CN110038446A - A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof - Google Patents
A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN110038446A CN110038446A CN201910469204.2A CN201910469204A CN110038446A CN 110038446 A CN110038446 A CN 110038446A CN 201910469204 A CN201910469204 A CN 201910469204A CN 110038446 A CN110038446 A CN 110038446A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention relates to a kind of antipollution aromatic polyamide composite reverse osmosis membranes and preparation method thereof, the preparation method of reverse osmosis membrane is that the polysulfone ultrafiltration membrane after cleaning is immersed in aqueous phase monomers solution, after taking-up is dried, single side is immersed in oil phase monomer solution, it is taken out after reaction a period of time and organic solvent volatilization is allowed to obtain nascent state reverse osmosis membrane completely；After nascent state reverse osmosis membrane surface coats one layer of pollution-resistant layer precursor solution, antipollution aromatic polyamide composite reverse osmosis membrane is obtained through Overheating Treatment, rinsing.Use one-step method of the invention constructs mixed-matrix pollution-resistant layer, design based on mixed substrate membrane containing nano-grade molecular sieve improves the permeability of functional layer, it realizes that mixed-matrix functional layer is fixed in the covalent bond of film surface by chemical graft and the method for chemical crosslinking, finally obtains the excellent anti-pollution reverse osmosis membrane of long-time stability.
Description
Technical field
The invention belongs to seperation film field, it is related to a kind of antipollution aromatic polyamide composite reverse osmosis membrane and its preparation side
Method.
Background technique
The reverse osmosis key technology for having become water process, water resource recycle with played in energy-saving and emission-reduction it is irreplaceable
Effect.Filmtec company, the U.S. was proposed FT-30 high-performance reverse osmosis composite membrane in 1980, realized reverse osmosis compound
The commercialization of film successfully develops a series of reverse osmosis composite membranes in succession.Due to the complexity of fouling membrane and to fouling membrane mechanism
Recognize unclear, increases the difficulty for solving membrane pollution problem, thus fouling membrane is always to restrict reverse osmosis further extensive use
Difficult point.
The method for solving reverse osmosis membrane pollution is pretreatment and Membrane cleaning, but is developed reverse osmosis with excellent stain resistance
Composite membrane is the most fundamental and most direct approach, is one of developing direction of membrane technology.Film surface hydrophily, roughness and lotus
It is electrically the important indicator for influencing reverse osmosis membrane antifouling property, anti-pollution reverse osmosis membrane preparation method mainly includes physics at present
Coating, chemical modification, blending and modifying.
The method coated using surface physics, other than it can be effectively improved film surface hydrophily, additionally it is possible to reduce table
Surface roughness enhances film stain resistance, is the modification mode mainly used in current business anti-pollution reverse osmosis membrane production.Mesh
Before, the companies such as Tao Shi, beautiful, the epoch Wo Dun in east are based on coating polyethylene alcohol and develop anti-pollution reverse osmosis membrane, but physical table
Face cladding process can introduce fine and close resistant layer in film surface, cause membrane flux to reduce, and lack between coating and film surface and stablize
Bonding action, will appear coating shedding phenomenon in During Process of Long-term Operation, lose anti-pollution effect.
Chemical graft is then that will there are the groups such as the functional molecular of reactivity and the imines of film surface, acyl chlorides to react, real
The chemical bonding of existing functional molecular and film surface, obtains the hydrophilic surface with good stability.But due to reverse osmosis membrane
The polyamide degree of cross linking of separating layer is high, makes the quantity and limited activity of film surface reactive group, and it is lower, poly- that there are grafting densities
Object chain is closed the problems such as being unevenly distributed on film.
Blend method is blended into hydrophilic polymer or nano material in oily phase or aqueous phase solution, in interfacial polymerization
It is embedded into desalination layer in film forming procedure, achievees the purpose that the anti-fouling performance for changing reverse osmosis membrane.But due to technology of preparing
It not yet grasps completely at present, this method would generally make the reduction of the polyamide degree of cross linking, cause the reduction of reverse osmosis membrane salt rejection rate, it is difficult to simultaneous
Care for the selectivity and resistance tocrocking of film.
