CN102553460B - 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 reverse osmosis of water treatment membrane separation technique field, be specifically related to a kind of pollution-resistant low-pressure reverse osmosis membrane and preparation method thereof.
Background technology
Reverse osmosis membrane is a kind of film of making, have semi-transparent performance by special material and processing method.It can make some compositional selectings of the aqueous solution see through under impressed pressure effect, thereby reaches the object of desalination, purification or concentrating and separating.1978, the scholars such as U.S. J.E.Cadotte were obtaining important breakthrough aspect reverse osmosis composite membrane technology of preparing and functional material research; Within 1980, Filmtec company of the U.S. has released FT-30 reverse osmosis composite membrane, realize the commercialization of reverse osmosis composite membrane technology, make reverse osmosis composite membrane technology obtain epoch-making progress, Filmtec company has succeeded in developing again conventional reverse osmosis composite membrane 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.Successful Application desalinization of polyamide reverse osmose membrane 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 large, application pH wide ranges, and resistance to biodegradation, it is low etc. that operating pressure requires, and shortcoming is resistance to oxidation not, performance sharp-decay after oxidation, ant-scaling and pollution capacity are poor etc.Be widely used in pure water and ultra-pure water preparation, the aspects such as water for industrial use processing.Around the stain resistance that improves polyamide reverse osmose membrane, film company and research unit have all carried out relevant research (CN200410068155.5).
With hydrophilic macromolecule, as acrylic acid and copolymer thereof, can prepare reverse osmosis membrane (CN1345626A) by being cross-linked at polysulfones porous film surface.Polyvinyl alcohol, as a kind of hydrophilic macromolecule, has good film forming.As using polyvinyl alcohol as filmogen, be directly 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 disclose " counter-infiltration compound and with it carry out the method for reverse-osmosis treated water " in use polyvinyl alcohol polyamide coating film, improved the stain resistance of film.But because polyvinyl alcohol is not crosslinked, resistance to backwash ability and less stable.In recent years, very extensive about the stain resistance research of amphoteric ion copolymer.Research shows that the material that contains amphion functional group has good water permeability and resistance tocrocking.Utilize good filming and the zwitterionic stain resistance of polyvinyl alcohol, the polyvinyl alcohol that preparation contains amphion group, set it as coating agent, the feature of amphion hydrophily and resistance tocrocking can be combined with polyamide interfacial polymerization masking feature easily and fast, prepare a kind of novel anti-pollution reverse osmosis membrane.
Summary of the invention
The problem existing for prior art, the object of the invention is to design provides the technical scheme of a kind of pollution-resistant low-pressure reverse osmosis membrane and preparation method thereof.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, it is characterized in that utilizing the organic solution of the polyamine aqueous solution and polynary acyl chlorides to prepare PA membrane by interfacial polycondensation on polysulfones perforated membrane, then apply and crosslinked layer of polyethylene alcohol grafting amphoteric ion copolymer film on PA membrane surface.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, is characterized in that comprising following steps:
1) in the polyvinyl alcohol water solution of 50 grams per liters, add that to account for polyvinyl alcohol water solution gross mass be 20～35% zwitterionic monomer, under nitrogen protection, add that to account for polyvinyl alcohol water solution gross mass be 0.25～1.0% oxidation-reduction initiator, at 55 DEG C, react 3～5 hours, product, through acetone precipitation, washing, is dried 3 hours, pulverizing in 60～80 DEG C, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
2) first polysulfones perforated membrane is immersed in the polyamine aqueous solution, floods 0.5～1 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the oil-phase solution that contains polynary acyl chlorides monomer, reacted 0.5～1 minute, by interfacial polymerization; Then in 40～60
oin C baking oven, solidify 20～40 minutes; Finally soak by deionized water, for subsequent use;
3) it is 0.2～0.5wt/v% aqueous solution that the polyvinyl alcohol graft copolymerized amphoteric ion copolymer first step 1) being 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 by step 2) PA membrane that obtains takes out flood 1～2 minute in the above-mentioned polyvinyl alcohol graft copolymerized amphoteric ion copolymer aqueous solution after, then 45～60
oin the baking oven of C temperature, crosslinking curing 3～6 hours, obtains pollution-resistant low-pressure reverse osmosis membrane.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, the degree of hydrolysis that it is characterized in that the vinylacetate in the polyvinyl alcohol molecule described in step 1) is 88～99%.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, it is characterized in that the zwitterionic monomer described in step 1) is N, the one in N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium or N-(3-sulfopropyl) 4-vinylpridine.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, it is characterized in that the oxidant in the oxidation-reduction initiator described in step 1) is ammonium persulfate or potassium peroxydisulfate, reducing agent in described oxidation-reduction initiator is 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 pollution-resistant low-pressure reverse osmosis membrane, is characterized in that step 2) described in polyamine monomer be the one in o-phenylenediamine or m-phenylene diamine (MPD); In aqueous phase solution, polyamine monomer concentration is 1.0～5.0wt/v%.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, is characterized in that step 2) described in polynary acyl chlorides monomer be the one in pyromellitic trimethylsilyl chloride or Polychlorinated biphenyls acyl chlorides; In organic phase solution, the concentration of polynary acyl chlorides monomer is 0.1～0.5wt/v%.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, is characterized in that step 2) described in the oil-phase solution of polynary acyl chlorides monomer in oil phase be the one in n-hexane or cyclohexane.
