CN114849473B - Secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and preparation method thereof - Google Patents
Secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and preparation method thereof Download PDFInfo
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
Abstract
The invention discloses a secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and a preparation method thereof, wherein the reverse osmosis membrane consists of an ultrafiltration membrane supporting layer, an aromatic polyamide layer, a secondary polymerization aromatic polyamide layer and ZIF-8, wherein the ultrafiltration membrane supporting layer is soaked in zinc ion solution, then an aromatic polyamide layer coated with metal ions is obtained by interfacial polymerization on the supporting layer, and then the secondary interfacial polymerization and the growth ZIF-8 are synchronously carried out to obtain the reverse osmosis membrane modified by the secondary polymerization synchronous sealing ZIF-8; the invention avoids the aggregation phenomenon of ZIF-8 in the water phase or the oil phase, so that the ZIF-8 material grows in the polyamide and ultrafiltration membrane supporting layer more uniformly, the defect of an aromatic polyamide layer caused by ZIF-8 is compensated by secondary polymerization, and the prepared reverse osmosis membrane polymer has high flux and higher interception performance.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membranes, in particular to a secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and a preparation method thereof.
Background
Due to the continuous growth of world population, continuous development of industrialization, uneven distribution of water resources and the like, the demand of people for fresh water resources is increasing increasingly, and the available fresh water resources only account for 0.8% of the reserves of global water resources, so that for the promotion of industrialization, the development of economy and the safety of water consumption of people, it is urgent to seek a solution for the shortage of fresh water resources. The technology of treating fresh water based on Reverse Osmosis (RO) is a key technology for producing fresh water from sea water, has the advantages of simple operation, low energy consumption and the like, and obtains wide attention.
The polyamide has good stability and hydrophilicity, and is commonly used for preparing a functional layer of the composite film. In contrast to nanofiltration membranes, reverse osmosis membranes are required to operate under high pressure conditions. Therefore, aromatic polyamides having a high degree of crosslinking are often selected for reverse osmosis membranes currently commercialized. Because of its high degree of crosslinking, the reverse osmosis membrane produced therefrom exhibits good selectivity but poor water permeability. It has been found that the addition of porous nanomaterials to polyamide materials can effectively improve the permeation properties of membranes, including nanosilica, and the like.
ZIF-8 is used as an emerging porous material in recent years and has complicated and various nano pore channels; and has high porosity, large specific surface area and good chemical stability. The excellent performance can effectively improve the water permeability of the reverse osmosis membrane, however, ZIF-8 materials directly added into the water phase or the oil phase are extremely easy to agglomerate, and the improvement of the reverse osmosis membrane performance is greatly limited. In the early stage, ZIF modified polyamide membranes are prepared by in-situ back diffusion, so that the aggregation of ZIF nano particles is effectively avoided, but the ZIF modified polyamide membranes are easy to break a compact aromatic polyamide layer, and the salt interception performance of the membranes is affected.
The self-sealing ZIF-8 method is adopted to modify the reverse osmosis membrane, ZIF-8 nano particles can be uniformly grown on the aromatic polyamide skin layer, the free volume is increased, an additional selective water channel is provided, and the permeability of the membrane is remarkably improved; the synchronous secondary polymerization can make up for the defects of an aromatic polyamide layer caused by ZIF-8 nano particles, so that the modified reverse osmosis membrane keeps high salt interception performance.
Disclosure of Invention
The invention aims to improve the performance of an original reverse osmosis membrane and provides a secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and a preparation method thereof.
The reverse osmosis membrane is composed of an ultrafiltration membrane supporting layer, an aromatic polyamide layer, a secondary polymerization aromatic polyamide layer and ZIF-8. Immersing an ultrafiltration membrane supporting layer in zinc ion solution, performing interfacial polymerization on the supporting layer to obtain an aromatic polyamide layer coated with metal ions, performing secondary interfacial polymerization and growth ZIF-8 synchronously, and performing steps such as airing, washing with sodium bicarbonate aqueous solution and the like to obtain the reverse osmosis membrane modified by the secondary polymerization synchronous sealing ZIF-8.