Therefore, how to prepare efficient antipollution aromatic polyamide composite reverse osmosis membrane is the technology for needing to solve at present
Problem.
Summary of the invention
The object of the present invention is to provide a kind of antipollution aromatic polyamide composite reverse osmosis membranes and preparation method thereof.The present invention
Use one-step method construct mixed-matrix pollution-resistant layer, based on mixed substrate membrane containing nano-grade molecular sieve design improve functional layer permeability,
It realizes that mixed-matrix functional layer is fixed in the covalent bond of film surface by chemical graft and the method for chemical crosslinking, finally obtains length
The anti-pollution reverse osmosis membrane of phase excellent in stability.
To achieve the above object, the present invention adopts the following technical scheme that
A kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane of the invention, comprising the following steps:
(1) polysulfone ultrafiltration membrane after cleaning is immersed in aqueous phase monomers solution, after taking-up is dried, single side is immersed in oily phase
In monomer solution, taking-up allows organic solvent volatilization to obtain nascent state reverse osmosis membrane completely after reacting a period of time；The water phase list
Liquid solution is the aqueous phase solution of m-phenylene diamine (MPD) or piperazine；The oil phase monomer solution is the oil-phase solution of pyromellitic trimethylsilyl chloride；
(2) after nascent state reverse osmosis membrane surface coats one layer of pollution-resistant layer precursor solution, through Overheating Treatment, drift
It washes to obtain antipollution aromatic polyamide composite reverse osmosis membrane.
As the further improvement of above-described embodiment, the solute in the pollution-resistant layer precursor solution includes amido
Block polyethylene glycol, polyvinyl alcohol, hydrophilic nanoparticles and glutaraldehyde and one of acid or alkali；Wherein, amido blocks
The mass fraction of polyethylene glycol is 0.01-0.5%；The mass fraction of polyvinyl alcohol is 0.5-5%；The matter of hydrophilic nanoparticles
Amount score is 0.1-1%；The mass fraction of glutaraldehyde is 0.5-10%；The mass fraction of acid is 0-2%；The mass fraction of alkali is
0-2%.
As the further improvement of above-described embodiment, the coating thickness of the pollution-resistant layer precursor solution is 10-
200 microns.
As the further improvement of above-described embodiment, the molecular weight that amido blocks polyvinyl alcohol is ten thousand dalton of 0.1-20；
The molecular weight of polyvinyl alcohol is ten thousand dalton of 2-30, degree of hydrolysis 70-95%.
As the further improvement of above-described embodiment, the hydrophilic nanoparticles be nano silver, Nanometer Copper, nanogold,
Nano-titanium dioxide, nano silica, nano-silicon, nano molecular sieve, nano metal organic frame compound, nanometer covalently have
One or more of machine framework compound, carbon nanotube, nanometer carbon dots, nano graphene oxide, partial size are 3-500 nanometers.
As the further improvement of above-described embodiment, it is described acid be one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid with
On, the alkali is one or more of sodium hydroxide, potassium hydroxide, triethylamine, ethanol amine, diethanol amine, triethanolamine.
As the further improvement of above-described embodiment, in step (1), monomer mass concentration range is in aqueous phase monomers solution
0.1-2wt%, the soaking temperature in aqueous phase monomers solution are 0-15 DEG C, and soaking time is 30-90 seconds；
In step (1), the mass concentration range of the pyromellitic trimethylsilyl chloride contained in oil phase monomer solution is 0.05-
0.3wt%, temperature are -20~5 DEG C, and the reaction time is 10-40 seconds；The volatilization time of organic solvent is 5-40s.
