CN109847586A - High-flux reverse osmosis membrane and its preparation method and application - Google Patents
High-flux reverse osmosis membrane and its preparation method and application Download PDFInfo
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- CN109847586A CN109847586A CN201811566175.3A CN201811566175A CN109847586A CN 109847586 A CN109847586 A CN 109847586A CN 201811566175 A CN201811566175 A CN 201811566175A CN 109847586 A CN109847586 A CN 109847586A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
The present invention relates to high-flux reverse osmosis membranes and its preparation method and application.The described method comprises the following steps: the polymer solution that preparation is dispersed with inorganic silicate nano material is coated on backing material as casting solution, is immersed in coagulating bath and is obtained basement membrane；Basement membrane is immersed into dopamine/ZIF-8 suspension, grows dopamine/ZIF-8 in membrane surface, obtains the modification basement membrane with nanometer layer among dopamine/ZIF-8；Modified basement membrane is immersed into aqueous phase solution, organic phase solution progress interfacial polymerization preparation functional layer, obtains primary film；Primary film is soaked in water, dissolution removes intermediate nanometer layer, obtains the high-flux reverse osmosis membrane.The functional layer of the reverse osmosis membrane is thin, effective infiltrating area is big, flux is greatly improved while not influencing salt rejection rate.The reverse osmosis membrane can be used for the processing, food processing, pharmaceutical industry of water treatment applications, industry or municipal wastewater.The invention further relates to membrane components and filtration system including the reverse osmosis membrane.
Description
Technical field
The present invention relates to membrane for water treatment technical fields, relate more specifically to reverse osmosis membrane technology field, in particular to a kind of
High-flux reverse osmosis membrane and its preparation method and application further relates to the membrane component for including the high-flux reverse osmosis membrane, filtering is
System.
Background technique
According to the data that the United Nations announces, the whole world and is arrived more than 1,000,000,000 inhabitants lives in water resource scarce areas at present
2025, this number will rise to 1,800,000,000.In addition, pursuit and worsening Drinking Water of the people to healthy living
Between form sharp contradiction.In order to solve the problems, such as water shortage, wastewater treatment and people's daily water consumption, various water treatment technologies
It comes into being, for example rejection is high, flux is big, chemical stability is good, operating pressure is low because having for reverse osmosis membrane separation technology
And the advantages that water body selectively capable of being purified and be separated, become in global water treatment field and is most widely used
A kind of isolation technics.
Separating property of the reverse osmosis polyamide functional layer structure concerning film, however between the flux of film and desalting performance usually
There are shifting relationship (Trade-off phenomenon) (Park et al., Science, 2017,356,1137).Existing market
On requirement to the membrane component of big flux and high water outlet quality it is more beneficial harsh, imply while improving the flux and salt ion of film
Rejection has become a kind of irreversible trend, this is also the bottleneck problem that current membrane for water treatment faces.
The regulation design for carrying out molecular structure to functional layer is of great significance to the performance for promoting film, for example develops advanced
Membrane material be modified to reduce resistance when water passes through functional layer, film can be promoted under the premise of the selectivity of not expendable film
Permeation flux, including development containing aquaporin, Nano-size Porous Graphite alkene, covalent triazine frame, two sulphur (oxygen) change molybdenum, have
Modified Membrane (Werber the et al., Nat.Rev.Mater., 2016,1,16018 of the materials such as the porous cage of machine, zeolite nanometer sheet；
CN201610280385.0).Wherein CN201610280385.0 describes a kind of coating modified fragrant adoption of graphene oxide
Amide reverse osmosis membrane and preparation method thereof, graphite oxide ene coatings are coated in dense separation layers surface, can effectively improve compound anti-
Salt rejection rate, antifouling property and the anti-chlorine performance of permeable membrane, but this method can not achieve large-scale industrial production, and
Modified film properties are unstable.
Reverse osmosis membrane can also be reduced to the resistance of water by preparing thinner functional layer by control interface polymerization process.Shan
Et al. by microfacies interface polymerization reaction control the diffusion of microfacies monomer and gradually polymerization to eliminate the loose knot of functional layer
The permeation flux of structure, the ultra-thin nanofiltration membrane being prepared using spraying technology is high, is 23 times of (Shan of general goods membrane flux
Et al., ACS Appl.Mater.Interfaces, 2017,9,44820-44827.), but this method is currently in test
Stage can not achieve industrialized production.CN201310038807.X describes a kind of double desalting layer composite reverse osmosis membrane, by desalination
Layer becomes loose desalination layer and fine and close desalination layer from traditional one layer, and functional layer overall thickness is constant, but fine and close desalination layer thickness drop
It is low to increase substantially water flux and salt rejection rate remains unchanged.
In addition, roughness height and random nanostructure middle layer such as inorganic nano can be prepared in support layer surface
Line, carbon nanotube, Cellulose nanocrystal body layer etc., provide more uniform medium holes, to increase considerably aqueous phase monomers
Surface area and distributing homogeneity are infiltrated, the release of monomer is when further control interface polymerize to prepare thinner functional layer
(Karan et al.,Science,2015,348,1347；Wang et al.,Nature Commun.,2018,9,2004；
CN201410157619.3).Wherein CN201410157619.3 describes a kind of sub- Nano filtering composite membrane and preparation method thereof, poly-
A strata dimethyl siloxane middle layer is coated on sulfone porous membrane layer, then passes through the interface of pyromellitic trimethylsilyl chloride and m-phenylene diamine (MPD)
Polymerization reaction obtains the reverse osmosis membrane with different molecular weight cut off and water flux, but the film is only used in small organic molecule
Removal in terms of.
Although the prior art can prepare permeation flux of the thinner functional layer to improve film, prepare thickness it is thin,
The aramid layer of zero defect and good mechanical property makes reverse osmosis membrane improve membrane flux under the premise of not losing other performances and still has
There is very big challenge.
