CN115228291A - Anti-pollution, antibacterial and large-flux reverse osmosis membrane and preparation method and application thereof - Google Patents
Anti-pollution, antibacterial and large-flux reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN115228291A CN115228291A CN202210953247.XA CN202210953247A CN115228291A CN 115228291 A CN115228291 A CN 115228291A CN 202210953247 A CN202210953247 A CN 202210953247A CN 115228291 A CN115228291 A CN 115228291A
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- reverse osmosis
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- 239000012528 membrane Substances 0.000 title claims abstract description 172
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 94
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000004907 flux Effects 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 84
- -1 stilbene compound Chemical class 0.000 claims description 44
- 229920002492 poly(sulfone) Polymers 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 40
- 239000004952 Polyamide Substances 0.000 claims description 29
- 229920002647 polyamide Polymers 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 22
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 22
- 238000000108 ultra-filtration Methods 0.000 claims description 22
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 21
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 21
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 21
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 20
- 235000021286 stilbenes Nutrition 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 17
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000012695 Interfacial polymerization Methods 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 239000002346 layers by function Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003373 anti-fouling effect Effects 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 4
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 claims description 3
- VALLWWIZOBWSFP-UHFFFAOYSA-N 5-amino-2-[2-(4-amino-2-sulfophenyl)ethenyl]benzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O VALLWWIZOBWSFP-UHFFFAOYSA-N 0.000 claims description 3
- GTXMHEHQFVZJCH-UHFFFAOYSA-N 5-amino-2-[2-(4-anilino-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical class N(C1=CC=CC=C1)C=1C=C(C(C=CC=2C(=CC(=CC2)N)S(=O)(=O)O)=CC1)S(=O)(=O)O GTXMHEHQFVZJCH-UHFFFAOYSA-N 0.000 claims description 3
- CMPCUZCLDZMYPQ-UHFFFAOYSA-N 5-amino-2-[2-[4-[2-(4-amino-2-sulfophenyl)ethenyl]phenyl]ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O CMPCUZCLDZMYPQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- PQBWURXXIAXNRC-UHFFFAOYSA-N benzyl(hexadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH2+]CC1=CC=CC=C1 PQBWURXXIAXNRC-UHFFFAOYSA-N 0.000 claims description 3
- TTWQNMGZIZBCEE-UHFFFAOYSA-N benzyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH2+]CC1=CC=CC=C1 TTWQNMGZIZBCEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000010612 desalination reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 2
- 244000005700 microbiome Species 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 abstract 1
- 239000008235 industrial water Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 21
- 238000012360 testing method Methods 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000003385 bacteriostatic effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-UHFFFAOYSA-N 0.000 description 3
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000001629 stilbenes Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical group 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 230000000813 microbial effect Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an anti-pollution and anti-bacteria large-flux reverse osmosis membrane, a preparation method and application thereof. Compared with the common reverse osmosis membrane, the reverse osmosis membrane has the advantages of taking organic pollution into consideration and effectively resisting bacteria on the premise of keeping higher desalination rate and water flux, can effectively inhibit microorganism adhesion and growth in the actual application process of the reverse osmosis membrane, and has better application prospect in the water treatment fields of wastewater reuse, industrial water supply and the like.
Description
Technical Field
The invention belongs to the technical field of water treatment materials, and particularly relates to an anti-pollution and antibacterial large-flux reverse osmosis membrane, and a preparation method and application thereof.
Background
With the rapid development of global urbanization and industrialization, the existing fresh water resources cannot meet the development requirements of society and economy, and the problem of water resource shortage becomes a hot point of world-wide attention. Compared with the traditional method, the membrane method water treatment technology has the irreplaceable advantages of low cost, high separation precision, no secondary pollution and the like, and the reverse osmosis membrane is widely applied to various fields of pharmacy, medical treatment, food, beverage, wine, chemical industry, electronics, semiconductors, environmental protection and the like, and is one of the most widely popularized and developed membrane technologies in China in recent years.
However, the reverse osmosis membrane is still limited in practical use by a series of problems, and due to differences in water quality conditions, membrane pollution, especially microbial pollution, is an important factor hindering the development of reverse osmosis membranes. The membrane pollution refers to a process that micro-particles, colloidal particles, organic solute macromolecules, particularly microorganisms and the like in reverse osmosis inflow water generate physical and chemical actions with the surface of a membrane to form attachment layers such as scales, filter cakes and the like on the surface of the membrane, and the deposition of pollutants can increase the permeation resistance of the membrane to cause reversible or irreversible reduction of flux on one hand and cause irreversible damage to an interface polymerization layer structure on the surface of the membrane to cause irreversible reduction of desalination rate on the other hand. The membrane pollution needs frequent cleaning, the whole service life of the membrane is shortened, the operation and replacement cost of the reverse osmosis membrane is increased, and the operation and replacement cost of the reverse osmosis membrane becomes one of main obstacles for preventing the technical development and progress of the reverse osmosis membrane, so that the improvement of the anti-pollution antibacterial activity of the reverse osmosis membrane is particularly important for the development of the reverse osmosis industry.
