CN109847586B - High-flux reverse osmosis membrane and preparation method and application thereof - Google Patents
High-flux reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN109847586B CN109847586B CN201811566175.3A CN201811566175A CN109847586B CN 109847586 B CN109847586 B CN 109847586B CN 201811566175 A CN201811566175 A CN 201811566175A CN 109847586 B CN109847586 B CN 109847586B
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- 239000012528 membrane Substances 0.000 title claims abstract description 194
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 210000004379 Membranes Anatomy 0.000 claims abstract description 123
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229960003638 dopamine Drugs 0.000 claims abstract description 53
- 230000004907 flux Effects 0.000 claims abstract description 39
- 239000002346 layers by function Substances 0.000 claims abstract description 38
- 238000005266 casting Methods 0.000 claims abstract description 37
- 239000002052 molecular layer Substances 0.000 claims abstract description 30
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 25
- 210000002469 Basement Membrane Anatomy 0.000 claims abstract description 24
- 239000008346 aqueous phase Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 22
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
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- 235000013305 food Nutrition 0.000 claims abstract description 5
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 5
- 239000010841 municipal wastewater Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 86
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
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- 239000002904 solvent Substances 0.000 claims description 26
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 17
- LENZDBCJOHFCAS-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1H-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
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- CTENFNNZBMHDDG-UHFFFAOYSA-N 4-(2-aminoethyl)benzene-1,2-diol;hydron;chloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 229960001149 Dopamine Hydrochloride Drugs 0.000 claims description 10
- LXEJRKJRKIFVNY-UHFFFAOYSA-N Terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 10
- 229960000892 attapulgite Drugs 0.000 claims description 10
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- 229940018564 M-PHENYLENEDIAMINE Drugs 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
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- 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 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M buffer Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
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- 239000001913 cellulose Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002496 poly(ether sulfone) Polymers 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
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- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 claims description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N O-Phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920001721 Polyimide Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 230000001476 alcoholic Effects 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 9
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 239000011780 sodium chloride Substances 0.000 description 5
- YQUVCSBJEUQKSH-UHFFFAOYSA-N Protocatechuic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WTDRDQBEARUVNC-LURJTMIESA-N 3-hydroxy-L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- IBGBGRVKPALMCQ-UHFFFAOYSA-N Protocatechuic aldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
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- 230000001788 irregular Effects 0.000 description 2
- 229960004502 levodopa Drugs 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002492 poly(sulfones) Polymers 0.000 description 2
- 230000034655 secondary growth Effects 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 102000010637 Aquaporins Human genes 0.000 description 1
- 108010063290 Aquaporins Proteins 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N Molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- 210000002356 Skeleton Anatomy 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229940041158 antibacterial for systemic use Imidazole derivatives Drugs 0.000 description 1
- 229940042051 antimycotic for systemic use Imidazole derivatives Drugs 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
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- 229940093910 gyncological antiinfectives Imidazole derivatives Drugs 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
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- 229940079865 intestinal antiinfectives Imidazole derivatives Drugs 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 relates to a high-flux reverse osmosis membrane and a preparation method and application thereof. The method comprises the following steps: preparing a polymer solution dispersed with an inorganic silicate nano material as a casting solution, coating the casting solution on a support material, and soaking the support material in a coagulating bath to obtain a base film; immersing the basement membrane into the dopamine/ZIF-8 suspension to enable the dopamine/ZIF-8 to grow on the surface of the basement membrane, so as to obtain a modified basement membrane with a dopamine/ZIF-8 intermediate nano layer; immersing the modified base membrane into the aqueous phase solution and the organic phase solution to carry out interfacial polymerization to prepare a functional layer to obtain a raw membrane; and (3) immersing the primary membrane in water, and dissolving to remove the middle nano layer to obtain the high-flux reverse osmosis membrane. The reverse osmosis membrane has the advantages of thin functional layer, large effective permeation area, and greatly improved flux without affecting desalination rate. The reverse osmosis membrane can be used in water treatment applications, industrial or municipal wastewater treatment, food processing, and pharmaceutical industries. The invention also relates to a membrane element and a filtration system comprising the reverse osmosis membrane.