Summary of the invention
Problems to be solved by the invention
It is an object of the invention to solve problem above existing in the prior art, a kind of reverse osmosis membrane of high throughput is provided
And its preparation method and application, the reverse osmosis membrane is greatly increased with effective infiltrating area and thinner, good mechanical property
Functional layer, and flux is greatly improved under the premise of not changing desalting performance.
The solution to the problem
The present inventor etc. after carrying out a intensive study in order to achieve the goal above, have found, by carrying out to basement membrane
It is modified, intermediate nanometer layer is grown in membrane surface, polyamide functional layer is further prepared by interfacial polymerization, and then dissolution removes
Fall intermediate nanometer layer, thinner and good mechanical property functional layer can be prepared, solve the salt rejection rate of reverse osmosis membrane with
The restriction of flux trade-off relationship improves the flux of reverse osmosis membrane under the premise of not changing desalting performance.
The intermediate nanometer layer prepared in the present invention is dissolved removal after polyamide functional layer is prepared, because
This, reverse osmosis membrane according to the present invention is also known as the reverse osmosis membrane containing intermediate nanometer sacrificial layer.
One aspect of the present invention is related to a kind of preparation method of high-flux reverse osmosis membrane, and the method includes following steps
It is rapid:
(1) polymer solution that preparation is dispersed with inorganic silicate nano material is coated in backing material as casting solution
On, it is then immersed in coagulating bath, obtains basement membrane；
(2) dopamine/ZIF-8 suspension is prepared, the basement membrane obtained in step (1) is immersed in the suspension, is made
Dopamine/ZIF-8 is grown in membrane surface, is then rinsed, and the modification basement membrane with nanometer layer among dopamine/ZIF-8 is obtained；
(3) basement membrane will be modified obtained in step (2) to immerse aqueous phase solution, carry out interfacial polymerization system in organic phase solution
Standby functional layer, obtains having the primary film of the complex reverse osmosis membrane of functional layer；
(4) the primary film obtained in step (3) is soaked in water, dissolution removes the intermediate nanometer layer, obtains high pass
Measure reverse osmosis membrane.
Method according to the present invention, wherein the backing material is non-woven fabrics, wherein the polymer solution includes
Polymer and solvent, the polymer are polysulfones, polyether sulfone, polyphenylsulfone, Kynoar, polyvinyl chloride, cellulose and its spread out
At least one of biology, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polyimides, polyethylene,
The solvent be N,N-dimethylformamide DMF, N, N- dimethyl pyrrolidone, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide,
N-hexane, hexamethylene, normal heptane, Isopars Isopar G, chloroform, chloroform, toluene, benzene, methanol, in propyl alcohol
It is at least one, it is preferable that concentration of the polymer in casting solution is 10wt% to 25wt%；Preferably, the inorganic silicon
Silicate nanometer material is aqueous rich magnesium aluminosilicate, and the concentration in casting solution is 0.5wt% to 5wt%, it is highly preferred that institute
Stating inorganic silicate nano material is attapulgite；Preferably, active hydrophilic stabilizer is added in the casting solution, is being cast
Concentration in film liquid is 0.5wt% to 5wt%, it is highly preferred that the active hydrophilic stabilizer is polyvinylpyrrolidone；Institute
Stating coagulating bath is water-bath, it is preferable that DMF is added in coagulating bath.
Method according to the present invention, wherein in the step (2), the dopamine/ZIF-8 suspension by with
It is prepared by lower step:
(a) by Zn (NO3)2·6H2The water of O and the mixed solution of alcohol are added in the alcoholic solution of 2-methylimidazole and are uniformly mixed
Obtain dispersion liquid, it is preferable that the alcohol is methanol；
(b) dopamine hydrochloride and tromethamine Tris-HCl buffer are added in the dispersion liquid obtained in step (a),
Obtain the dopamine/ZIF-8 suspension；
Preferably, the growth and flushing carry out primary or repeat repeatedly.
Method according to the present invention the, wherein Zn (NO3)2·6H2Concentration of the O in the mixed solution of water and alcohol
For 1.0mol/L to 2.5mol/L, the concentration in the alcoholic solution of the 2-methylimidazole is 5mol/L to 15mol/L；Preferably,
Zn (the NO3)2·6H2The volumetric concentration of the water of O and the mixed solution of alcohol in the dopamine/ZIF-8 suspension is
50vol% to 70vol%；Preferably, body of the alcoholic solution of the 2-methylimidazole in the dopamine/ZIF-8 suspension
Product concentration is 30vol% to 60vol%；Preferably, the dopamine hydrochloride is in the dopamine/ZIF-8 suspension
Concentration is 0.40g/L to 0.60g/L；Preferably, range of the tromethamine Tris-HCl pH of cushioning fluid 7.5 to 9.2
It is interior.
Method according to the present invention, wherein including aqueous phase monomers and water in the aqueous phase solution, it is preferable that the water
Phase monomer be m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, to toluenediamine, toluylenediamine, ortho-toluene diamine, benzidine
At least one of, it is highly preferred that concentration of the aqueous phase monomers in the aqueous phase solution is 0.5wt% to 5wt%；It is described
It include organic phase monomer and solvent in organic phase solution, it is preferable that the organic phase monomer is o-phthaloyl chloride, isophthalic diformazan
Acyl chlorides, paraphthaloyl chloride, 4, at least one of 4 '-biphenyl dimethyl chlorides, pyromellitic trimethylsilyl chloride, it is preferable that the solvent
For at least one of n-hexane, hexamethylene, normal heptane, Isopars Isopar G, it is preferable that the organic phase monomer
Concentration in the organic phase solution is 0.005wt% to 3wt%.
Another aspect of the present invention is related to a kind of high-flux reverse osmosis membrane of method preparation according to the present invention.
High-flux reverse osmosis membrane according to the present invention, wherein the bottom of the polyamide functional layer has nanoscale thick
Rugosity, bottom have fold-like structures.
An additional aspect of the present invention is related to the purposes of high-flux reverse osmosis membrane, is used for water treatment applications, industry or city
The processing of city's waste water, food processing, pharmaceutical industry.