In order to solve the above problems, various methods have been disclosed to prepare an anti-fouling, bacteriostatic reverse osmosis membrane. Patent CN101130444A discloses a preparation method of a modified reverse osmosis membrane based on PVA coating, PVA is a polyhydroxy polymer, the coating can improve the hydrophilicity of the membrane surface and can effectively reduce the contact between the membrane surface and the intercepted molecules, thereby reducing the membrane pollution, however, the PVA and the polyamide layer surface are physically combined, the PVA can be gradually dissolved and finally fall off in the process of washing the reverse osmosis membrane surface, and the membrane performance is reduced. Patent CN109876674A discloses that a layer of nano silver ions is coated on the surface of a membrane, thereby improving the biological pollution resistance of a reverse osmosis membrane and slowing down the life loss of the reverse osmosis membrane, but the nano particles are only limited to laboratory research and cannot realize large-scale production in a short period of time. Patent CN109603585A discloses a method for preparing a quaternary ammonium salt modified polyamide reverse osmosis membrane, which utilizes the reaction of aliphatic amine and epoxy group to graft quaternary ammonium salt on the surface of the reverse osmosis membrane, thereby preparing a high antibacterial reverse osmosis membrane, but the flux improvement effect is not seen, and the antibacterial activity is still limited.
Even so, still do not have at present and can not lose under the prerequisite of flux and desalination, compromise organic matter pollution and effective antibacterial reverse osmosis membrane, but in the practical application process, be difficult to avoid multiple pollution coexistence, must pass through high temperature acid-base washing simultaneously after polluting, present technique is a lot of unstable under high temperature, can lead to antibacterial and antipollution performance to descend, consequently, urgent need develop a high temperature stable antipollution, antibacterial, big flux reverse osmosis membrane.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention aims to provide a high-temperature stable anti-pollution, antibacterial, and large-flux reverse osmosis membrane, which can give consideration to organic pollution and effective antibacterial performance on the premise of not losing flux and salt rejection, and can maintain the original anti-pollution and antibacterial functions after high-temperature cleaning.
The invention also aims to provide a preparation method of the anti-pollution, bacteriostatic and large-flux reverse osmosis membrane with high-temperature stability.
It is a further object of the present invention to provide the use of such a high temperature stable, anti-fouling, bacteriostatic, high flux reverse osmosis membrane.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an anti-pollution, antibacterial and large-flux reverse osmosis membrane comprises a polyester non-woven fabric, a polysulfone ultrafiltration support layer and a polyamide functional layer formed on the polysulfone base membrane, wherein the surface of the polyamide functional layer comprises a stilbene compound containing amino and sulfonic acid structures and an aromatic quaternary ammonium salt blend.
In a specific embodiment, the stilbene compound containing an amino group and a sulfonic acid structure is a stilbene compound containing at least 2 primary amino groups or secondary amino groups and at least 1 sulfonic acid group; preferably one or more selected from the group consisting of 4,4' -diaminostilbene-2, 2' -disulfonic acid sodium, 4' -diaminostilbene-2, 2' -disulfonic acid, 4' -bis (4-amino-1-naphthylazo) stilbene-2, 2' -disulfonic acid, 2' - (1, 4-phenylenedi-2, 1-ethenylene) bis [ 5-aminobenzenesulfonic acid ] acid, 4-phenylamino-4 ' aminostilbene-2, 2' -disulfonic acid salt.
In a specific embodiment, the aromatic quaternary ammonium salt is a long-chain alkane-containing monocyclic quaternary ammonium salt, preferably selected from monocyclic quaternary ammonium salts of C3-C18 alkyl groups, more preferably one or more of N-pentadecyl-N-benzyl ammonium chloride, N-hexadecyl-N-benzyl ammonium chloride and N-octadecyl-N-benzyl ammonium chloride.
In a specific embodiment, the polyamide functional layer is aromatic polyamide with a three-dimensional network structure and is formed by an interfacial polymerization reaction of an aqueous phase solution of m-phenylenediamine as a monomer and an organic phase solution of trimesoyl chloride as a monomer; the polysulfone ultrafiltration support layer is a polysulfone support film layer formed on a non-woven fabric.
On the other hand, the preparation method of the anti-pollution, antibacterial and large-flux reverse osmosis membrane comprises the following steps:
1) Contacting a polysulfone ultrafiltration support layer with an aqueous phase solution containing m-phenylenediamine monomers, and removing the excess aqueous phase solution on the surface of the polysulfone ultrafiltration support layer;
2) Contacting the prepared oil phase organic solution containing trimesoyl chloride with a polysulfone ultrafiltration supporting layer, so that m-phenylenediamine and trimesoyl chloride generate interfacial polymerization reaction on the surface of the polysulfone supporting layer, pouring off the redundant organic solution, and removing the residual organic solvent on the surface to form a polyamide reverse osmosis membrane;
3) Contacting the prepared aqueous solution containing the stilbene compounds containing amino and sulfonic acid structures with the reverse osmosis membrane formed in the step 2), removing redundant solution, putting the solution into an oven for heat treatment, and taking out the membrane for washing;
4) Contacting the prepared water solution containing the aromatic quaternary ammonium salt with the reverse osmosis membrane formed in the step 3), removing the redundant solution, putting the water solution into an oven for heat treatment again, and taking out the membrane for washing;
5) Exposing the cleaned polyamide composite membrane in a nitrous acid solution for post-treatment; rinsing and drying to obtain the anti-pollution, antibacterial and large-flux reverse osmosis membrane.