Description
Technical Field
The invention relates to the technical field of water treatment membranes, in particular to a high-flux reverse osmosis membrane, a preparation method and application thereof, and a membrane element and a filtration system comprising the high-flux reverse osmosis membrane.
Background
According to the published data of the united nations, more than one billion of people live in water resource scarce areas worldwide, and by 2025, this number will rise to 18 billion. Furthermore, there is a sharp conflict between people's pursuit of healthy life and increasingly worse living drinking water. Various water treatment technologies are developed in order to solve the problems of water shortage, wastewater treatment and daily water use of people, for example, a reverse osmosis membrane separation technology is the most widely applied separation technology in the global water treatment industry because of the advantages of high rejection rate, high flux, good chemical stability, low operation pressure, capability of selectively purifying and separating water bodies and the like.
The functional layer structure of reverse osmosis polyamide is relevant for the separation performance of the membrane, however there is usually a Trade-off relationship between the flux and the desalination performance of the membrane (Park et al, Science,2017,356,1137). The more and more severe requirements on membrane elements with large flux and high effluent quality in the current market are, which indicates that the simultaneous improvement of the flux and the salt ion rejection rate of the membrane becomes an irreversible trend, and the bottleneck problem of the current water treatment membrane is also faced.
The design of the functional layer for controlling the molecular structure is of great significance in improving the performance of the membrane, such as the development of advanced membrane materials for modification to reduce the resistance of water passing through the functional layer and the improvement of the permeation flux of the membrane without sacrificing the selectivity of the membrane, including the development of modified membranes containing materials such as aquaporins, nanoporous graphene, covalent triazine framework, molybdenum disulfide (oxide), organic porous cages, zeolite nanosheets, etc. (Werber et al, nat. rev. mater.,2016,1, 16018; CN 201610280385.0). CN201610280385.0 describes an aromatic polyamide reverse osmosis membrane modified by a graphene oxide coating and a preparation method thereof, the graphene oxide coating is coated on the surface of a compact separation layer, and the desalination rate, pollution resistance and chlorine resistance of the composite reverse osmosis membrane can be effectively improved, but the method cannot realize large-scale industrial production, and the modified membrane is unstable in performance.
The resistance of the reverse osmosis membrane to water can also be reduced by controlling the interfacial polymerization process to produce a thinner functional layer. Shan et al control microphase monomer diffusion and gradual polymerization termination through microphase interfacial polymerization reaction to eliminate loose structure of the functional layer, and the ultra-thin nanofiltration membrane prepared by using the spraying technology has extremely high permeation flux which is 23 times of the flux of common commercial membrane (Shan et al, ACS appl.Mater. Interfaces,2017,9, 44820-. CN201310038807.X describes a double-desalination-layer composite reverse osmosis membrane, which changes a traditional desalination layer into a loose desalination layer and a compact desalination layer, and the total thickness of functional layers is not changed, but the thickness of the compact desalination layer is reduced, so that the water flux can be greatly improved, and the desalination rate is kept unchanged.
In addition, a high-roughness and irregular nano-structure intermediate layer such as an inorganic nanowire, a carbon nanotube, a cellulose nanocrystal layer and the like can be prepared on the surface of the support layer, so that more uniform medium holes are provided, the wetting surface area and the distribution uniformity of the aqueous phase monomer are greatly increased, the release of the monomer during interfacial polymerization is further controlled, and a thinner functional layer is prepared (Karan et al, Science,2015,348,1347; Wang et al, Nature Commun, 2018,9, 2004; CN 201410157619.3). CN201410157619.3 describes a sub-nanofiltration composite membrane and a preparation method thereof, wherein a polydimethylsiloxane intermediate layer is coated on a polysulfone porous membrane layer, and then a reverse osmosis membrane with different molecular weight cut-off and water flux is obtained through the interfacial polymerization reaction of trimesoyl chloride and m-phenylenediamine, but the membrane is only applied to the aspect of removing small molecular organic matters.