Other aspects of the invention are related to a kind of membrane component comprising high-flux reverse osmosis membrane above-mentioned.
Other aspects of the invention are related to a kind of filtration system comprising membrane component above-mentioned.
The effect of invention
The advantages of preparation method of the high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer provided through the invention is,
Basement membrane is obtained by the way that the casting solution for being dispersed with inorganic silicate nano material to be coated on backing material, the machine of obtained basement membrane
Tool performance, hydrophily, roughness etc. are all improved.Further, by the way that basement membrane is immersed dopamine/ZIF-8 suspension
It grows dopamine/ZIF-8 in membrane surface, obtains having the basement membrane of nanometer layer among dopamine/ZIF-8, it is hydrophily, thick
Rugosity further enhances, and can be conducive to preparation and be more evenly distributed and thinner functional layer；Further carry out boundary
Face polymerize to obtain the compound reverse osmosis primary film with polyamide functional layer；Primary film is impregnated in pure water, in dissolution removing
Between nanometer layer, high-flux reverse osmosis membrane of the invention can be made.
The thickness of the high-flux reverse osmosis membrane being prepared by means of the present invention not only functional layer is thin, mechanical performance
Get well, be evenly distributed, effective infiltrating area it is big, and flux is increased substantially under the premise of not influencing desalting performance.
Specific embodiment
One aspect of the present invention is related to high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer and preparation method thereof and uses
On the way.The invention further relates to the membrane components and filtration system that include the high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer.
I, the preparation method of the high-flux reverse osmosis membrane of the invention containing intermediate nanometer sacrificial layer
As the preparation method of the high-flux reverse osmosis membrane of the invention containing intermediate nanometer sacrificial layer, following step is specifically included
It is rapid:
(1) polymer solution that preparation is dispersed with inorganic silicate nano material is coated in backing material as casting solution
On, it is then immersed in coagulating bath, obtains basement membrane；
(2) dopamine/ZIF-8 suspension is prepared, the basement membrane obtained in step (1) is immersed in the suspension, is made
Dopamine/ZIF-8 is grown in membrane surface, is then rinsed, and the modification basement membrane with nanometer layer among dopamine/ZIF-8 is obtained；
(3) basement membrane will be modified obtained in step (2) to immerse aqueous phase solution, carry out interfacial polymerization system in organic phase solution
Standby polyamide functional layer, obtains having the primary film of the complex reverse osmosis membrane of polyamide functional layer；
(4) the primary film obtained in step (3) is soaked in water, dissolution removes the intermediate nanometer layer, obtains high pass
Measure reverse osmosis membrane.
The polymer solution being used in the present invention includes polymer and solvent.The polymer being used in the present invention is poly-
Sulfone, polyether sulfone, polyphenylsulfone, Kynoar, polyvinyl chloride, cellulose and its derivates, polycarbonate, poly-methyl methacrylate
At least one of ester, polyethyl methacrylate, polyimides, polyethylene, it is preferable that be polysulfones, polyether sulfone, more preferably
For polysulfones.
The polysulfones being used in the present invention is not particularly limited, and can be bisphenol A-type PSF (i.e. usually said PSF), gathers
Fragrant sulfone and polyether sulfone.It can be used alone polysulfones or any combination using a variety of polysulfones.Gather when using a variety of different
When the combination of sulfone, the mass ratio of different types of polysulfones is not particularly limited.
The solvent that the polymer solution being used in the present invention includes is not particularly limited, and can be N, N- dimethyl formyl
Amine DMF, N, it is N- dimethyl pyrrolidone, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, n-hexane, hexamethylene, normal heptane, different
At least one of structure alkane solvent Isopar G, chloroform, chloroform, toluene, benzene, methanol, propyl alcohol.
Preferably, casting solution is prepared as described below:
Inorganic silicate nano material is evenly dispersed in a solvent, it can be using ultrasonic disperse mode, mechanical stirring point
The mode of dissipating is, it is preferable to use ultrasonic disperse mode.It preferably, is that 0.2 μm of microfiltration membranes is depressurized with aperture after being uniformly dispersed
It filters, removes impurity, obtain inorganic silicate nano material filtrate.
Preferably, active hydrophilic stabilizer is added into the filtrate under stirring, continues to stir, until activity
Hydrophilic stabilizer is uniformly dispersed in filtrate.While being kept stirring, polymer and surplus is added in heat temperature raising thereto
Solvent, continue stirring until polymer be completely dissolved, thus obtain casting solution.Wherein, temperature is increased to 80 DEG C to 95 DEG C
Range can promote decomposition and solvent of the dissolution of polymer without will lead to polymer when controlling within this temperature range
Volatilization, accelerate solution rate, shorten dissolution time, more preferable heating temperature is within the scope of 85-95 DEG C, even more preferably
85-90 DEG C, solution rate can be further speeded up and shorten dissolution time.
Preferably, the inorganic silicate nano material is aqueous rich magnesium aluminosilicate, and more preferably attapulgite is excellent
Selection of land, concentration of the inorganic silicate nano material in casting solution are 0.5wt% to 5wt%.Preferably 0.5wt% is extremely
2wt%, more preferably 0.8wt% are to 1.2wt%.
Concentration of the polymer in casting solution be 10wt% to 25wt%, when concentration in the range when, it is obtained
The quality (such as film strength, pore size) of film is more excellent.If concentration of the polymer in casting solution is lower than 10wt%, casting
Membrane concentration is too low, and the structure of preparation gained basement membrane is excessively loose to cause film strength to decline, and is easily damaged, and aperture is too big,
It is unable to reach that rejection effect or even casting solution viscosity are too low to be caused to form a film.If concentration of the polymer in casting solution is super
25wt% is crossed, then casting solution concentration is too high, and viscosity is larger, and preparation gained based film structure excessively densification leads to porosity, roughness
Reduction, the defect of film are more, and cutoff performance is poor.Preferably 10wt% to 20wt%, more preferably 16wt% are to 20wt%.It can
Further to promote the quality of membrane material obtained.