In a specific embodiment, the mass concentration of the aqueous phase solution containing m-phenylenediamine monomer in step 1) is 1.5 to 3.5wt%.
In a specific embodiment, the mass concentration of the oil phase organic solution containing trimesoyl chloride in the step 2) is 0.1-0.2 wt%; wherein the organic solvent is one or more of aliphatic alkane, aromatic alkane or halogenated alkane; preferably aliphatic alkanes, and more preferably one or more kinds selected from n-decane, isopar G, isopar L and isopar H isoparaffins.
In a specific embodiment, the mass concentration of the aqueous solution of stilbene compounds containing amino and sulfonic acid structures in step 3) is 0.01 to 1wt%, preferably 0.1 to 0.5wt%.
In a specific embodiment, the mass concentration of the aromatic quaternary ammonium salt in the step 4) is 0.05 to 2wt%, preferably 0.1 to 1.0wt%; more preferably, the mass ratio of the stilbene compound to the aromatic quaternary ammonium salt in the steps 3) and 4) is 0.05 to 10, preferably 0.1 to 5.
In a specific embodiment, the contact time of the polysulfone ultrafiltration support layer in step 1) with the aqueous phase solution containing m-phenylenediamine monomer and the oil phase organic solution containing trimesoyl chloride in step 2) is 10-300s, preferably 30-60s.
In a specific embodiment, the mass concentration of the nitrous acid solution in the step 5) is 0.1-1.0%, the pH is 2-3, and more preferably, the polyamide composite membrane is exposed to the nitrous acid solution for 0.5-5min at a temperature of 5-20 ℃.
In a specific embodiment, after the composite membrane is treated by the nitrous acid solution in the step 5), the residual nitrous acid solution on the composite membrane is removed by rinsing with a reducing agent, and then the composite membrane is rinsed and dried by hot water at the temperature of 60-100 ℃; preferably, the reducing agent is a 0.5-2wt% sodium sulfite solution.
In yet another aspect, an application of the anti-pollution, antibacterial and large-flux reverse osmosis membrane or the anti-pollution, antibacterial and large-flux reverse osmosis membrane prepared by the preparation method in a water treatment component or a water treatment method.
Compared with the prior art, the invention has the beneficial effects that:
1) On the basis of a non-woven fabric, a polysulfone supporting layer and a polyamide reverse osmosis membrane, the membrane surface is subjected to modification treatment of stilbene compounds, quaternary ammonium salts and nitrous acid through multi-step post-treatment, so that the reverse osmosis membrane which is capable of giving consideration to organic pollution and effective bacteriostasis is obtained on the premise of not losing flux and desalination rate.
2) The invention chemically grafts the stilbene compound and the quaternary ammonium salt on the surface of the polyamide layer through a multi-step post-treatment process, the stilbene compound and the quaternary ammonium salt containing hydroxyl have unique antibacterial property, and the benzene ring structure of the stilbene compound further enhances the antibacterial stability of the quaternary ammonium salt. In addition, the stilbene compounds contain abundant hydrophilic groups such as hydroxyl groups or sulfonic acid groups, so that the membrane after post-treatment has stronger hydrophilic capacity, the membrane flux can be increased to a certain extent, organic matters can be prevented from being attached and deposited on the surface of the membrane, and the great attenuation of the membrane flux caused by pollutant accumulation can be relieved. After the interfacial polymerization is finished, the antibacterial layer is introduced, so that the crosslinking degree is not influenced in the primary interfacial polymerization process, and the membrane desalination rate is not influenced.
3) The anti-pollution and antibacterial large-flux reverse osmosis membrane disclosed by the invention is good in high-temperature thermal stability, meanwhile, the service life of the membrane can be prolonged, the membrane loss cost is reduced, the method is simple to operate, the industrial production can be realized, and the wide application is easy.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following embodiments, the scope of the present invention is not limited to the following specific embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work belong to the scope of the present invention.
The anti-pollution, antibacterial and large-flux reverse osmosis membrane comprises a polyester non-woven fabric, a polysulfone ultrafiltration supporting layer and a polyamide functional layer formed on the polysulfone base membrane, wherein the polyamide functional layer of the reverse osmosis membrane is a blend of a stilbene compound with an amino group and a sulfonic acid structure and a quaternary ammonium salt grafted on the surface of the conventional polyamide functional layer in the field.