The technical scheme of the invention is as follows:
a self-sealing ZIF-8 modified reverse osmosis membrane is formed by an ultrafiltration membrane supporting layer, an aromatic polyamide layer, a secondary polymerization aromatic polyamide layer and ZIF-8, wherein the secondary polymerization and the ZIF-8 growth are performed simultaneously.
The ultrafiltration membrane supporting layer is prepared from one or more of polysulfone, polyethersulfone, polyetherketone, polyarylsulfone, polyacrylonitrile and polyvinylidene fluoride.
The preparation method of the secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane comprises the following steps:
(1) After the ultrafiltration membrane supporting layer is washed by deionized water and dried, the zinc salt aqueous solution is paved on the surface of the supporting layer, kept for 2-4 min, and then poured out for drying;
the concentration of the aqueous solution of the zinc salt is 0.05-0.25 mol/L, and the zinc salt is zinc nitrate hexahydrate preferably;
(2) Immersing the membrane material treated in the step (1) in an aqueous phase solution containing aromatic amine monomers for 2-4 min, and taking out and airing;
the mass fraction of aromatic amine monomers in the aqueous phase solution is 2%; the aromatic amine monomer is selected from one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 4, 5-dichloro-o-phenylenediamine and trimellitic amine; the solvent of the aqueous phase solution is water;
(3) Immersing the membrane material treated in the step (2) in an organic phase solution containing an aromatic chloroformyl monomer for 60s, and then taking out and drying;
the mass fraction of the aromatic chloracyl monomer in the organic phase solution is 0.1%; the aromatic acyl chloride monomer is selected from one or more of isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride and polybasic aromatic sulfonyl chloride; the solvent of the organic phase solution is one or more of normal hexane, cyclohexane, toluene, benzene, ethyl acetate and dodecane;
(4) Immersing the membrane material treated in the step (3) in a mixed solution of an aromatic amine monomer and 2-methylimidazole for 10min, and taking out and airing;
in the mixed solution, the mass fraction of the aromatic amine monomer is 1-10%, and the mass fraction of the 2-methylimidazole is 5-20%; the aromatic amine monomer is selected from one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 4, 5-dichloro-o-phenylenediamine and trimellitic amine; the solvent of the mixed solution is 75% alcohol water solution by mass fraction, and the alcohol is one or more selected from methanol, ethanol, glycol, glycerol and isopropanol;
(5) Sequentially cleaning the membrane material treated in the step (4) with sodium bicarbonate aqueous solution and deionized water, and airing to obtain a reverse osmosis membrane modified by the secondary polymerization synchronous self-sealing ZIF-8;
the mass fraction of the sodium bicarbonate aqueous solution is 0.2%, and the cleaning time is 2min.
The reverse osmosis membrane modified by the secondary polymerization synchronous self-sealing ZIF-8 not only maintains high retention rate of 95.4-98.1 percent, but also has water flux of 65-75 Lm -2 h -1 bar -1 (5.5 MPa) is more than 2 times of the unmodified reverse osmosis membrane.
The invention has the beneficial effects that:
the aggregation phenomenon of ZIF-8 in a water phase or an oil phase is avoided, so that the ZIF-8 material grows in the polyamide and ultrafiltration membrane supporting layer more uniformly, and the defect of an aromatic polyamide layer caused by ZIF-8 is overcome by secondary polymerization. The prepared reverse osmosis membrane polymer has high flux and higher interception performance, and the preparation method is simple, easy to operate and low in cost, can be applied to the fields of domestic water purification, industrial wastewater treatment, food processing, sea water desalination and the like, and has good application prospects.
Drawings
FIG. 1 is a graph showing the separation performance (water flux and NaCl cut-off) of comparative example membranes of the respective examples.
FIG. 2 is a scanning electron microscope surface view of example 1, in which a pronounced leaf-like structure is observed to be uniformly distributed on the film surface.