As the further improvement of above-described embodiment, in step (2), heat treatment temperature is 90-120 DEG C, and the time is 3-5 points
Clock；PH is used successively to rinse when rinsing for the acid of 1-4, the alkali of pH10-14 and pure water, rinsing time is respectively 5-10 minutes.
As the further improvement of above-described embodiment, the solvent of the oil phase monomer solution is n-hexane.
The present invention also provides a kind of antipollutions of the preparation method of antipollution aromatic polyamide composite reverse osmosis membrane preparation
Aromatic polyamide composite reverse osmosis membrane.
The basic principle of the invention are as follows: acid chloride groups are contained on nascent state reverse osmosis membrane surface, can with before pollution-resistant layer
It drives in liquid solution and is reacted containing amido, hydroxyl, so that pollution-resistant layer is fixed to reverse osmosis membrane surface；Meanwhile in forerunner
In liquid solution under the catalytic action of acid or alkali and high temperature, amido blocks polyethylene glycol, amido and hydroxyl in polyvinyl alcohol, with
Condensation reaction occurs for glutaraldehyde, forms the bigger macromolecular structure of three-dimensional network shape, while again by receiving in precursor solution
Rice corpuscles is sealed up for safekeeping in three-dimensional net structure, it is ensured that it is not lost in use.
The utility model has the advantages that
The present invention is by coating pollution-resistant layer precursor solution, thermally treated and drift on nascent state reverse osmosis membrane surface
Anti-pollution reverse osmosis membrane is obtained after washing, it is advantageous that not changing original filming technology, functional layer is with three-dimensional net structure
And be fixed on reverse osmosis membrane by covalent bond, hydrone resistance to mass tranfer is low.Wherein, amido sealing end polyethylene glycol is by function
Layer is fixed to " anchor chain " in polyamide separating layer, and polyvinyl alcohol and glutaraldehyde are the ingredients to form three-dimensional net structure, acid, alkali
Microsphere catalyst, nanoparticle are the ingredient that three-dimensional net structure is sealed up for safekeeping, primarily serve the effect for reducing functional layer resistance to mass tranfer.
The prior art has the reverse osmosis membrane modified by physics coating, i.e., simple covering is simple to be blended, functional layer with
There is no chemical interaction between separating layer, functional layer is mainly linear polymeric, and function layer formation process is not related to chemistry
Reaction, stability are poor；And the functional layer of this patent is to be fixed to reverse osmosis membrane surface by chemical bond；It is to pass through chemical crosslinking
What effect was formed, there is three-dimensional net structure, and nanoparticle is mothballed in three-dimensional network, stability is high.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
For convenience, the example takes following operating condition: the test film pair first at 5.5MPa
The water flux F of 32000ppm sodium chloride solution1With salt rejection rate R1；Then at 5.5MPa, with 32000ppm sodium chloride, 1% ox
Haemocyanin and 1% humic acid mixed solution (25 DEG C of temperature), operation 120 hours after test flux；Finally use deionization
Water rinses, and surveys the water flux F to 32000ppm sodium chloride solution2With salt rejection rate R2, calculate flux recovery rate RF, characterization of membrane it is anti-
Pollutant performance.
RF=(F2/F1) × 100%.
Embodiment 1
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration mass concentration range is 2%, and temperature is 15 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then single side is immersed in oil
In phase monomer solution, the mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is -20 DEG C,
Reaction time is 40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；Nascent
State reverse osmosis membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.5wt%), poly- second by amido
Enol (mass fraction 5%), Nano silver grain (mass fraction 1%, partial size are 3-10 nanometers), glutaraldehyde (mass fraction
For 0.5%), hydrochloric acid (mass fraction 0.2%) constitute, wherein amido block polyvinyl alcohol molecular weight be 0.5 ten thousand dongles
?；The molecular weight of polyvinyl alcohol is 100,000 dalton, and degree of hydrolysis 85%, precursor solution coating thickness is 10 microns；90
DEG C heat treatment 5 minutes, then respectively with pH be 1,14,7 aqueous solution in rinse 10 minutes, obtain polyamide reverse osmose membrane, RF
=99.6%, F1=42.3L/m2/ h, R1=99.55%, R2=99.57%.