Preferably, active hydrophilic stabilizer is added in casting solution.Preferably, the active hydrophilic stabilizer is polyethylene
Base pyrrolidones.Preferably, concentration of the active hydrophilic stabilizer in casting solution is 0.5wt% to 5wt%.Preferably
0.5wt% to 2wt%, more preferably 0.8wt% are to 1.2wt%.
Preferably, it filters, is cooled to room temperature after the casting solution prepared as described above is carried out vacuum defoamation processing.
Further, casting solution derived above is coated on backing material, coating method is not particularly limited,
Coating method usually used in reverse osmosis membrane preparation field, such as the tape casting, dip coating, knife coating etc. can be used, it is more excellent
It is selected as knife coating.Coated in being followed by immersed in coagulating bath on backing material, so that casting solution freezing film.
The backing material being used in the present invention is non-woven fabrics, the material of non-woven fabrics is not particularly limited, Ke Yiwei
Polypropylene (PP), terylene (PET), polyamide fibre (PA), viscose rayon, acrylic fibers, polyethylene (HDPE), polyvinyl chloride fibre (PVC), cellulose and its spread out
Biology etc., preferably polypropylene (PP) non-woven fabrics and terylene (PET) non-woven fabrics, more preferably polypropylene (PP) non-woven fabrics.
The coagulating bath is water-bath, it is preferable that DMF is added in coagulating bath.DMF is further added in coagulating bath can be with
The interaction parameter between solvent and non-solvent is weakened, macropore can be inhibited by changing casting film lyogel double diffusion process
It is formed, the content of component 1 is higher in coagulating bath within the scope of a certain concentration, then the aperture of film is smaller.Preferably, it adds
The DMF of 0.5wt% to 3wt%, more preferably 1.0wt% are to 2.0wt%.
The temperature of coagulating bath is 5-25 DEG C, preferably 5-20 DEG C, more preferably 15-20 DEG C.By the temperature for adjusting coagulating bath
Degree, also can achieve the purpose of the pore size of adjusting film, the temperature of coagulating bath is lower, and the aperture of film is smaller.
By liquid-liquid phase conversion process, macromolecule freezing film in casting solution is bonded in nonwoven surface, and with nothing
There is certain cementation between woven fabric.Processing time, that is, inversion of phases time in coagulating bath is 20-80 seconds, preferably
30-60 seconds.If the inversion of phases time is more than 80 seconds, film occurs mutually to separate completely, continue extend the time will no longer change film
Phase separation degree.If the inversion of phases time be lower than 20 seconds, since the inversion of phases time is shorter, although film surface mutually separate it is complete
At, but do not separated mutually completely inside film, a large amount of solvents will be remained inside film, finally will affect film properties.
Preferably, it is further arranged in deionized water and is rinsed after forming a film by coagulating bath processing, when to rinsing
Between be not particularly limited, can be 100 seconds to 250 seconds, preferably 150 seconds to 200 seconds, thus obtain through inorganic silicate nanometer
The basement membrane of material modification.
Good mechanical property through the nano-material modified obtained basement membrane of inorganic silicate has excellent hydrophily, water
Contact angle is dripped in the range of 50o to 80o.
The present inventor etc. thinks that principle based on technical solution provided by the invention is as follows:
Inorganic silicate nano material is more specifically aqueous rich magnesium aluminosilicate clays mineral especially attapulgite, is
A kind of aqueous rich magnesium aluminosilicate clays mine with chain layer structure, material good hydrophilic property itself and have one-dimensional rod-like knot
Structure, the basement membrane good mechanical property after inorganic silicate is nano-material modified, the high porosity of membrane surface and narrow aperture point
Cloth can be conducive to subsequent nano material middle layer to be prepared and sprawl more evenly, excellent hydrophily can be conducive to basement membrane with
The combination of subsequent middle layer to be prepared is closer.
In the step (2), the dopamine/ZIF-8 suspension is prepared by following steps:
(a) by Zn (NO3)2·6H2The water of O and the mixed solution of alcohol are added in the alcoholic solution of 2-methylimidazole and are uniformly mixed
Obtain dispersion liquid, it is preferable that the alcohol is methanol；
(b) dopamine hydrochloride and tromethamine Tris-HCl buffer are added in the dispersion liquid obtained in step (a),
It is uniformly mixed and obtains the dopamine/ZIF-8 suspension.
Zn (the NO3)2·6H2Concentration of the O in the mixed solution of water and alcohol is 1.0mol/L to 2.5mol/L, preferably
For 1.5mol/L to 2.5mol/L.The volume ratio of water and alcohol is 1:1 to 1:3, preferably 1:1 to 1:2.
The 2-methylimidazole alcoholic solution concentration be 5mol/L to 15mol/L, preferably 10mol/L to 15mol/L,
More preferably 10mol/L to 12.5mol/L.
Preferably, the alcohol is methanol.
Zn (the NO3)2·6H2The water of O and the mixed solution of alcohol are relative to the dopamine/ZIF-8 suspension volume
Concentration is 50vol% to 70vol%, preferably 50vol% to 60vol%.
The alcoholic solution of the 2-methylimidazole is 30vol% relative to the dopamine/ZIF-8 suspension volumetric concentration
To 60vol%, preferably 30vol% to 50vol%, preferably 30vol% to 40vol%.
The dopamine hydrochloride is 0.40g/L to 0.60g/L relative to the dopamine/ZIF-8 suspension concentration,
Preferably 0.40g/L to 0.50g/L.The pH value of the buffer is in the range of 7.5 to 9.2, and preferably 7.5 to 9, more preferably
It is 8 to 9.