FIG. 3 is an EDS chart of example 1, in which Zn elements were uniformly distributed on the surface of the film, and it was confirmed that ZIF-8 particles were successfully dispersed in the polyamide layer.
FIG. 4 is a cross-sectional view of a scanning electron microscope of example 1, in which ZIF-8 particles were successfully dispersed in a polysulfone layer.
FIG. 5 is a surface view of a scanning electron microscope of comparative example 1, whose surface has a larger and irregular blade structure than that of example 1.
FIG. 6 is a cross-sectional view of a scanning electron microscope of comparative example 1, in which ZIF nanoparticles were not observed.
FIG. 7 is a reaction scheme.
Detailed Description
The present invention is further described below by way of specific examples, but the scope of the present invention is not limited thereto.
The preparation environment of all reverse osmosis membranes in the examples is: the temperature is 22 ℃, the humidity is 50% and the pressure is normal.
Example 1 secondary polymerization synchronous growth ZIF-8:
(1) Spreading 0.12mol/L zinc nitrate hexahydrate water solution on a polysulfone ultrafiltration support membrane, immersing for 2min, pouring out the solution, and airing the membrane;
(2) Immersing the obtained film in 2wt% m-phenylenediamine water solution for 3min, pouring the solution out, and airing the film;
(3) The obtained film is contacted with 0.1 weight percent of trimesoyl chloride n-hexane solution, and after interfacial polymerization for 60 seconds, the film is placed in a 60 ℃ oven for 10 minutes;
(4) Soaking the obtained membrane in an aqueous solution of 3wt% of m-phenylenediamine and 10wt% of isopropanol with the mass fraction of 75% of 2-methylimidazole for 10min, and airing the membrane;
(5) The obtained membrane is placed in 0.2wt% sodium bicarbonate aqueous solution for 2min, taken out, washed with deionized water, dried and stored in a deionized manner.
Analytical testing was performed on the films obtained in example 1:
the reverse osmosis membrane prepared in this example was put into a membrane performance test apparatus under experimental conditions: pre-pressing for 1h at 20 ℃ under 5.5MPa with 32000ppm NaCl salt solution; test results: water flux: 65.5Lm -2 h -1 NaCl retention rate: 97.67%.
Example 2 varying the concentration of secondary polymerization synchronized growth ZIF solution:
(1) Spreading 0.12mol/L zinc nitrate hexahydrate water solution on a polysulfone ultrafiltration support membrane, immersing for 2min, pouring out the solution, and airing the membrane;
(2) Immersing the obtained film in 2wt% m-phenylenediamine water solution for 3min, pouring the solution out, and airing the film;
(3) The obtained film is contacted with 0.1 weight percent of trimesoyl chloride n-hexane solution, and after interfacial polymerization for 60 seconds, the film is placed in a 60 ℃ oven for 10 minutes;
(4) Soaking the obtained membrane in an aqueous solution of 5wt% of m-phenylenediamine and 10wt% of isopropanol with the mass fraction of 75% of 2-methylimidazole for 10min, and airing the membrane;
(5) The obtained membrane is placed in 0.2wt% sodium bicarbonate aqueous solution for 2min, taken out, washed with deionized water, dried and stored in a deionized manner.
Analytical testing was performed on the films obtained in example 2:
film performance test conditions were the same as in example 1, test results: water flux: 66.5Lm -2 h -1 NaCl retention rate: 97.65%.
Comparative example 1 only performs interfacial polymerization:
(1) Immersing a polysulfone ultrafiltration support membrane in a 2wt% m-phenylenediamine aqueous solution for 3min, pouring out the solution, and airing the membrane;
(2) The resulting film was contacted with 0.1wt% trimesoyl chloride n-hexane solution and polymerized at the interface for 60 s;
(3) The resulting film was cured in an oven at 60℃for 10min and removed to give an initial blank film.
Analytical testing was performed on the films obtained in comparative example 1:
film performance test conditions were the same as in example 1, test results: water flux: 26.5Lm -2 h -1 NaCl retention rate: 97.21%.