The polyamide functional layer is aromatic polyamide with a three-dimensional net structure, and is formed by performing interfacial polymerization reaction on an aqueous phase solution of m-phenylenediamine as a monomer and an organic phase solution of trimesoyl chloride as a monomer; the polysulfone ultrafiltration support layer is a polysulfone support membrane formed on non-woven fabric; the biggest innovation of the method is that the blend of stilbene compounds with amino and sulfonic acid structures and quaternary ammonium salt is grafted on the surface of the polyamide functional layer, so that the reverse osmosis membrane has stable high-temperature anti-pollution, antibacterial and high-flux performances, and the antibacterial property of the reverse osmosis membrane is still ensured even after high-temperature acid-base cleaning.
The preparation method of the anti-pollution, antibacterial and large-flux reverse osmosis membrane comprises the following steps:
1) Immersing a polysulfone ultrafiltration support layer into an aqueous solution containing m-phenylenediamine monomer for contact, taking out, and removing the excess aqueous solution on the surface of the support layer by using a squeezing roller;
2) Pouring the prepared oil phase organic solution containing trimesoyl chloride on the surface of an ultrafiltration supporting layer to ensure that m-phenylenediamine and trimesoyl chloride generate interfacial polymerization reaction on the surface of a polysulfone supporting layer, pouring out the redundant organic solution, and removing the residual organic solvent on the surface by an effective means to form the polyamide reverse osmosis membrane;
3) Pouring the prepared aqueous solution containing the stilbene compounds containing amino and sulfonic acid structures on the surface of the reverse osmosis membrane formed in the step 2), pouring the excessive solution, putting the reverse osmosis membrane into an oven for heat treatment, and taking out the membrane for washing;
4) Pouring the prepared water solution containing the quaternary ammonium salt on the surface of the reverse osmosis membrane formed in the step 3), pouring the redundant solution, putting the reverse osmosis membrane into an oven for heat treatment again, and taking out the membrane for washing;
5) Exposing the cleaned polyamide composite membrane to a nitrous acid solution for post-treatment; rinsing and drying to obtain the cleaning-resistant reverse osmosis membrane.
It should be noted that the "contacting" in the present invention may be to immerse the surface of the polysulfone ultrafiltration support layer in the corresponding solution and then take out, to pour or coat the corresponding solution on the surface of the polysulfone ultrafiltration support layer, or to combine the two and other "contacting" means commonly used in the art, and the key point is to coat the surface of the polysulfone ultrafiltration support layer with the corresponding reaction material to prepare for the subsequent polycondensation or grafting reaction. Interfacial contact is preferred in the present invention such that interfacial polymerization preferably occurs at the interface. Such "contacting" is within the scope of the present invention, as will be appreciated by those skilled in the art.
In the present invention, the mass concentration of the m-phenylenediamine in the aqueous solution in the step 1) is usually 1.5 to 3.5wt%, for example, including but not limited to 2wt%, 2.5wt%, 3.0wt%; the mass concentration of the trimesoyl chloride organic phase solution in step 2) is usually 0.1wt% to 0.2wt%, for example, including but not limited to 0.1wt%, 0.15wt%, 0.2wt%; the organic solvent in the organic phase solution is one or more of aliphatic alkane, aromatic alkane and halogenated alkane, preferably aliphatic alkane, such as one or more of n-decane, isopar G, isopar L and isopar H isoparaffin.
The concentration of stilbenes in step 3) is from 0.01 to 1% by weight, including for example but not limited to 0.02%, 0.03%, 0.04%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, preferably from 0.1 to 0.5%. Wherein the stilbene compounds containing amino and sulfonic acid structures are stilbene compounds containing at least 2 primary or secondary amino groups and at least 1 sulfonic acid group, such as but not limited to one or more of 4,4' -diaminostilbene-2, 2' -disulfonic acid sodium, 4' -diaminostilbene-2, 2' -disulfonic acid, 4' -bis (4-amino-1-naphthylazo) stilbene-2, 2' -disulfonic acid, 2' - (1, 4-phenylenedi-2, 1-ethenylene) bis [ 5-aminobenzenesulfonic acid ] acid, 4-phenylamino-4 ' -aminostilbene-2, 2' -disulfonic acid salt. It will be understood by those skilled in the art that other stilbenes having at least 2 primary or 2 secondary amino groups and at least 1 sulfonic acid group are capable of performing the effects of the present invention and are within the scope of the present invention.
The concentration of quaternary ammonium salt in step 4) is 0.05 to 2wt%, for example including but not limited to 0.05wt%, 0.08wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, preferably 0.1 to 1.0wt%; the aromatic quaternary ammonium salt is a single aromatic ring quaternary ammonium salt containing long-chain alkane, preferably selected from C3-C18 alkyl single aromatic ring quaternary ammonium salts, and more preferably one or more of N-pentadecyl-N-benzyl ammonium chloride, N-hexadecyl-N-benzyl ammonium chloride and N-octadecyl-N-benzyl ammonium chloride.
In the present invention, the mass ratio of the stilbene compound to the quaternary ammonium salt is 0.05 to 10, for example, but not limited to, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, preferably 0.1 to 5.