Preferably, dopamine/ZIF-8 suspension is prepared as described below:
At normal temperature, while agitating by Zn (NO3)2·6H2The water of O and the mixed solution of alcohol pour into rapidly 2- methyl
In the alcoholic solution of imidazoles, continue to be uniformly mixing to obtain milky dispersion liquid, continues that dopamine hydrochloride and ammonia are added thereto
Butantriol Tris-HCl buffer, continues to stir, and is uniformly mixed and obtains dopamine/ZIF-8 suspension of Dark grey.
Dopamine of the present invention is a kind of organic molecule containing dihydroxy phenyl part and its derivative, including and
It is not limited to DOPA (DOPA), dopamine (dopamine), 3,4- dihydroxy benzenes methylamine, 3,4- 4-dihydroxy benzaldehyde, 3,4- dihydroxy
Base phenylacetaldehyde, 3,4- dihydroxy-benzoic acid or 3,4- dihydroxyphenyl acetic acid.
ZIFs (zeolitic imidazolate frameworks) is a kind of zeolite type imidazole skeleton structural material, is
The one kind for being connect with imidazoles or imdazole derivatives by metallic atoms such as Zn, Co and being generated is novel, with zeolite topological
Porous material, with permanent hole, high surface area, hydrophobicity, the metallic site of opening, excellent thermal stability and change
Learn stability.ZIF-8 is by the N in metal Zn atom and methylimidazole as a kind of skeleton structure representational in ZIFs
The ZnN that atom is connected to form4Tetrahedral structural unit is constituted.
Preferably, dopamine/ZIF-8 nanoparticle is grown in membrane surface:
Preparation as described above will be immersed through the nano-material modified basement membrane of inorganic silicate obtained in the step (1)
Obtained dopamine/ZIF-8 suspension, stands certain time at room temperature, makes dopamine/ZIF-8 nanoparticle in basement membrane table
Grown on face, use water and alcohol repeated flushing after taking-up respectively, 50 DEG C to 70 DEG C, preferably 60 DEG C to 70 DEG C at a temperature of it is dry,
Obtain the modification basement membrane with nanometer layer among dopamine/ZIF-8 of single growth.Wherein it is preferred to which the alcohol is methanol.
The present inventor thinks that the introducing of nanometer layer is prepared on backing material surface among dopamine/ZIF-8
Roughness height and random nanostructured layers, provide more uniform medium holes, increase the hydrophilicity of basement membrane, favorably
In increasing considerably aqueous phase monomers when preparing polyamide functional layer in epilamellar infiltration surface area and distributing homogeneity；Pass through
Dopamine modification keeps the combination between ZIF-8 nano material and polysulfones basement membrane and polyamide functional layer closer, dopamine/ZIF-
8 layers of nanostructure, high porosity and rugged surface can be conducive to preferably control and prepare polyamide functional layer
The release of monomer when interfacial polymerization.
Preferably, the growth and flushing carry out primary or repeat repeatedly, then to dry, the tool repeatedly grown
There is the modification basement membrane of nanometer layer among dopamine/ZIF-8.More preferably repeat growth 2 times to 5 times, arrives for still more preferably 2 times
4 times.When growing number is 1 time, intermediate nanometer layer growth is not uniform enough, and the nano material grown is less, to reverse osmosis membrane
It influences smaller.When grow number be more than 5 times after, intermediate nanometer layer is too thick, is not easy to be completely dissolved removing, also result in basement membrane and
The phenomenon that connection defective tightness between functional layer, even generation functional layer falls off.
Further, the modification basement membrane with nanometer layer among dopamine/ZIF-8 obtained as described above is immersed into water phase
Interfacial polymerization is carried out in solution, organic phase solution prepares polyamide functional layer, it is dry, obtain that there is the compound reverse osmosis of functional layer
The primary film of film.
It include aqueous phase monomers and water in the aqueous phase solution, the aqueous phase monomers are m-phenylene diamine (MPD), p-phenylenediamine, adjacent benzene two
Amine, at least one of toluenediamine, toluylenediamine, ortho-toluene diamine, benzidine.The aqueous phase monomers are in the water
Concentration in phase solution is 0.5wt% to 5wt%, preferably 1wt% to 3wt%, more preferably 1.5wt% to 2.5wt%.It is excellent
Selection of land adds alkali in aqueous phase solution, and the alkali is at least one of sodium hydroxide, potassium hydroxide, and the alkali is relative to institute
The concentration for stating aqueous phase solution is 0.1wt% to 3wt%, preferably 0.2wt% to 1wt%.
In the organic phase solution include organic phase monomer and solvent, the organic phase monomer be o-phthaloyl chloride,
Phthalyl chloride, paraphthaloyl chloride, 4, at least one of 4 '-biphenyl dimethyl chlorides, pyromellitic trimethylsilyl chloride, preferably adjacent benzene
Dimethyl chloride, m-phthaloyl chloride, pyromellitic trimethylsilyl chloride, more preferably o-phthaloyl chloride.The solvent is n-hexane, hexamethylene
At least one of alkane, normal heptane, Isopars Isopar G, preferably n-hexane, Isopars Isopar G,
More preferably Isopars Isopar G.Concentration of the organic phase monomer in the organic phase solution is
0.005wt% to 3wt%, preferably 0.05wt% are to 2wt%, more preferably 0.1wt% to 1wt%.
Preferably, polyamide functional layer is prepared as described below:
The modification basement membrane with nanometer layer among dopamine/ZIF-8 prepared as described above is soaked in aqueous phase solution
Contact certain time, such as 100 seconds to 200 seconds, preferably 100 seconds to 150 seconds, more preferable 100 seconds to 120 seconds.Make aqueous phase solution
It penetrates into the hole of ZIF-8 nanometer layer.
It is filtered dry excessive aqueous phase solution, diaphragm is immersed in organic phase solution and reacts certain time, such as 20 seconds to 60 seconds,
It is preferred that 20 seconds to 50 seconds, more preferable 20 to 40 seconds.Organic phase solution is discharged after reaction, diaphragm is dry, such as 70 DEG C-
At a temperature of 90 DEG C, thus obtain that there is the primary film of the complex reverse osmosis membrane of polyamide functional layer.