Comparative example 1
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 2%, and temperature is 15 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, the mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is -20 DEG C, the reaction time
It is 40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；5 are heat-treated at 90 DEG C
Minute, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 76.6%, F1
=42.7L/m2/ h, R1=99.53%, R2=99.56%.
The difference of the present invention and comparative example 1 is that the present invention contains functional layer, R of the present inventionFIt is apparently higher than the R of comparative example 1F,
And R2Value is of substantially equal with documents 1, and illustrating polyamide reverse osmose membrane of the invention not only has good antifouling property,
And salt rejection rate is held essentially constant, and is had excellent performance.
Embodiment 2
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 0.1%, and temperature is 0 DEG C, and soaking time is 90 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer
In solution, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.05%, and temperature is 5 DEG C, when reaction
Between be 40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.2wt%), polyvinyl alcohol by amido
(mass fraction 2%), mesoporous silicon dioxide nano particle (mass fraction 0.5%, partial size are 50-150 nanometers), glutaraldehyde
(mass fraction 0.5%), sodium hydroxide (mass fraction 1%) constitute, wherein amido sealing end polyvinyl alcohol molecular weight be
0.5 ten thousand dalton；The molecular weight of polyvinyl alcohol is 100,000 dalton, and degree of hydrolysis 85%, precursor solution coating thickness is 100
Micron；It is heat-treated 3 minutes at 90 DEG C, then is rinsed 5 minutes in the aqueous solution for being respectively 4,10,7 with pH, obtain polyamide reverse osmosis
Film, RFFor 99.2%, F1=65.0L/m2/ h, R1=93.35%, R2=93.57%.
Embodiment 3
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 1.5%, and temperature is 0 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer
In solution, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.15%, and temperature is 0 DEG C, when reaction
Between be 10 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 50s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.1%), polyvinyl alcohol (matter by amido
Amount score be 3%), (mass fraction is for graphene oxide (mass fraction 0.5%, piece diameter are 20-250 nanometers), glutaraldehyde
0.8%), sodium hydroxide (mass fraction 2%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 0.1 ten thousand dongles
?；The molecular weight of polyvinyl alcohol is 150,000 dalton, and degree of hydrolysis 80%, precursor solution coating thickness is 20 microns；120
DEG C heat treatment 5 minutes, then respectively with pH be 1,14,7 aqueous solution in rinse 10 minutes, obtain polyamide reverse osmose membrane, RF
It is 99.7%, F1=45.8L/m2/ h, R1=99.65%, R2=99.66%.
Embodiment 4
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 1.5%, and temperature is 0 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer
In solution, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.15%, and temperature is 0 DEG C, when reaction
Between be 10 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 5s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.1%), polyvinyl alcohol (matter by amido
Measure score be 0.5%), (mass fraction is for carbon nanotube (mass fraction 0.1%, length be 100 nanometers), glutaraldehyde
10%), sodium hydroxide (mass fraction 1.8%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 50,000 dalton；
The molecular weight of polyvinyl alcohol is 20,000 dalton, and degree of hydrolysis 95%, precursor solution coating thickness is 20 microns；In 120 DEG C of heat
Processing 3 minutes, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor
98.6%, F1=44.3L/m2/ h, R1=99.50%, R2=99.51%.
Embodiment 5
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 2%, and temperature is 0 DEG C, and soaking time is 40 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.25%, and temperature is -10 DEG C, when reaction
Between be 30 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 15s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.5%), polyvinyl alcohol (matter by amido
Measure score be 5%), (mass fraction is for molecular sieve ZIF-8 (mass fraction 0.5%, partial size be 500 nanometers), glutaraldehyde
10%), ethanol amine (mass fraction 3%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 200,000 dalton；It is poly-
The molecular weight of vinyl alcohol is 100,000 dalton, and degree of hydrolysis 85%, precursor solution coating thickness is 20 microns；In 120 DEG C of heat
Processing 5 minutes, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor
99.0%, F1=40.8L/m2/ h, R1=99.72%, R2=99.74%.