The contact time of the polysulfone porous support layer in the step 2) with the aqueous phase solution containing m-phenylenediamine and the organic phase solution containing trimesoyl chloride in the step 3) is 10-300s, such as but not limited to 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 130s, 150s, 170s, 200s, 220s, 250s, 280s and 300s, preferably 30-60s.
The mass concentration of the nitrous acid solution in the step 5) is 0.1-1.0%, such as but not limited to 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, and the pH is 2-3, preferably, the composite membrane is exposed to the nitrous acid solution for 0.5-5min at a temperature of 5-20 ℃. After the composite membrane is treated by the nitrous acid solution, the residual nitrous acid solution on the composite membrane is removed by rinsing with a reducing agent, and then the composite membrane is rinsed and dried by hot water at the temperature of 60-100 ℃; preferably, the reducing agent is a 0.5-2% sodium sulfite solution.
The preparation process of the anti-pollution, bacteriostatic and large-flux reverse osmosis membrane comprises the step of contacting a porous polysulfone supporting layer with m-phenylenediamine aqueous phase solution, and then contacting with trimesoyl chloride organic phase solution to obtain the polyamide composite membrane. The inventor of the application unexpectedly finds that after the primary interfacial polymerization reaction of m-phenylenediamine and trimesoyl chloride, the polyamide composite membrane can be remarkably improved in pollution resistance and bacterial inhibition by sequentially carrying out the grafting reaction of an aqueous solution containing sulfonic acid and aminostilbene compounds and an aqueous solution of quaternary ammonium salt and combining a nitrous acid treatment method, the flux is improved to a certain extent, the desalination rate is kept not to be reduced, and the original pollution resistance and bacterial inhibition functions can be kept after high-temperature cleaning.
The possible mechanism is presumed to be as follows: when a polyamide membrane passes through an aqueous solution containing sulfonic acid and aminostilbenes, the amino group of a specific stilbenes compound can react with the residual acyl chloride group of trimesoyl chloride on the surface of the membrane so as to be grafted and fixed on the surface of the membrane through a chemical bond, simultaneously, the sulfonic acid group and part of unreacted amino group are dissociated, the membrane passes through an aqueous solution of single aromatic ring quaternary ammonium salt containing long-chain alkane again, the sulfonic acid group is easy to react with the quaternary ammonium group, the quaternary ammonium group is deposited on the surface of the membrane, and after nitrous acid treatment, part of dissociated amino group can undergo azo reaction, and the generated diazonium salt is partially hydrolyzed into phenolic hydroxyl; on one hand, the stilbene compound containing hydroxyl and the quaternary ammonium salt have unique antibacterial property to achieve complementary effect, the stilbene substance can make up the weakness of the quaternary ammonium salt in partial strains, particularly fungi, and improve the overall antibacterial property of the reverse osmosis membrane, and meanwhile, the benzene ring structure of the stilbene compound enables the quaternary ammonium salt containing single aromatic ring to be changed into a structure containing multiple aromatic rings, so that the antibacterial thermal stability of the quaternary ammonium salt is further enhanced, and the antibacterial property of the quaternary ammonium salt can be still ensured after high-temperature acid-base cleaning; on the other hand, the stilbene compounds contain abundant hydrophilic groups such as hydroxyl groups or sulfonic acid groups and the like, so that the membrane flux can be increased to a certain extent, and the antibacterial layer is introduced after the interfacial polymerization is completed, so that the crosslinking degree is not influenced in the primary interfacial polymerization process, and the membrane desalting rate is not influenced.
The present invention is further illustrated by the following more specific examples, which are not to be construed as limiting in any way.
The following is a description of the methods used or possible to be used in the examples of the invention:
1) Evaluation of salt rejection and permeation flux
The permeation flux and the salt rejection rate are two important parameters for evaluating the separation performance of the reverse osmosis membrane.
According to GB/T32373-2015 reverse osmosis membrane test method, the separation performance of the reverse osmosis membrane is evaluated.
The salt rejection (R) is defined as: under certain operating conditions, the salt concentration (C) of the feed liquid f ) With the salt concentration (C) in the permeate p ) The difference is divided by the salt concentration (C) of the feed solution f ) As shown in formula (1).
Permeate flux is defined as: the volume of water per membrane area per unit time is L/(m) under certain operating conditions 2 ·h)。
The reverse osmosis membrane performance measurement adopts the following operating conditions: the feed solution was 2000ppm aqueous sodium chloride solution, the pH of the solution was 7.0. + -. 0.5, the operating pressure was 1.55MPa, and the operating temperature was 25. + -. 0.5 ℃.