The primary film obtained as described above is soaked in water, dissolution removes the intermediate nanometer layer, it is preferable that is rinsed with water
Repeatedly, the high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer is obtained.
The present inventor thinks, can inhibit the hydrolysis of ZIF-8 nanoparticle, therefore interface under aqueous basic conditions
ZIF-8 nanoparticle is able to maintain stable shaped when polymerization, but soaking a period of time ZIF-8 nanoparticle can be complete in water
All-hydrolytic.The aramid layer bottom for dissolving ZIF-8 nanoparticle has nanoscale rough degree, and a large amount of fold-like structures in bottom increase
Add effective infiltrating area of polyamide functional layer, so that increase relative to the permeation flux in basement membrane unit shaded area, it can
The flux of reverse osmosis membrane is increased substantially under the premise of not influencing salt rejection rate.
II, the high-flux reverse osmosis membrane of the invention containing intermediate nanometer sacrificial layer
The high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer that method according to the present invention obtains, wherein described poly-
The bottom of amide functional layer has nanoscale rough degree, and bottom has fold-like structures.Method preparation through the invention
The thickness of obtained high-flux reverse osmosis membrane not only functional layer is thin, good mechanical property, be evenly distributed, effective infiltrating area is big, and
And flux is increased substantially under the premise of not influencing desalting performance.
The purposes of III, the high-flux reverse osmosis membrane of the invention containing intermediate nanometer sacrificial layer
High-flux reverse osmosis membrane according to the present invention containing intermediate nanometer sacrificial layer can be used for water treatment applications, work
Fluid separation in the processing of industry or municipal wastewater, food-processing industry and pharmaceutical industry.
IV, membrane component and filtration system including the high-flux reverse osmosis membrane of the invention containing intermediate nanometer sacrificial layer
Membrane component according to the present invention comprising the high-throughput reverse osmosis according to the present invention containing intermediate nanometer sacrificial layer
Permeable membrane.
Filtration system according to the present invention comprising the high throughput according to the present invention containing intermediate nanometer sacrificial layer is anti-
Permeable membrane.
Embodiment
Present invention be described in more detail combined with specific embodiments below, but the present invention is not limited to following embodiment.It needs
It is noted that the reagent and raw material that use in the embodiment of the present invention are unless stated otherwise, it is all the conventional products being obtained commercially.
For the basement membrane of following preparation, hydrophily is evaluated as follows.
Using preparation gained basement membrane, water droplet contact angle is measured as described below: diaphragm sample being placed in pure water and is impregnated for 24 hours,
It is dried at 20 DEG C.Contact angle tester model are as follows: German KRUSS DSA30 research contact angle measurement.By diaphragm sample
It is laid on testboard, is dripped to pure water on diaphragm with the injection needle of contact angle measurement, when drop falls in 10 seconds on diaphragm
Record the contact angle of water droplet.The volume of every drop pure water drop is about 3uL, and each sample randomly selects five points and tested, number
According to being averaged.
The following are the company-informations of substance specifically used in embodiment.
Polysulfones, Sinopharm Chemical Reagent Co., Ltd.
Attapulgite, Sinopharm Chemical Reagent Co., Ltd.
N,N-Dimethylformamide, Sinopharm Chemical Reagent Co., Ltd.
Polyvinylpyrrolidone, Sinopharm Chemical Reagent Co., Ltd.
Zn(NO3)2·6H2O, Sigma-Aldrich
Methanol, Sinopharm Chemical Reagent Co., Ltd.
2-methylimidazole, Alfa-Aesar
Dopamine hydrochloride, Alfa-Aesar
Tromethamine, Alfa-Aesar
P-phenylenediamine, BASF
Pyromellitic trimethylsilyl chloride, BASF
Isopars Isopar G, Sinopharm Chemical Reagent Co., Ltd.
Embodiment 1
Prepare polysulfones basement membrane
(1) 40wt%N is dispersed under ultrasonic state by 1wt% attapulgite, in dinethylformamide DMF, warp
It is uniformly dispersed after 300W supersonic cleaning machine ultrasound 3h, carries out decompression suction filtration with 0.2 μm of the microfiltration membranes in aperture, remove impurity, obtain
DMF filtrate；
(2) under stirring, into the filtrate be added 1wt% polyvinylpyrrolidone, use mixing speed for
60r/min is stirred, so that polyvinylpyrrolidone is uniformly dispersed in filtrate, mixing speed is maintained to be warming up to 90
DEG C, 18wt% polysulfones and 40wt%DMF are added thereto, stirring 4h obtains casting solution；
(3) it filters, is cooled to room temperature after casting solution being carried out vacuum defoamation processing at -80kPa, it is equal using doctor blade system
Even to be coated on PP non-woven fabrics base material and enter in coagulating bath, coagulating bath is the DMF aqueous solution of 1.0wt%, and temperature is 20 DEG C, is coagulated
Admittedly the processing time is 30s；Then it is placed in deionized water, adjustment temperature is 20 DEG C, after rinsing processing 200 seconds, is obtained through bumps
The modified polysulfones basement membrane of stick stone；Through measuring, the water droplet contact angle through the modified polysulfones basement membrane of attapulgite is 56 °；With a thickness of
(5.5-6mil 1mil=0.0254mm).
Preparation load has dopamine/ZIF-8 nanometer layer modified polysulfone basement membrane
(1) under normal temperature environment, by the Zn (NO containing 0.1mol in the state of being kept stirring3)2·6H2The 40mL methanol of O
It is poured into rapidly in the 40mL methanol solution of the 2-methylimidazole containing 0.4mol with the mixed solution of 20mL water, stirring 1h obtains milky white
Color dispersion liquid；The tromethamine buffer (pH=8.5) of 50mg dopamine hydrochloride and 10mL0.1mol is added, is stirred under room temperature
5h obtains Dark grey suspension；
(2) above-mentioned suspension will be immersed through the modified polysulfones basement membrane of attapulgite and stand 12h at room temperature, make dopamine/
ZIF-8 nanoparticle is grown in polysulfones membrane surface.After using distilled water and methanol repeated flushing respectively after taking-up, at 60 DEG C
Dry 0.5h, obtains the counterdie of single growth；Above-mentioned growth course is repeated, dopamine/ZIF-8 diauxic growth polysulfones base is obtained
Film.