The preparation method of described a kind of pollution-resistant low-pressure reverse osmosis membrane, it is characterized in that step 3) described in polyaldehyde be the one in MDA or 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 pollution-resistant low-pressure reverse osmosis membrane, is characterized in that using sulphur acid for adjusting pH value in described step 3).
The preparation method of above-mentioned a kind of pollution-resistant low-pressure reverse osmosis membrane, reasonable in design, the organic solution of utilizing the polyamine aqueous solution and polynary acyl chlorides on polysulfones perforated membrane is prepared and on PA membrane, is applied cross-linking polyvinyl alcohol grafting amphoteric ion copolymer by interfacial polycondensation, improve the hydrophily on film surface, reduce organic matter tack, this kind of reverse osmosis membrane, in long-term operation, shows good stain resistance.This film has very strong resistance to backwash ability and stability, and this film is at 25 DEG C, under 1.5MPa pressure, for 3.5g.L
-1the salt rejection of the NaCl aqueous solution can reach more than 97.0%.
Detailed description of the invention
Further illustrate the present invention below in conjunction with specific embodiment.
Embodiment 1
Be in 99% the reactor of polyvinyl alcohol water solution the degree of hydrolysis of 50 grams per liters (degree of hydrolysis of vinylacetate in referring to polyvinyl alcohol molecule) is housed, add mass percent (to refer to N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium accounts for the mass percent of polyvinyl alcohol water solution gross mass) the concentration N that is 20%, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.0) of 0.25%, at 55 DEG C, react 5 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use,
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 1wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the hexane solution that concentration is 0.1wt/v trimesoyl chloride monomer, reacted 0.5 minute; Then in 40 DEG C of baking ovens, solidify 40 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
It is in 0.2% the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer that glutaraldehyde is joined to mass concentration, 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 in above-mentioned aqueous copolymers solution (aqueous solution of the polyvinyl alcohol graft copolymerized amphoteric ion copolymer that contains glutaraldehyde) to taking-up in 1 minute, 45
oin the baking oven of C, crosslinking curing 6 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 97.8%, and water flux is 32.5L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 2
In the reactor of the polyvinyl alcohol water solution that is 88% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 35% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 1%, at 55 DEG C, react 3 hours, product is through acetone precipitation, washing, be dried 3 hours in 80 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 5wt/v, floods 1 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the hexane solution that concentration is 0.5wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 60 DEG C of baking ovens, solidify 20 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.5% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 2 minutes, 60
oin the baking oven of C, crosslinking curing 3 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 98.2%, and water flux is 27.6L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 3
In the reactor of the polyvinyl alcohol water solution that is 88% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the hexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.3% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 98.8%, and water flux is 31.5L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 4
In the reactor of the polyvinyl alcohol water solution that is 95% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 28% N-(3-sulfopropyl) 4-vinylpridine, under nitrogen protection, adding mass percent concentration is 0.3% ammonium persulfate-sodium bisulfite (ammonium persulfate and sodium hydrogensulfite mass ratio are 1.0:2.0), at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 2wt/v, floods 1 minute, take out and get rid of the excessive solution in surface; Being immersed in concentration is in the cyclohexane solution of 0.1wt/v Polychlorinated biphenyls acyl chlorides monomer again, reacts 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.3% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 97.5%, and water flux is 33.4L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 5
In the reactor of the polyvinyl alcohol water solution that is 98% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 25% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.5%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 3wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Being immersed in concentration is in the hexane solution of 0.2wt/v Polychlorinated biphenyls acyl chlorides monomer again, reacts 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; ; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.3% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 98.4%, and water flux is 28.5L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 6