2) Evaluation of anti-pollution Properties
According to the change of the permeation flux and the salt rejection of the reverse osmosis membrane before and after the protein pollution test, the anti-pollution performance of the reverse osmosis membrane is characterized, and the method mainly comprises the following steps: taking a mixed aqueous solution of 2000ppm sodium chloride and 100ppm bovine serum albumin as a feed water raw material solution, continuously running for 24 hours at an operating pressure of 1.55MPa and a temperature of 25 +/-1 ℃, respectively recording the permeation flux and the desalination rate of a reverse osmosis membrane at the beginning and the end of a protein pollution test, and calculating the flux attenuation rate of the membrane:
flux decay rate = (flux before contamination-flux after contamination)/flux before contamination × 100%.
3) Evaluation of bacteriostatic Properties
In the patent, escherichia coli and saccharomycetes are taken as strains respectively, and an antibacterial performance experiment is carried out according to GB/T37206-2018;
the reference number A indicates that the blank reverse osmosis membrane prepared in comparative example 3 was used for blank reference, B1 to B13 correspond to the reverse osmosis membranes prepared in examples 1 to 13, B14 to B15 correspond to the reverse osmosis membranes prepared in comparative examples 1 and 2, and B16 to B18 correspond to the reverse osmosis membranes prepared in comparative examples 4 to 6.
Cutting the membrane to be tested into a round shape with the diameter of (20 +/-1) mm, and carrying out sterilization treatment after multiple times of cleaning; taking 20 sterile surface dishes, numbering A and B1-B18, and transferring 0.4mL of test bacterial suspension liquid to the surface dishes; respectively and uniformly contacting the correspondingly numbered patches with the bacterial suspension, and putting the patches into a constant-temperature constant-humidity incubator with the temperature of 37 ℃ and the humidity of 90% for 2h; taking out the reverse osmosis membrane, washing the membrane and the watch glass by using a phosphate buffer solution, diluting 1mL by 10 times step by step, and fully mixing; uniformly coating 1mL of diluent on plate counting agar, culturing for 24h in a constant-temperature constant-humidity environment at 37 ℃, taking out, and counting colonies;
the formula for calculating the bacteriostasis rate (K) is as follows:
K(％)＝((A-B)/A)×100％
in the formula:
k-bacteriostatic rate,%;
a, colony count after blank culture, CFU;
b-the colony count, CFU, of the reverse osmosis membranes in examples 1-13, comparative examples 1-2, 4-6.
4) Zeta potential of film surface
The Zeta potential of the reverse osmosis membrane reflects the surface charge distribution of the membrane to a certain extent and also has an important influence on the membrane performance.
The invention adopts a Surpass3 Zeta potential tester to test the Zeta potential of the membrane, and the test conditions are as follows: the Gap Height is 100 + -5 μm, the temperature is 20 + -3 deg.C, the solution is 1mM KCl solution, the test pH is 6.7 + -0.2, after washing with pure water before each test, rinsing with the test solution for 2-4 times, testing for 4 times in each shop, and taking the average value.
5) Acid and alkali cleaning method
The purpose of the test is to verify the antibacterial property comparison of the reverse osmosis membranes before and after acid-base cleaning, and the specific operation is to circularly clean the reverse osmosis membranes for 4 hours in NaOH solution with pH =10 and at the temperature of 40 ℃, circularly clean the reverse osmosis membranes for 1 hour in hydrochloric acid solution with pH =4 and at the temperature of 40 ℃ after clean water washing, and take out the membranes for later use after pure water washing.
The sources of the raw materials used in the examples of the present invention and comparative examples are shown in Table 1, and all of them are commercially available conventional raw materials unless otherwise specified.
6) Elemental analysis (XPS) of film surface
An X-ray photoelectron spectrum analyzer (XPS) is a very sensitive surface analysis method, detection signals come from 2-5nm of the surface of a material, and the types and the percentage contents of various elements on the surface can be represented.
The method adopts XPS to represent the types and the percentage content of elements on the surface of the reverse osmosis membrane, before the test, the reverse osmosis membrane is placed in a vacuum oven at 40 ℃ for drying for 24 hours, three points are taken for testing each sample, and the test results are averaged.
The main raw material sources for the following examples are as in table 1 below:
TABLE 1 information of the main materials
The examples of the present invention and the comparative examples uniformly used polysulfone support membranes prepared by the following conventional methods and will not be described separately.
Preparation of polysulfone support membrane: dissolving 16.5wt% of polysulfone resin in dimethylformamide to obtain a polysulfone membrane casting solution; then uniformly coating and scraping the filtered and defoamed polysulfone membrane casting solution on a polyester non-woven fabric; and then the membrane is put into water to be converted into a membrane, and the polysulfone support membrane is obtained after cleaning, wherein the aperture of the prepared polysulfone base membrane is between 30 and 50 nm.