The preparation of polyamide functional layer
(1) dopamine/ZIF-8 diauxic growth polysulfones basement membrane is soaked in m-phenylene diamine (MPD) containing 2wt% and 0.5wt% hydrogen-oxygen
Change and contacted 100 seconds in the aqueous phase solution of sodium, penetrates into aqueous phase solution in the hole of ZIF-8 nanometer layer；
(2) it is filtered dry excessive aqueous phase solution, diaphragm is immersed into the n-hexane organic phase containing 0.1wt% o-phthaloyl chloride
It is reacted 20 seconds in solution, organic phase solution is discharged after reaction, diaphragm is placed in vacuum drying oven at 90 DEG C dry 5min,
Compound reverse osmosis primary film is made, is cut into two halves, is denoted as M1-RO1 and M1-RO2 respectively.
Remove the preparation of the reverse osmosis membrane of intermediate nanometer sacrificial layer
Above-mentioned M1-RO2 reverse osmosis membrane is immersed into 30min in pure water, and with pure water rinsing 3~5 times, dissolves ZIF-8 and receives
Rice corpuscles, reverse osmosis membrane RO-M1 needed for being made.
Embodiment 2
To prepare polysulfones basement membrane with same way described in embodiment 1.
Preparation load has dopamine/ZIF-8 nanometer layer modified polysulfone basement membrane
(1) under normal temperature environment, by the Zn (NO containing 0.13mol in the state of being kept stirring3)2·6H2The 40mL first of O
The mixed solution of pure and mild 20mL water pours into rapidly in the 40mL methanol solution of the 2-methylimidazole containing 0.45mol, and stirring 1h is obtained
Milky dispersion liquid；The tromethamine buffer (pH=8.5) of 50mg dopamine hydrochloride and 10mL0.1mol is added, under room temperature
5h is stirred, Dark grey suspension is obtained；
(2) above-mentioned suspension will be immersed through the modified polysulfones basement membrane of attapulgite and stand 12h at room temperature, make dopamine/
ZIF-8 nanoparticle is grown in polysulfones membrane surface.After using distilled water and methanol repeated flushing respectively after taking-up, at 60 DEG C
Dry 0.5h, obtains the counterdie of single growth；Above-mentioned growth course is repeated, the polysulfones base of tri- secondary growth of dopamine/ZIF-8 is obtained
Film.
The preparation of polyamide functional layer
(1) the polysulfones basement membrane of tri- secondary growth of dopamine/ZIF-8 is soaked in m-phenylene diamine (MPD) containing 2wt% and 0.5wt% hydrogen-oxygen
Change and contacted 100 seconds in the aqueous phase solution of sodium, penetrates into aqueous phase solution in the hole of ZIF-8 nanometer layer；
(2) it is filtered dry excessive aqueous phase solution, diaphragm is immersed into the n-hexane organic phase containing 0.1wt% o-phthaloyl chloride
It is reacted 20 seconds in solution, organic phase solution is discharged after reaction, diaphragm is placed in vacuum drying oven at 90 DEG C dry 5min,
Compound reverse osmosis primary film is made, is cut into two halves, is denoted as M2-RO1 and M2-RO2 respectively.
The preparation of reverse osmosis membrane containing intermediate nanometer sacrificial layer
Above-mentioned M2-RO2 reverse osmosis membrane is immersed into 30min in pure water, and with pure water rinsing 3~5 times, dissolves ZIF-8 and receives
Required reverse osmosis membrane RO-M2 can be made in rice corpuscles.
Test
Above-mentioned M1-RO1, RO-M1, M2-RO1 are cut respectively, and RO-M2 film and 2 kinds of epoch Wo Dun Science and Technology Ltd.s are commercial
Reverse osmosis membrane (being denoted as RO-1 and RO-2 respectively) is tested, and every kind of diaphragm cuts three test diaphragms respectively, cuts area
It for 3.4cm × 3.4cm, is placed on cross-current type check-out console and tests, test condition is 2000ppm sodium-chloride water solution, 150Psi behaviour
Make pressure, raw water temperature is 25 DEG C, pH=7, and each testing time is 30min.Record salt rejection rate obtained by every group of Membrane probing and
The average value of flux, the results are shown in Table 1.The reverse osmosis membrane M1-RO1 and M2-RO1 containing intermediate nanometer layer is shown in table 1, is removed
Remove fertile reverse osmosis membrane RO-M1 and RO-M2, epoch commercial reverse osmosis membrane of intermediate nanometer layer (that is, containing intermediate nanometer sacrificial layer)
The test data of RO-1 and RO-2, as shown in Table 1, the reverse osmosis membrane that method of the present invention is prepared can effectively improve
Permeation flux is without changing its desalting performance, and reverse osmosis membrane after the intermediate nanometer layer of removing (that is, containing intermediate nanometer sacrificial layer)
Flux is higher.
Table 1
Concrete mode of the invention is disclosed in above-described embodiment, but above-described embodiment is only example, and without limitation
Property explain.Obvious various modifications are certainly included in the scope of the present invention to those skilled in the art.
Industrial availability
The preparation method of high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer of the invention, it is low in cost, it is easy to operate,
It is capable of providing high-flux reverse osmosis membrane.The thickness of high-flux reverse osmosis membrane containing intermediate nanometer sacrificial layer of the invention not only functional layer
Spend thin, good mechanical property, be evenly distributed, effective infiltrating area it is big, and significantly mentioned under the premise of not influencing desalting performance
It is high-throughput.It therefore, is useful for the processing, food processing, pharmaceutical industry of water process, industry or municipal wastewater.