Embodiment 6
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 2%, and temperature is -5 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.25%, and temperature is -10 DEG C, when reaction
Between be 40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 25s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.05%), polyvinyl alcohol (matter by amido
Measure score be 1%), the organic mine valence compound MIL-101 of metal (mass fraction 0.5%, partial size be 200 nanometers), glutaraldehyde
(mass fraction 2%), nitric acid (mass fraction 1%) are constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 80,000
Er Dun；The molecular weight of polyvinyl alcohol is 300,000 dalton, and degree of hydrolysis 70%, precursor solution coating thickness is 5 microns；?
120 DEG C are heat-treated 5 minutes, then rinse 10 minutes in the aqueous solution for being respectively 1,14,7 with pH, obtain polyamide reverse osmose membrane,
RFFor 99.8%, F1=41.7L/m2/ h, R1=99.68%, R2=99.70%.
Embodiment 7
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 1%, and temperature is -5 DEG C, and soaking time is 40 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is 0 DEG C, and the reaction time is
40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis membrane
Surface coats an one functional layer precursor solution, and the solution is by amido sealing end polyethylene glycol (0.05%), polyvinyl alcohol (quality point
Number for 2.5%), covalent organic frame compound COF-108 (mass fraction 1%, partial size be 300 nanometers), glutaraldehyde (quality
Score be 3%), sulfuric acid (mass fraction 2%) constitute, wherein amido block polyvinyl alcohol molecular weight be 150,000 dalton；
The molecular weight of polyvinyl alcohol is 120,000 dalton, and degree of hydrolysis 84%, precursor solution coating thickness is 15 microns；At 120 DEG C
Heat treatment 5 minutes, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor
99.1%, F1=45.6L/m2/ h, R1=99.45%, R2=99.46%.
Embodiment 8
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein matter containing m-phenylene diamine (MPD)
Measuring concentration range is 1.8%, and temperature is 10 DEG C, and soaking time is 30 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer
In solution, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.15%, and temperature is -5 DEG C, when reaction
Between be 30 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 15s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis
Permeable membrane surface coats an one functional layer precursor solution, which blocks polyethylene glycol (0.01%), polyvinyl alcohol (matter by amido
Measure score be 4%), nanometer copper particle (mass fraction 1%, partial size be 3-15 nanometers), glutaraldehyde (mass fraction 1%),
Diethanol amine (mass fraction 5%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 100,000 dalton；Polyethylene
The molecular weight of alcohol is 50,000 dalton, and degree of hydrolysis 90%, precursor solution coating thickness is 50 microns；5 are heat-treated at 110 DEG C
Minute, then respectively with pH to rinse 8 minutes in 3,12,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 99.45%, F1
=44.9L/m2/ h, R1=99.44%, R2=99.45%.
Embodiment 9
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein quality containing piperazine is dense
Spending range is 1.5%, and temperature is 8 DEG C, and soaking time is 60 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer solution
In, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.15%, and temperature is -5 DEG C, and the reaction time is
30 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 15s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis membrane
Surface coats an one functional layer precursor solution, and the solution is by amido sealing end polyethylene glycol (0.01%), polyvinyl alcohol (quality point
Number for 4%), nano Au particle (mass fraction 1%, partial size be 5-15 nanometers), glutaraldehyde (mass fraction 1%), three second
Hydramine (mass fraction 5%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 0.5 ten thousand dalton；Polyvinyl alcohol
Molecular weight is 100,000 dalton, and degree of hydrolysis 85%, precursor solution coating thickness is 70 microns；5 points are heat-treated at 110 DEG C
Clock, then respectively with pH to rinse 8 minutes in 3,12,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 99.47%, F1=
42L/m2/ h, R1=99.55%, R2=99.57%.