Example 1
The polysulfone support membrane prepared by the method is adopted, and the reverse osmosis membrane is prepared by the following method:
1) Preparing m-phenylenediamine aqueous phase solution with the mass concentration of 2.5wt%, and stirring at room temperature to completely dissolve the m-phenylenediamine aqueous phase solution;
2) Preparing an oil phase solution of trimesoyl chloride with the mass concentration of 0.12wt%, and stirring at room temperature to completely dissolve the trimesoyl chloride, wherein the organic solvent is isopar G isoparaffin;
3) Preparing a 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution with the mass concentration of 0.25wt%, and stirring at room temperature to completely dissolve the 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution;
4) Preparing 0.5wt% quaternary ammonium salt aqueous solution, and stirring at room temperature to completely dissolve the quaternary ammonium salt aqueous solution;
5) Preparing a nitrous acid solution with the mass concentration of 0.5 percent and the pH of 2-3, and keeping the temperature at 10 ℃ for later use;
6) Preparing 0.5% sodium sulfite solution, and stirring at room temperature until the sodium sulfite solution is completely dissolved;
7) Immersing the polysulfone ultrafiltration support layer in an aqueous solution containing m-phenylenediamine monomers for contact for 30s, taking out, and removing the redundant aqueous solution on the surface of the support layer by using a squeezing roller;
8) Pouring the prepared oil phase organic solution containing trimesoyl chloride on the surface of an ultrafiltration support layer, contacting for 30s to enable m-phenylenediamine and trimesoyl chloride to generate interfacial polymerization reaction on the surface of a polysulfone support layer, pouring off the redundant organic solution, and uniformly blowing by using a wind knife until no residual solvent is left on the surface of the membrane, thus forming the polyamide reverse osmosis membrane;
9) Pouring the prepared 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution onto the surface of the reverse osmosis membrane formed in the step 2), pouring off the redundant solution, putting the reverse osmosis membrane into an oven for heat treatment for 1min, taking out the membrane and washing the membrane with water;
10 Pouring the prepared aqueous solution of N-benzyl-N-pentadecyl-ammonium chloride on the surface of the reverse osmosis membrane formed in the step 3), pouring out the excessive solution, putting the reverse osmosis membrane into an oven for heat treatment again for 1min, taking out the membrane and washing the membrane with water;
11 Immersing the cleaned polyamide composite membrane in 0.5wt% nitrous acid solution for 1min; rinsing, immersing into sodium sulfite solution for treatment for 1min, rinsing with pure water, and drying at 80 ℃ to obtain the reverse osmosis membrane.
Examples 2 to 15
Reverse osmosis membranes of examples 2 to 15 were prepared in substantially the same manner as in example 1, respectively, except that the types and ratios of the raw materials were added in correspondence with Table 2.
Comparative examples 1 to 6
The reverse osmosis membranes of comparative examples 1 to 6 were prepared in substantially the same manner as in example 1, respectively, except that the kinds and ratios of the raw materials were added correspondingly with reference to table 2.
Table 2 raw material information of each example
The reverse osmosis membranes prepared in examples and comparative examples were subjected to salt rejection, permeation flux, anti-contamination test, bacteriostatic test before and after washing, and Zeta potential test, and the results are recorded in the permeability of the reverse osmosis membranes in table 3.
TABLE 3 film Properties of examples and comparative examples
By performing elemental analysis on the membrane surface, the relevant results are shown in Table 4, and it can be seen that the surface element composition and the ratio change, sulfur is detected in example 2, and it is presumed that stilbene compounds are successfully grafted to the surface, while the quaternary ammonium salt does not contain O, and the C/O ratio is increased, and it is presumed that quaternary ammonium salt exists on the surface.
Table 4 film surface element analysis results
By combining the experimental results shown in tables 2 and 3, when the polyamide membrane is modified by sulfonic acid and aminostilbenes and is subjected to post-treatment by adding nitrous acid, the reverse osmosis membrane which is capable of considering organic pollution and effective antibacterial performance on the premise of flux increase and desalination rate maintenance is obtained, and the antibacterial stability can be maintained after high-temperature acid-base cleaning.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An anti-pollution, antibacterial and large-flux reverse osmosis membrane comprises a polyester non-woven fabric, a polysulfone ultrafiltration support layer and a polyamide functional layer formed on the polysulfone base film, and is characterized in that the surface of the polyamide functional layer comprises a stilbene compound containing amino and sulfonic acid structures and an aromatic quaternary ammonium salt blend.
2. The reverse osmosis membrane of claim 1, wherein the stilbene compound containing an amino group and a sulfonic acid structure is a stilbene compound containing at least 2 primary or secondary amino groups and at least 1 sulfonic acid group; preferably one or more selected from the group consisting of 4,4' -diaminostilbene-2, 2' -disulfonic acid sodium, 4' -diaminostilbene-2, 2' -disulfonic acid, 4' -bis (4-amino-1-naphthylazo) stilbene-2, 2' -disulfonic acid, 2' - (1, 4-phenylenedi-2, 1-ethenylene) bis [ 5-aminobenzenesulfonic acid ] acid, 4-phenylamino-4 ' aminostilbene-2, 2' -disulfonic acid salt.
3. A reverse osmosis membrane according to claim 1 wherein the aromatic quaternary ammonium salt is a long chain alkane containing mono-aromatic ring quaternary ammonium salt, preferably selected from C3 to C18 alkyl mono-aromatic ring quaternary ammonium salts, more preferably one or more of N-pentadecyl-N-benzyl ammonium chloride, N-hexadecyl-N-benzyl ammonium chloride, N-octadecyl-N-benzyl ammonium chloride.