Claims (10)
1. a kind of preparation method of high-flux reverse osmosis membrane, the method are characterised by comprising following steps:
(1) polymer solution that preparation is dispersed with inorganic silicate nano material is coated on backing material, connects as casting solution
Be immersed in coagulating bath, obtain basement membrane；
(2) dopamine/ZIF-8 suspension is prepared, the basement membrane obtained in step (1) is immersed in the suspension, DOPA is made
Amine/ZIF-8 is grown in membrane surface, obtains the modification basement membrane with nanometer layer among dopamine/ZIF-8；
(3) basement membrane will be modified obtained in step (2) to immerse aqueous phase solution, carry out interfacial polymerization in organic phase solution and prepare function
Ergosphere obtains having the primary film of the complex reverse osmosis membrane of functional layer；
(4) the primary film obtained in step (3) is soaked in water, dissolution removes the intermediate nanometer layer, obtains high-throughput anti-
Permeable membrane.
2. preparation method according to claim 1, wherein the backing material is non-woven fabrics, wherein the polymer solution
Comprising polymer and solvent, the polymer be polysulfones, polyether sulfone, polyphenylsulfone, Kynoar, polyvinyl chloride, cellulose and
Its derivative, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polyimides, at least one in polyethylene
Kind, the solvent is n,N-Dimethylformamide DMF, N, and N- dimethyl pyrrolidone, n,N-dimethylacetamide, dimethyl are sub-
Sulfone, n-hexane, hexamethylene, normal heptane, Isopars Isopar G, chloroform, chloroform, toluene, benzene, methanol, propyl alcohol
At least one of, it is preferable that concentration of the polymer in casting solution is 10wt% to 25wt%；Preferably, the nothing
Machine silicate nano material is aqueous rich magnesium aluminosilicate, and the concentration in casting solution is 0.5wt% to 5wt%, more preferably
Ground, the inorganic silicate nano material are attapulgite；Preferably, active hydrophilic stabilizer is added in the casting solution,
Its concentration in casting solution is 0.5wt% to 5wt%, it is highly preferred that the active hydrophilic stabilizer is polyvinylpyrrolidine
Alkanone；The coagulating bath is water-bath, it is preferable that DMF is added in coagulating bath.
3. preparation method according to claim 1 or 2, wherein the dopamine/ZIF-8 suspends in the step (2)
Liquid is prepared by following steps:
(a) by Zn (NO3)2·6H2The water of O and the mixed solution of alcohol, which are added to be uniformly mixed in the alcoholic solution of 2-methylimidazole, to be obtained
Dispersion liquid, it is preferable that the alcohol is methanol；
(b) dopamine hydrochloride and tromethamine Tris-HCl buffer are added in the dispersion liquid obtained in step (a), obtains
The dopamine/ZIF-8 suspension；
Preferably, the growth and flushing carry out primary or repeat repeatedly.
4. preparation method according to claim 3 the, wherein Zn (NO3)2·6H2O is in the mixed solution of water and alcohol
Concentration is 1.0mol/L to 2.5mol/L, and the concentration in the alcoholic solution of the 2-methylimidazole is 5mol/L to 15mol/L；It is preferred that
Ground, the Zn (NO3)2·6H2The volumetric concentration of the water of O and the mixed solution of alcohol in the dopamine/ZIF-8 suspension is
50vol% to 70vol%；Preferably, body of the alcoholic solution of the 2-methylimidazole in the dopamine/ZIF-8 suspension
Product concentration is 30vol% to 60vol%；Preferably, the dopamine hydrochloride is in the dopamine/ZIF-8 suspension
Concentration is 0.40g/L to 0.60g/L；Preferably, range of the tromethamine Tris-HCl pH of cushioning fluid 7.5 to 9.2
It is interior.
5. preparation method according to claim 1-4, wherein include aqueous phase monomers and water in the aqueous phase solution,
Preferably, the aqueous phase monomers be m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, to toluenediamine, toluylenediamine, adjacent toluene
At least one of diamines, benzidine, it is highly preferred that concentration of the aqueous phase monomers in the aqueous phase solution is
0.5wt% to 5wt%；It include organic phase monomer and solvent in the organic phase solution, it is preferable that the organic phase monomer is neighbour
Phthalyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, 4,4 '-biphenyl dimethyl chlorides, at least one in pyromellitic trimethylsilyl chloride
Kind, it is preferable that the solvent be at least one of n-hexane, hexamethylene, normal heptane, Isopars Isopar G, it is excellent
Selection of land, concentration of the organic phase monomer in the organic phase solution are 0.005wt% to 3wt%.
6. a kind of high-flux reverse osmosis membrane of method preparation according to claim 1-5.
7. high-flux reverse osmosis membrane according to claim 6, wherein the bottom of the polyamide functional layer has nanoscale
Roughness, bottom have fold-like structures.
8. the purposes of high-flux reverse osmosis membrane according to claim 6 or 7 is used for water treatment applications, industry or city
The processing of waste water, food processing, pharmaceutical industry.
9. a kind of membrane component comprising high-flux reverse osmosis membrane according to claim 6 or 7.
10. a kind of filtration system comprising membrane component according to claim 9.
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| CN114713042B (en) * | 2022-04-20 | 2023-05-12 | 杭州水处理技术研究开发中心有限公司 | Nanofiltration membrane with high resolution and water flux and preparation method thereof |
| CN115920679A (en) * | 2022-12-27 | 2023-04-07 | 威海智洁环保技术有限公司 | Preparation method and application of MOFs transition layer modified solvent-resistant nanofiltration membrane |
| CN115920679B (en) * | 2022-12-27 | 2023-07-18 | 威海智洁环保技术有限公司 | Preparation method and application of MOFs transition layer modified solvent-resistant nanofiltration membrane |
| CN116531968A (en) * | 2023-03-26 | 2023-08-04 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
| CN116531968B (en) * | 2023-03-26 | 2024-03-22 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
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