subsequent use;
2) earlier the polysulfones perforated membrane is immersed in the polyamine aqueous solution, flooded 0.5～1 minute, taking-up is also got rid of the excessive solution in surface; Again it is immersed in the oil-phase solution that contains polynary acyl chlorides monomer, reacted 0.5～1 minute, through interfacial polymerization; Then in 40～60
oSolidified in the C baking oven 20～40 minutes; Soak with deionized water at last, subsequent use;
3) it is 0.2～0.5wt/v% aqueous solution that the polyvinyl alcohol graft copolymerized amphoteric ion copolymer that earlier step 1) is obtained is configured to mass concentration; Polyaldehyde is joined in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer; Regulator solution pH value to 2～5; Again with step 2) PA membrane that obtains takes out after in the above-mentioned polyvinyl alcohol graft copolymerized amphoteric ion copolymer aqueous solution, flooding 1～2 minute, then 45～60
oCrosslinking curing is 3～6 hours in the baking oven of C temperature, obtains anti-pollution low pressure reverse osmosis film.
3. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2, the degree of hydrolysis that it is characterized in that the vinylacetate in the polyvinyl alcohol molecule described in the step 1) is 88～99%.
4. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2; It is characterized in that the zwitterionic monomer described in the step 1) is N, a kind of in N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium or N-(3-sulfopropyl) 4-vinylpridine.
5. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2; It is characterized in that the oxidant in the oxidation-reduction initiator described in the step 1) is ammonium persulfate or potassium peroxydisulfate; Reducing agent in the described oxidation-reduction initiator is a sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.0～2.0.
6. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2 is characterized in that step 2) described in the polyamine monomer be a kind of in o-phenylenediamine or the m-phenylene diamine (MPD); The polyamine monomer concentration is 1.0～5.0wt/v% in the aqueous phase solution.
7. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2 is characterized in that step 2) described in polynary acyl chlorides monomer be a kind of in pyromellitic trimethylsilyl chloride or the Polychlorinated biphenyls acyl chlorides; The concentration of polynary acyl chlorides monomer is 0.1～0.5wt/v% in the organic phase solution.
8. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2 is characterized in that step 2) described in the oil-phase solution of polynary acyl chlorides monomer in oil phase be a kind of in n-hexane or the cyclohexane.
9. the preparation method of a kind of anti-pollution low pressure reverse osmosis film according to claim 2; It is characterized in that the polyaldehyde described in the step 3) is a kind of in MDA or the glutaraldehyde, the concentration of polyaldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1～0.3wt/v%.
10. the preparation method of a kind of anti-pollution low pressure reverse osmosis film as claimed in claim 2 is characterized in that using in the described step 3) sulphur acid for adjusting pH value.
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