Comparative example 2
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein quality containing piperazine is dense
Spending range is 1.5%, and temperature is 8 DEG C, and soaking time is 60 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer solution
In, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.15%, and temperature is -5 DEG C, and the reaction time is
30 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 15s, obtains nascent state reverse osmosis membrane；5 points are heat-treated at 110 DEG C
Clock, then respectively with pH to rinse 8 minutes in 3,12,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 85.6%, F1=
42L/m2/ h, R1=99.55%, R2=99.57%.
Equally, the embodiment of the present invention 9 and comparative example 2 compare, it can be found that the polyamide reverse osmose membrane being film-made using piperazine
It is that functional layer of the invention equally has good antifouling property, and guarantees the effect that salt rejection rate is held essentially constant.
Embodiment 10
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein quality containing piperazine is dense
Spending range is 1%, and temperature is -5 DEG C, and soaking time is 40 seconds, after taking-up is dried；Then single side is immersed in oil phase monomer solution
In, the mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is 0 DEG C, the reaction time 40
Second；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis membrane table
Face coats an one functional layer precursor solution, which blocks polyethylene glycol (0.05%), polyvinyl alcohol (mass fraction by amido
For 2.5%), nano-titanium dioxide (mass fraction 1%, partial size be 15-100 nanometers), glutaraldehyde (mass fraction 3%),
Hydrochloric acid (mass fraction 1.5%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 30,000 dalton；Polyvinyl alcohol
Molecular weight is 90,000 dalton, and degree of hydrolysis 84%, precursor solution coating thickness is 15 microns；It is heat-treated 5 minutes at 120 DEG C,
It is rinsed 10 minutes in the aqueous solution for being respectively again 1,14,7 with pH, obtains polyamide reverse osmose membrane, RFFor 99.2%, F1=
52.3L/m2/ h, R1=90.25%, R2=90.26%.
Embodiment 11
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein quality containing piperazine is dense
Spending range is 1.3%, and temperature is -10 DEG C, and soaking time is 35 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is 0 DEG C, and the reaction time is
40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis membrane
Surface coats an one functional layer precursor solution, and the solution is by amido sealing end polyethylene glycol (0.05%), polyvinyl alcohol (quality point
Number for 2.5%), nanometer carbon dots (mass fraction 1.5%, partial size be 25-110 nanometers), glutaraldehyde (mass fraction 3%),
Formic acid (mass fraction 1.5%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 4.5 ten thousand dalton；Polyvinyl alcohol
Molecular weight be 100,000 dalton, degree of hydrolysis 85%, precursor solution coating thickness be 15 microns；5 points are heat-treated at 120 DEG C
Clock, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 99.4%, F1=
55.8L/m2/ h, R1=90.45%, R2=90.47%.
Embodiment 12
Polysulfone ultrafiltration membrane after deionized water is sufficiently cleaned is immersed in aqueous phase monomers solution, wherein quality containing piperazine is dense
Spending range is 1.3%, and temperature is -10 DEG C, and soaking time is 35 seconds, after taking-up is dried；Then it is molten to be immersed in oil phase monomer for single side
In liquid, mass concentration range in oil phase monomer solution containing pyromellitic trimethylsilyl chloride is 0.3%, and temperature is 0 DEG C, and the reaction time is
40 seconds；Taking-up makes organic solvent volatilization complete, and the volatilization time is 40s, obtains nascent state reverse osmosis membrane；In nascent state reverse osmosis membrane
Surface coats an one functional layer precursor solution, and the solution is by amido sealing end polyethylene glycol (0.05%), polyvinyl alcohol (quality point
Number for 2.5%), nanometer carbon dots (mass fraction 1.5%, partial size be 25-110 nanometers), glutaraldehyde (mass fraction 3%),
Formic acid (mass fraction 1.5%) is constituted, wherein the molecular weight that amido blocks polyvinyl alcohol is 9.5 ten thousand dalton；Polyvinyl alcohol
Molecular weight be 150,000 dalton, degree of hydrolysis 80%, precursor solution coating thickness be 15 microns；5 points are heat-treated at 120 DEG C
Clock, then respectively with pH to rinse 10 minutes in 1,14,7 aqueous solution, obtain polyamide reverse osmose membrane, RFFor 99.3%, F1=
55.6L/m2/ h, R1=90.08%, R2=90.11%.