In the reactor of the polyvinyl alcohol water solution that is 88% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.0) of 1%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the hexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
MDA is joined in 0.4% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 98.9%, and water flux is 32.5L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 7
In the reactor of the polyvinyl alcohol water solution that is 88% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain after polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the o-phenylenediamine aqueous solution that concentration is 2wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.3% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 99.1%, and water flux is 33.7L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 8
In the reactor of the polyvinyl alcohol water solution that is 99% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 30% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:2.0) of 0.3%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
MDA is joined in 0.2% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 99.4%, and water flux is 31.8L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 9
In the reactor of the polyvinyl alcohol water solution that is 99% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 25% N-(3-sulfopropyl) 4-vinylpridine, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.3%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones perforated membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 1.5wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the cyclohexane solution that concentration is 0.2wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.15% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 99.2%, and water flux is 32.7L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Embodiment 10
In the reactor of the polyvinyl alcohol water solution that is 88% at the degree of hydrolysis that 50 grams per liters are housed, adding mass percent concentration is 25% N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium, under nitrogen protection, adding mass percent concentration is potassium peroxydisulfate-sodium hydrogensulfite (potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1.0:1.5) of 0.3%, at 55 DEG C, react 4 hours, product is through acetone precipitation, washing, be dried 3 hours in 60 DEG C, pulverize, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
Polysulfones porous support membrane is immersed in the m-phenylene diamine (MPD) aqueous solution that concentration is 2wt/v, floods 0.5 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the cyclohexane solution that concentration is 0.25wt/v trimesoyl chloride monomer, reacted 1 minute; Then in 50 DEG C of baking ovens, solidify 30 minutes; Finally soak by deionized water, obtain PA membrane, for subsequent use;
Glutaraldehyde is joined in 0.2% the aqueous solution of 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 in above-mentioned aqueous copolymers solution to taking-up in 1 minute, 50
oin the baking oven of C, crosslinking curing 4 hours, obtains anti-pollution reverse osmosis membrane.
This film is at 25 DEG C, under 1.5MPa pressure, is: salt rejection is 99.6%, and water flux is 30.6L.m for the separating resulting of the NaCl aqueous solution of 2000ppm
-2.h
-1.
Claims (9)
1. the preparation method of a pollution-resistant low-pressure reverse osmosis membrane, it is characterized in that utilizing the organic solution of the polyamine aqueous solution and polynary acyl chlorides to prepare PA membrane by interfacial polycondensation on polysulfones perforated membrane, then apply and crosslinked layer of polyethylene alcohol grafting amphoteric ion copolymer film on PA membrane surface, specifically comprise following steps:
1) in the polyvinyl alcohol water solution of 50 grams per liters, add that to account for polyvinyl alcohol water solution gross mass be 20～35% zwitterionic monomer, under nitrogen protection, add that to account for polyvinyl alcohol water solution gross mass be 0.25～1.0% oxidation-reduction initiator, at 55 DEG C, react 3～5 hours, product, through acetone precipitation, washing, is dried 3 hours, pulverizing in 60～80 DEG C, obtain polyvinyl alcohol graft copolymerized amphoteric ion copolymer, for subsequent use;
2) first polysulfones perforated membrane is immersed in the polyamine aqueous solution, floods 0.5～1 minute, take out and get rid of the excessive solution in surface; Be immersed in again in the oil-phase solution that contains polynary acyl chlorides monomer, reacted 0.5～1 minute, by interfacial polymerization; Then in 40～60
oin C baking oven, solidify 20～40 minutes; Finally soak by deionized water, for subsequent use;
3) it is 0.2～0.5wt/v% aqueous solution that the polyvinyl alcohol graft copolymerized amphoteric ion copolymer first step 1) being 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 by step 2) PA membrane that obtains takes out flood 1～2 minute in the above-mentioned polyvinyl alcohol graft copolymerized amphoteric ion copolymer aqueous solution after, then 45～60
oin the baking oven of C temperature, crosslinking curing 3～6 hours, obtains pollution-resistant low-pressure reverse osmosis membrane.
2. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, the degree of hydrolysis that it is characterized in that the vinylacetate in the polyvinyl alcohol molecule described in step 1) is 88～99%.
3. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, it is characterized in that the zwitterionic monomer described in step 1) is N, the one in N-dimethyl N-(2-methylacryoyloxyethyl) N-(2-sulfoethyl) ammonium or N-(3-sulfopropyl) 4-vinylpridine.
4. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, it is characterized in that the oxidant in the oxidation-reduction initiator described in step 1) is ammonium persulfate or potassium peroxydisulfate, reducing agent in described oxidation-reduction initiator is sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.0～2.0.
5. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, is characterized in that step 2) described in polyamine monomer be the one in o-phenylenediamine or m-phenylene diamine (MPD); In aqueous phase solution, polyamine monomer concentration is 1.0～5.0wt/v%.
6. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, is characterized in that step 2) described in polynary acyl chlorides monomer be the one in pyromellitic trimethylsilyl chloride or Polychlorinated biphenyls acyl chlorides; In organic phase solution, the concentration of polynary acyl chlorides monomer is 0.1～0.5wt/v%.
7. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, is characterized in that step 2) described in the oil-phase solution of polynary acyl chlorides monomer in oil phase be the one in n-hexane or cyclohexane.
8. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane according to claim 1, it is characterized in that step 3) described in polyaldehyde be the one in MDA or glutaraldehyde, the concentration of polyaldehyde in the aqueous solution of polyvinyl alcohol graft copolymerized amphoteric ion copolymer is 0.1～0.3wt/v%.
9. the preparation method of a kind of pollution-resistant low-pressure reverse osmosis membrane as claimed in claim 1, is characterized in that using sulphur acid for adjusting pH value in described step 3).
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| CN102921315B (en) * | 2012-11-02 | 2014-12-10 | 北京碧水源膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN103894073A (en) * | 2014-04-21 | 2014-07-02 | 哈尔滨工业大学 | Method for hydrophilic modification of porous filter membrane by using diluted solution interfacial polymerization behavior |
| CN104607067B (en) * | 2014-12-05 | 2016-07-06 | 北京碧水源净水科技有限公司 | A kind of preparation method of ultralow pressure high-flux reverse osmosis membrane |
| CN105642137B (en) * | 2015-12-31 | 2018-06-12 | 南京理工大学 | Reverse osmosis membrane, preparation method and application thereof |
| CN107970776A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
| CN107970787A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
| CN107970793B (en) * | 2016-10-21 | 2019-12-24 | 中国石油化工股份有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN106512733A (en) * | 2016-12-12 | 2017-03-22 | 苏州富艾姆工业设备有限公司 | Preparation method of anti-pollution reverse osmosis membrane |
| CN108043252B (en) * | 2017-12-01 | 2020-10-30 | 时代沃顿科技有限公司 | High-performance reverse osmosis composite membrane and preparation method thereof |
| CN109078503B (en) * | 2018-08-17 | 2021-01-12 | 东华大学 | Hydrophilic treatment process for PET precision transfusion filtering nuclear pore membrane |
| CN111167322B (en) * | 2020-01-03 | 2020-12-22 | 安徽智泓净化科技股份有限公司 | Anti-fouling reverse osmosis membrane |
| CN111744373A (en) * | 2020-07-07 | 2020-10-09 | 杭州易膜环保科技有限公司 | Method for constructing amphoteric anti-pollution coating on polyamide surface |
| CN113244780B (en) * | 2021-05-17 | 2022-02-08 | 江苏泷膜环境科技有限公司 | Preparation method of anti-scaling and anti-yellowing composite reverse osmosis membrane |
| CN114146572B (en) * | 2021-12-07 | 2023-06-30 | 天津大学 | Preparation method of amide chain segment embedded covalent organic framework composite membrane and filter membrane thereof |
| CN114177774B (en) * | 2021-12-27 | 2024-05-31 | 杭州天创环境科技股份有限公司 | Construction method of polyamide reverse osmosis composite membrane anti-pollution coating |
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