Comparative example 2 only back diffusion growth ZIF was performed without secondary polymerization:
(1) Spreading 0.12mol/L zinc nitrate hexahydrate water solution on a polysulfone ultrafiltration support membrane, immersing for 2min, pouring out the solution, and airing the membrane;
(2) Immersing the obtained film in 2wt% m-phenylenediamine water solution for 3min, pouring the solution out, and airing the film;
(3) The obtained film is contacted with 0.1 weight percent of trimesoyl chloride n-hexane solution, and after interfacial polymerization for 60 seconds, the film is placed in a 60 ℃ oven for 10 minutes;
(4) Soaking the obtained membrane in an aqueous solution of 10wt% of isopropyl alcohol with the mass fraction of 75% of 2-methylimidazole for 10min, and airing the membrane;
(5) The obtained membrane is placed in 0.2wt% sodium bicarbonate aqueous solution for 2min, taken out, washed with deionized water, dried and stored in a deionized manner.
Analytical testing was performed on the films obtained in comparative example 2:
film performance test conditions were the same as in example 1, test results: water flux: 44Lm -2 h -1 NaCl retention rate: 94.46%.
Claims (3)
1. The secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane is characterized by comprising an ultrafiltration membrane supporting layer, an aromatic polyamide layer, a secondary polymerization aromatic polyamide layer and ZIF-8, wherein the secondary polymerization and the ZIF-8 growth are carried out simultaneously;
the preparation method of the secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane comprises the following steps:
(1) After the ultrafiltration membrane supporting layer is washed by deionized water and dried, the zinc salt aqueous solution is paved on the surface of the supporting layer, kept for 2-4 min, and then poured out for drying;
the concentration of the aqueous solution of the zinc salt is 0.05-0.25 mol/L, and the zinc salt is zinc nitrate hexahydrate;
(2) Immersing the membrane material treated in the step (1) in an aqueous phase solution containing aromatic amine monomers for 2-4 min, and taking out and airing;
the mass fraction of aromatic amine monomers in the aqueous phase solution is 2%; the aromatic amine monomer is selected from one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 4, 5-dichloro-o-phenylenediamine and trimellitic amine; the solvent of the aqueous phase solution is water;
(3) Immersing the membrane material treated in the step (2) in an organic phase solution containing an aromatic chloroformyl monomer for 60s, and then taking out and drying;
the mass fraction of the aromatic chloracyl monomer in the organic phase solution is 0.1%; the aromatic acyl chloride monomer is selected from one or more of isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride and polybasic aromatic sulfonyl chloride; the solvent of the organic phase solution is one or more of normal hexane, cyclohexane, toluene, benzene, ethyl acetate and dodecane;
(4) Immersing the membrane material treated in the step (3) in a mixed solution of an aromatic amine monomer and 2-methylimidazole for 10min, and taking out and airing;
in the mixed solution, the mass fraction of the aromatic amine monomer is 1-10%, and the mass fraction of the 2-methylimidazole is 5-20%; the aromatic amine monomer is selected from one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 4, 5-dichloro-o-phenylenediamine and trimellitic amine; the solvent of the mixed solution is 75% alcohol water solution by mass fraction, and the alcohol is one or more selected from methanol, ethanol, glycol, glycerol and isopropanol;
(5) And (3) cleaning the membrane material treated in the step (4) with sodium bicarbonate aqueous solution and deionized water in sequence, and airing to obtain the reverse osmosis membrane modified by the secondary polymerization synchronous self-sealing ZIF-8.
2. The secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane of claim 1, wherein the ultrafiltration membrane supporting layer is prepared from one or more of polysulfone, polyethersulfone, polyetherketone, polyarylsulfone, polyacrylonitrile and polyvinylidene fluoride.
3. The secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane according to claim 1, wherein in the preparation method step (5), the mass fraction of the sodium bicarbonate aqueous solution is 0.2%, and the cleaning time is 2min.
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