Although the prior art can prepare a thinner functional layer for improving the permeation flux of the membrane, the preparation of a polyamide layer with thin thickness, no defects and good mechanical properties still has great challenges for improving the membrane flux of the reverse osmosis membrane on the premise of not losing other properties.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the problems in the prior art and provides a high-flux reverse osmosis membrane, a preparation method and application thereof.
Means for solving the problems
The inventors of the present invention have made extensive studies to achieve the above object, and as a result, have found that a functional layer having a thinner thickness and good mechanical properties can be prepared by modifying a base film, growing an intermediate nano layer on the surface of the base film, further preparing a polyamide functional layer by interfacial polymerization, and then dissolving and removing the intermediate nano layer, thereby solving the restriction on the trade-off relationship between the salt rejection rate and flux of a reverse osmosis membrane and improving the flux of the reverse osmosis membrane without changing the salt rejection rate.
The intermediate nanolayer prepared in the present invention is dissolved and removed after the polyamide functional layer is prepared, and thus the reverse osmosis membrane according to the present invention is also called a reverse osmosis membrane containing an intermediate nanolayer sacrificial layer.
One aspect of the present invention relates to a method of preparing a high flux reverse osmosis membrane, the method comprising the steps of:
(1) preparing a polymer solution dispersed with an inorganic silicate nano material as a membrane casting solution, coating the membrane casting solution on a support material, and then soaking the membrane casting solution in a coagulating bath to obtain a base membrane;
(2) preparing a dopamine/ZIF-8 suspension, immersing the basement membrane obtained in the step (1) into the suspension to enable the dopamine/ZIF-8 to grow on the surface of the basement membrane, and then washing to obtain a modified basement membrane with a dopamine/ZIF-8 intermediate nano layer;
(3) immersing the modified base membrane obtained in the step (2) into an aqueous phase solution and an organic phase solution for interfacial polymerization to prepare a functional layer, so as to obtain the composite reverse osmosis membrane raw membrane with the functional layer;
(4) and (4) immersing the primary membrane obtained in the step (3) in water, and dissolving to remove the middle nano layer to obtain the high-flux reverse osmosis membrane.
The method according to the invention, wherein the support material is a non-woven fabric, wherein the polymer solution comprises a polymer and a solvent, the polymer is at least one of polysulfone, polyethersulfone, polyphenylsulfone, polyvinylidene fluoride, polyvinyl chloride, cellulose and its derivatives, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polyimide, polyethylene, and the solvent is at least one of N, N-dimethylformamide DMF, N-dimethylpyrrolidone, N-dimethylacetamide, dimethyl sulfoxide, N-hexane, cyclohexane, N-heptane, isoparaffin solvent Isopar G, chloroform, toluene, benzene, methanol, propanol, preferably, the concentration of the polymer in the casting solution is 10 wt% to 25 wt%; preferably, the inorganic silicate nano-material is an aqueous magnesium-rich aluminosilicate with a concentration of 0.5 wt% to 5 wt% in the casting solution, more preferably, the inorganic silicate nano-material is attapulgite; preferably, adding an active hydrophilic stabilizer into the membrane casting solution, wherein the concentration of the active hydrophilic stabilizer in the membrane casting solution is 0.5 wt% to 5 wt%, and more preferably, the active hydrophilic stabilizer is polyvinylpyrrolidone; the coagulation bath is a water bath, and preferably, DMF is added to the coagulation bath.
The method according to the present invention, wherein in the step (2), the dopamine/ZIF-8 suspension is prepared by the steps of:
(a) adding Zn (NO)3)2·6H2Adding a mixed solution of water and alcohol of O into an alcohol solution of 2-methylimidazole, and uniformly mixing to obtain a dispersion liquid, wherein preferably, the alcohol is methanol;
(b) adding dopamine hydrochloride and tromethamine Tris-HCl buffer solution into the dispersion liquid obtained in the step (a) to obtain the dopamine/ZIF-8 suspension liquid;
preferably, the growing and rinsing are performed once or repeatedly a plurality of times.