4. A reverse osmosis membrane according to any one of claims 1 to 3, wherein the polyamide functional layer is an aromatic polyamide having a three-dimensional network structure formed by an interfacial polymerization reaction of an aqueous phase solution of m-phenylenediamine as a monomer and an organic phase solution of trimesoyl chloride as a monomer; the polysulfone ultrafiltration support layer is a polysulfone support film layer formed on a non-woven fabric.
5. The method of preparing an anti-fouling, antibacterial, high flux reverse osmosis membrane according to any one of claims 1-4 comprising the steps of:
1) Contacting a polysulfone ultrafiltration support layer with an aqueous phase solution containing m-phenylenediamine monomers, and removing the excess aqueous phase solution on the surface of the polysulfone ultrafiltration support layer;
2) Contacting the prepared oil phase organic solution containing trimesoyl chloride with a polysulfone ultrafiltration support layer to ensure that m-phenylenediamine and trimesoyl chloride have interfacial polymerization reaction on the surface of the polysulfone support layer, pouring out redundant organic solution, and removing residual organic solvent on the surface to form a polyamide reverse osmosis membrane;
3) Contacting the prepared aqueous solution containing stilbene compounds containing amino and sulfonic acid structures with the reverse osmosis membrane formed in the step 2), removing redundant solution, putting the solution into an oven for heat treatment, and taking out the membrane for washing;
4) Contacting the prepared water solution containing the aromatic quaternary ammonium salt with the reverse osmosis membrane formed in the step 3), removing the redundant solution, putting the water solution into an oven for heat treatment again, and taking out the membrane for washing;
5) Exposing the cleaned polyamide composite membrane to a nitrous acid solution for post-treatment; rinsing and drying to obtain the anti-pollution, antibacterial and large-flux reverse osmosis membrane.
6. The production method according to claim 5, wherein the mass concentration of the aqueous phase solution containing m-phenylenediamine monomer in step 1) is 1.5 to 3.5wt%; preferably, the mass concentration of the oil phase organic solution containing trimesoyl chloride in the step 2) is 0.1-0.2 wt%; wherein the organic solvent is one or more of aliphatic alkane, aromatic alkane or halogenated alkane; preferably aliphatic alkanes, and more preferably one or more kinds selected from n-decane, isopar G, isopar L and isopar H isoparaffins.
7. The preparation method according to claim 5, wherein the mass concentration of the aqueous solution of stilbene compounds containing amino and sulfonic acid structures in step 3) is 0.01-1 wt%, preferably 0.1-0.5 wt%; preferably, the mass concentration of the aromatic quaternary ammonium salt in the step 4) is 0.05 to 2wt%, preferably 0.1 to 1.0wt%; more preferably, the mass ratio of the stilbene compound to the aromatic quaternary ammonium salt in the steps 3) and 4) is 0.05 to 10, preferably 0.1 to 5.
8. The method according to claim 5, wherein the contact time of the polysulfone ultrafiltration support layer in step 1) with the aqueous solution containing m-phenylenediamine monomer and the contact time of the polysulfone ultrafiltration support layer in step 2) with the oil phase organic solution containing trimesoyl chloride are both 10-300s, preferably 30-60s; preferably, the mass concentration of the nitrous acid solution in the step 5) is 0.1-1.0%, and the pH is 2-3, and more preferably, the polyamide composite membrane is exposed to the nitrous acid solution for 0.5-5min at a temperature of 5-20 ℃.
9. The preparation method of claim 8, wherein the composite membrane in step 5) is treated with nitrous acid solution, and then rinsed with a reducing agent to remove residual nitrous acid solution on the composite membrane, and then rinsed with hot water at 60-100 ℃ and dried; preferably, the reducing agent is a 0.5-2wt% sodium sulfite solution.
10. Use of the anti-fouling, antibacterial, high flux reverse osmosis membrane of any one of claims 1 to 4 or prepared by the method of manufacture of any one of claims 5 to 9 in a water treatment component or a water treatment process.
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| JP2000263706A (en) * | 1999-03-11 | 2000-09-26 | Toyobo Co Ltd | Antibacterial laminated film |
| CN103464011A (en) * | 2013-09-21 | 2013-12-25 | 淮海工学院 | Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane |
| CN105148750A (en) * | 2015-08-21 | 2015-12-16 | 浙江大学 | Method for modifying surface of polyamide composite film |
| CN110433666A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling polyamide composite film, raw material, preparation method and application |
| CN113385049A (en) * | 2021-06-04 | 2021-09-14 | 中国石油大学(华东) | High-selectivity self-micropore polyamide nanofiltration composite membrane and preparation method thereof |
| CN113694731A (en) * | 2021-08-24 | 2021-11-26 | 江苏沛尔膜业股份有限公司 | Negatively charged ultrafiltration membrane for resisting microbial pollution and preparation method thereof |
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