Claims (10)
1. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane, characterized in that the following steps are included:
(1) polysulfone ultrafiltration membrane after cleaning is immersed in aqueous phase monomers solution, after taking-up is dried, single side is immersed in oil phase monomer
In solution, taking-up allows organic solvent volatilization to obtain nascent state reverse osmosis membrane completely after reacting a period of time；The aqueous phase monomers are molten
Liquid is the aqueous phase solution of m-phenylene diamine (MPD) or piperazine；The oil phase monomer solution is the oil-phase solution of pyromellitic trimethylsilyl chloride；
(2) it after nascent state reverse osmosis membrane surface coats one layer of pollution-resistant layer precursor solution, through Overheating Treatment, rinses
To antipollution aromatic polyamide composite reverse osmosis membrane.
2. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 1, feature exist
In the solute in the pollution-resistant layer precursor solution includes amido sealing end polyethylene glycol, polyvinyl alcohol, hydrophilic nano
Particle and glutaraldehyde and one of acid or alkali；Wherein, the mass fraction of amido sealing end polyethylene glycol is 0.01-0.5%；It is poly-
The mass fraction of vinyl alcohol is 0.5-5%；The mass fraction of hydrophilic nanoparticles is 0.1-1%；The mass fraction of glutaraldehyde
For 0.5-10%；The mass fraction of acid is 0-2%；The mass fraction of alkali is 0-2%.
3. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 1, feature exist
In the coating thickness of the pollution-resistant layer precursor solution is 10-200 microns.
4. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 2, feature exist
In the molecular weight that amido blocks polyvinyl alcohol is ten thousand dalton of 0.1-20；The molecular weight of polyvinyl alcohol is ten thousand dalton of 2-30, water
Xie Du is 70-95%.
5. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 2, feature exist
In, hydrophilic nanoparticles be nano silver, Nanometer Copper, nanogold, nano-titanium dioxide, nano silica, nano-silicon,
Nano molecular sieve, nanometer covalent organic framework compound, carbon nanotube, nanometer carbon dots, is received nano metal organic frame compound
One or more of rice graphene oxide, partial size are 3-500 nanometers.
6. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 2, feature exist
In the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, and the alkali is sodium hydroxide, potassium hydroxide, three
One or more of ethamine, ethanol amine, diethanol amine, triethanolamine.
7. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 1, feature exist
In in step (1), monomer mass concentration range is 0.1-2wt%, the immersion in aqueous phase monomers solution in aqueous phase monomers solution
Temperature is 0-15 DEG C, and soaking time is 30-90 seconds.
8. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 1, feature exist
In in step (1), the mass concentration range of the pyromellitic trimethylsilyl chloride contained in oil phase monomer solution is 0.05-0.3wt%, temperature
Degree is -20~5 DEG C, and the reaction time is 10-40 seconds；The volatilization time of organic solvent is 5-40s.
9. a kind of preparation method of antipollution aromatic polyamide composite reverse osmosis membrane according to claim 1, feature exist
In in step (2), heat treatment temperature is 90-120 DEG C, and the time is 3-5 minutes；Use pH for the acid of 1-4, pH10-14 when rinsing
Alkali and pure water successively rinse, rinsing time be respectively 5-10 minutes.
10. the preparation method system of -9 any a kind of antipollution aromatic polyamide composite reverse osmosis membranes according to claim 1
Standby antipollution aromatic polyamide composite reverse osmosis membrane.
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Application publication date: 20190723 |