The method according to the present invention, wherein said Zn (NO)3)2·6H2The concentration of O in the mixed solution of water and alcohol is 1.0mol/L to 2.5mol/L, and the concentration of the 2-methylimidazole in the alcohol solution is 5mol/L to 15 mol/L; preferably, the Zn (NO)3)2·6H2The volume concentration of the mixed solution of water and alcohol of O in the dopamine/ZIF-8 suspension is 50-70 vol%; preferably, the alcoholic solution of 2-methylimidazole has a volume concentration of 30 to 60 vol% in the dopamine/ZIF-8 suspension; preferably, the concentration of said dopamine hydrochloride in said dopamine/ZIF-8 suspension is from 0.40g/L to 0.60 g/L; preferably, the tromethamine Tris-HCl buffer pH is in the range of 7.5 to 9.2.
The method according to the present invention, wherein the aqueous phase solution comprises an aqueous phase monomer and water, preferably, the aqueous phase monomer is at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-toluenediamine, m-toluenediamine, o-toluenediamine, and biphenyldiamine, more preferably, the concentration of the aqueous phase monomer in the aqueous phase solution is 0.5 wt% to 5 wt%; the organic phase solution comprises an organic phase monomer and a solvent, wherein the organic phase monomer is preferably at least one of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 4' -biphenyldicarbonyl chloride and trimesoyl chloride, the solvent is preferably at least one of n-hexane, cyclohexane, n-heptane and an isoparaffin solvent Isopar G, and the concentration of the organic phase monomer in the organic phase solution is preferably 0.005 wt% to 3 wt%.
Another aspect of the invention is directed to a high flux reverse osmosis membrane made according to the method of the invention.
The high-flux reverse osmosis membrane provided by the invention is characterized in that the bottom of the polyamide functional layer has nano-scale roughness, and the bottom has a corrugated structure.
Yet another aspect of the invention relates to the use of a high flux reverse osmosis membrane for water treatment applications, treatment of industrial or municipal wastewater, food processing, pharmaceutical industry.
Other aspects of the invention relate to a membrane element comprising the aforementioned high flux reverse osmosis membrane.
Other aspects of the invention relate to a filtration system comprising the membrane element described above.
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation method of the high-flux reverse osmosis membrane containing the middle nano sacrificial layer has the advantages that the base membrane is obtained by coating the casting solution dispersed with the inorganic silicate nano material on the supporting material, and the mechanical property, the hydrophilicity, the roughness and the like of the obtained base membrane are improved. Further, the basement membrane is immersed into the suspension of the dopamine/ZIF-8 to enable the dopamine/ZIF-8 to grow on the surface of the basement membrane, so that the basement membrane with the intermediate dopamine/ZIF-8 nano layer is obtained, the hydrophilicity and the roughness of the basement membrane are further enhanced, and the preparation of a functional layer which is more uniform in distribution and thinner in thickness can be facilitated; further carrying out interfacial polymerization to obtain a composite reverse osmosis raw membrane with a polyamide functional layer; and (3) soaking the raw membrane in pure water, and dissolving to remove the middle nano layer to obtain the high-flux reverse osmosis membrane.
The high-flux reverse osmosis membrane prepared by the method has the advantages of thin thickness of the functional layer, good mechanical property, uniform distribution and large effective permeation area, and greatly improves the flux on the premise of not influencing the desalting performance.
Detailed Description
One aspect of the invention relates to a high flux reverse osmosis membrane comprising an intermediate nano sacrificial layer, a method of making the same, and uses thereof. The invention also relates to a membrane element and a filtration system comprising the high flux reverse osmosis membrane with the intermediate nano sacrificial layer.
I. The invention relates to a preparation method of a high-flux reverse osmosis membrane containing a middle nano sacrificial layer
The preparation method of the high-flux reverse osmosis membrane containing the middle nano sacrificial layer specifically comprises the following steps:
(1) preparing a polymer solution dispersed with an inorganic silicate nano material as a membrane casting solution, coating the membrane casting solution on a support material, and then soaking the membrane casting solution in a coagulating bath to obtain a base membrane;
(2) preparing a dopamine/ZIF-8 suspension, immersing the basement membrane obtained in the step (1) into the suspension to enable the dopamine/ZIF-8 to grow on the surface of the basement membrane, and then washing to obtain a modified basement membrane with a dopamine/ZIF-8 intermediate nano layer;
(3) immersing the modified base membrane obtained in the step (2) into a water phase solution and an organic phase solution for interfacial polymerization to prepare a polyamide functional layer, so as to obtain the composite reverse osmosis membrane raw membrane with the polyamide functional layer;
(4) and (4) immersing the primary membrane obtained in the step (3) in water, and dissolving to remove the middle nano layer to obtain the high-flux reverse osmosis membrane.
The polymer solution used in the present invention comprises a polymer and a solvent. The polymer used in the present invention is at least one of polysulfone, polyethersulfone, polyphenylsulfone, polyvinylidene fluoride, polyvinyl chloride, cellulose and its derivatives, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polyimide, polyethylene, preferably polysulfone, polyethersulfone, more preferably polysulfone.
The polysulfone used in the present invention is not particularly limited, and may be bisphenol a type PSF (so-called PSF), polyarylsulfone and polyethersulfone. One polysulfone may be used alone or any combination of polysulfones may be used. When a combination of a plurality of different polysulfones is used, the mass ratio for the different species of polysulfone is not particularly limited.
The solvent contained in the polymer solution used in the present invention is not particularly limited, and may be at least one of N, N-dimethylformamide DMF, N-dimethylpyrrolidone, N-dimethylacetamide, dimethyl sulfoxide, N-hexane, cyclohexane, N-heptane, isoparaffin solvent Isopar G, chloroform, toluene, benzene, methanol, and propanol.
Preferably, the casting solution is prepared as follows:
the inorganic silicate nano material is uniformly dispersed in the solvent, and an ultrasonic dispersion mode and a mechanical stirring dispersion mode can be adopted, and the ultrasonic dispersion mode is preferably used. Preferably, after the uniform dispersion, a microfiltration membrane with the pore diameter of 0.2 μm is used for vacuum filtration to remove impurities, and inorganic silicate nano-material filtrate is obtained.
Preferably, the active hydrophilic stabilizer is added to the filtrate under stirring, and stirring is continued until the active hydrophilic stabilizer is uniformly dispersed in the filtrate. While maintaining the stirring, heating to raise the temperature, adding the polymer and the rest of the solvent, and stirring until the polymer is completely dissolved to obtain the casting solution. Among them, raising the temperature to the range of 80 ℃ to 95 ℃ when controlled within this temperature range can promote the dissolution of the polymer without causing the decomposition of the polymer and the volatilization of the solvent, accelerate the dissolution speed, shorten the dissolution time, more preferably the heating temperature is in the range of 85 to 95 ℃, even more preferably 85 to 90 ℃, can further accelerate the dissolution speed and shorten the dissolution time.
Preferably, the inorganic silicate nanomaterial is an aqueous magnesium-rich aluminosilicate, more preferably attapulgite, and preferably the concentration of the inorganic silicate nanomaterial in the casting solution is 0.5 wt% to 5 wt%. Preferably 0.5 to 2 wt%, more preferably 0.8 to 1.2 wt%.
The concentration of the polymer in the casting solution is 10 wt% to 25 wt%, and when the concentration is within this range, the quality of the produced membrane (e.g., strength, pore size, etc.) is more excellent. If the concentration of the polymer in the membrane casting solution is lower than 10 wt%, the concentration of the membrane casting solution is too low, the prepared base membrane has an excessively loose structure, so that the strength of the membrane is reduced, the membrane is easy to damage, the aperture is too large, the interception effect cannot be achieved, and even the viscosity of the membrane casting solution is too low, so that the membrane cannot be formed. If the concentration of the polymer in the membrane casting solution exceeds 25 wt%, the concentration of the membrane casting solution is too high, the viscosity is high, and the prepared base membrane has an excessively compact structure, so that the porosity and the roughness are reduced, the membrane has more defects, and the interception performance is poor. Preferably 10 to 20 wt%, more preferably 16 to 20 wt%. The quality of the prepared membrane material can be further improved.
Preferably, an active hydrophilic stabilizer is added to the casting solution. Preferably, the active hydrophilic stabilizer is polyvinylpyrrolidone. Preferably, the concentration of the active hydrophilic stabilizer in the casting solution is 0.5 wt% to 5 wt%. Preferably 0.5 to 2 wt%, more preferably 0.8 to 1.2 wt%.
Preferably, the casting solution prepared as described above is subjected to vacuum defoaming treatment, filtered, and cooled to room temperature.
The coating method is not particularly limited, and a coating method generally used in the field of reverse osmosis membrane production, for example, a casting method, a dip coating method, a blade coating method, and the like can be used, and a blade coating method is more preferable. The coating on the support material is followed by immersion in a coagulation bath, so that the casting solution is coagulated into a film.
The support material used in the present invention is a nonwoven fabric, and the material of the nonwoven fabric is not particularly limited, and may be polypropylene (PP), Polyester (PET), Polyamide (PA), viscose, acrylic, polyethylene (HDPE), polyvinyl chloride (PVC), cellulose, a derivative thereof, or the like, and is preferably a polypropylene (PP) nonwoven fabric and a Polyester (PET) nonwoven fabric, and more preferably a polypropylene (PP) nonwoven fabric.
The coagulation bath is a water bath, and preferably, DMF is added to the coagulation bath. The further addition of DMF to the coagulation bath can weaken the interaction parameters between the solvent and the non-solvent, inhibit the formation of macropores by changing the double diffusion process of the casting solution gel, and the higher the content of component 1 in the coagulation bath in a certain concentration range, the smaller the pore size of the membrane. Preferably, 0.5 to 3 wt% DMF is added, more preferably 1.0 to 2.0 wt%.
The temperature of the coagulation bath is 5 to 25 ℃, preferably 5 to 20 ℃, more preferably 15 to 20 ℃. The purpose of adjusting the pore size of the membrane can also be achieved by adjusting the temperature of the coagulation bath, the lower the temperature of the coagulation bath, the smaller the pore size of the membrane.
Through the liquid-liquid phase conversion process, the polymer in the casting solution is solidified into a film, and the film is adhered to the surface of the non-woven fabric and has a certain adhesion effect with the non-woven fabric. The treatment time in the coagulation bath, i.e. the phase inversion time, is from 20 to 80 seconds, preferably from 30 to 60 seconds. If the phase inversion time exceeds 80 seconds, the membrane has completely phase separated and continued extension will not alter the degree of phase separation of the membrane. If the phase inversion time is less than 20 seconds, since the phase inversion time is short, although the phase separation on the surface of the film is completed, the phase separation is not completely performed inside the film, a large amount of solvent remains inside the film, and finally the film performance is affected.
Preferably, the film is further rinsed in deionized water after being processed by the coagulation bath to form a film, and the rinsing time is not particularly limited and may be 100 seconds to 250 seconds, preferably 150 seconds to 200 seconds, thereby obtaining the base film modified by the inorganic silicate nanomaterial.
The base membrane obtained by modifying the inorganic silicate nano material has good mechanical property and excellent hydrophilicity, and the water drop contact angle is in the range of 50-80 degrees.
The inventor of the invention thinks that the principle according to the technical scheme provided by the invention is as follows:
the inorganic silicate nano material is more specifically an aqueous magnesium-rich aluminum silicate clay mineral, particularly attapulgite, and is an aqueous magnesium-rich aluminum silicate clay mineral with a chain lamellar structure, the material has good hydrophilicity and a one-dimensional rod-shaped structure, a base membrane modified by the inorganic silicate nano material has good mechanical property, the high porosity and narrow pore size distribution on the surface of the base membrane can be beneficial to more uniform spreading of a nano material intermediate layer to be prepared subsequently, and the excellent hydrophilicity can be beneficial to more compact combination of the base membrane and the intermediate layer to be prepared subsequently.
In the step (2), the dopamine/ZIF-8 suspension is prepared by:
(a) adding Zn (NO)3)2·6H2Adding a mixed solution of water and alcohol of O into an alcohol solution of 2-methylimidazole, and uniformly mixing to obtain a dispersion liquid, wherein preferably, the alcohol is methanol;
(b) adding dopamine hydrochloride and tromethamine Tris-HCl buffer solution into the dispersion liquid obtained in the step (a), and uniformly mixing to obtain the dopamine/ZIF-8 suspension.
The Zn (NO)3)2·6H2The concentration of O in the mixed solution of water and alcohol is 1.0 to 2.5mol/L, preferably 1.5 to 2.5 mol/L. The volume ratio of water to alcohol is 1:1 to 1:3, preferably 1:1 to 1: 2.
The concentration of the 2-methylimidazole in the alcohol solution is 5mol/L to 15mol/L, preferably 10mol/L to 15mol/L, and more preferably 10mol/L to 12.5 mol/L.
Preferably, the alcohol is methanol.
The Zn (NO)3)2·6H2The volume concentration of the mixed solution of water and alcohol of O relative to the dopamine/ZIF-8 suspension is 50-70 vol%, preferably 50-60 vol%.
The volume concentration of the 2-methylimidazole alcohol solution relative to the dopamine/ZIF-8 suspension is 30 to 60 vol%, preferably 30 to 50 vol%, and preferably 30 to 40 vol%.
The concentration of the dopamine hydrochloride relative to the dopamine/ZIF-8 suspension is 0.40 to 0.60g/L, preferably 0.40 to 0.50 g/L. The pH of the buffer is in the range of 7.5 to 9.2, preferably 7.5 to 9, more preferably 8 to 9.
Preferably, the dopamine/ZIF-8 suspension is prepared as follows:
zn (NO) is added under stirring at normal temperature3)2·6H2Quickly pouring the mixed solution of water and alcohol of O into the alcoholic solution of 2-methylimidazole, continuously and uniformly stirring to obtain milky dispersion, continuously adding dopamine hydrochloride and tromethamine Tris-HCl buffer solution, continuously stirring, and uniformly mixing to obtain dark gray dopamine/ZIF-8 suspension.
Dopamine in the present invention is an organic molecule containing a dihydroxyphenyl moiety and its derivatives, including but not limited to DOPA (DOPA), dopamine (dopamine), 3, 4-dihydroxybenzenemethamine, 3, 4-dihydroxybenzaldehyde, 3, 4-dihydroxybenzoic acid, or 3, 4-dihydroxybenzoic acid.
Zifs (zeolitic imidazole frameworks) are a zeolite type imidazole framework material, and are a novel porous material with a zeolite topology structure, which is generated by connecting metal atoms such as Zn, Co and the like with imidazole or imidazole derivatives, and has permanent pores, high surface area, hydrophobicity, open metal sites, excellent thermal stability and chemical stability. ZIF-8, a representative skeleton structure of ZIFs, is ZnN formed by linking a metal Zn atom to an N atom in methylimidazole4A tetrahedral structural unit.
Preferably, dopamine/ZIF-8 nanoparticles are grown on the surface of the basement membrane as follows:
immersing the basement membrane modified by the inorganic silicate nano material obtained in the step (1) into the dopamine/ZIF-8 suspension prepared as described above, standing for a certain time at room temperature to enable dopamine/ZIF-8 nano particles to grow on the surface of the basement membrane, taking out, repeatedly washing with water and alcohol respectively, and drying at the temperature of 50-70 ℃, preferably 60-70 ℃ to obtain the modified basement membrane with the dopamine/ZIF-8 intermediate nano layer growing for one time. Wherein, preferably, the alcohol is methanol.
The inventor of the invention thinks that the introduction of the dopamine/ZIF-8 intermediate nano layer prepares a high-roughness and irregular nano structure layer on the surface of the support material, provides more uniform medium holes, increases the hydrophilic performance of the base film, and is beneficial to greatly increasing the infiltration surface area and the distribution uniformity of the aqueous phase monomer on the base film when the polyamide functional layer is prepared; the combination of the ZIF-8 nanometer material, the polysulfone-based membrane and the polyamide functional layer is tighter through dopamine modification, and the nanometer structure, high porosity and rugged surface of the dopamine/ZIF-8 layer can be beneficial to better controlling the release of monomers during the interfacial polymerization for preparing the polyamide functional layer.
Preferably, the growing and washing are performed once or repeatedly for a plurality of times, and then the drying is performed, so that the modified basement membrane with the dopamine/ZIF-8 middle nano-layer is obtained through a plurality of times of growing. More preferably, the growth is repeated 2 to 5 times, still more preferably 2 to 4 times. When the growth frequency is 1 time, the growth of the middle nano layer is not uniform enough, and the grown nano material is less, so that the influence on the reverse osmosis membrane is less. When the growth times exceed 5 times, the intermediate nano-layer is too thick to be completely dissolved and removed, and the relationship between the base film and the functional layer is not tight enough, even the functional layer falls off.
Further, the modified basement membrane with the dopamine/ZIF-8 intermediate nano-layer obtained in the way is immersed in aqueous phase solution and organic phase solution for interfacial polymerization to prepare a polyamide functional layer, and the polyamide functional layer is dried to obtain the composite reverse osmosis membrane raw membrane with the functional layer.
The aqueous phase solution comprises an aqueous phase monomer and water, wherein the aqueous phase monomer is at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-toluenediamine, m-toluenediamine, o-toluenediamine and biphenyldiamine. The concentration of the aqueous phase monomer in the aqueous phase solution is 0.5 wt% to 5 wt%, preferably 1 wt% to 3 wt%, more preferably 1.5 wt% to 2.5 wt%. Preferably, a base is added to the aqueous phase solution, wherein the base is at least one of sodium hydroxide and potassium hydroxide, and the concentration of the base relative to the aqueous phase solution is 0.1 wt% to 3 wt%, preferably 0.2 wt% to 1 wt%.
The organic phase solution comprises an organic phase monomer and a solvent, wherein the organic phase monomer is at least one of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 4' -biphenyldicarbonyl chloride and trimesoyl chloride, preferably phthaloyl chloride, isophthaloyl chloride and trimesoyl chloride, and more preferably phthaloyl chloride. The solvent is at least one of n-hexane, cyclohexane, n-heptane and an isoparaffin solvent Isopar G, preferably n-hexane and the isoparaffin solvent Isopar G, and more preferably the isoparaffin solvent Isopar G. The concentration of the organic phase monomer in the organic phase solution is 0.005 wt% to 3 wt%, preferably 0.05 wt% to 2 wt%, more preferably 0.1 wt% to 1 wt%.
Preferably, the polyamide functional layer is prepared as follows:
the modified base film having the dopamine/ZIF-8 intermediate nano layer prepared as described above is soaked in an aqueous solution for a certain time, for example, 100 seconds to 200 seconds, preferably 100 seconds to 150 seconds, more preferably 100 seconds to 120 seconds. The aqueous solution was allowed to penetrate into the pores of the ZIF-8 nanolayer.
The excess aqueous solution is drained and the membrane is immersed in the organic solution for a certain period of time, for example 20 to 60 seconds, preferably 20 to 50 seconds, more preferably 20 to 40 seconds. After the reaction is finished, the organic phase solution is discharged, and the membrane is dried, for example, at a temperature of 70 ℃ to 90 ℃, thereby obtaining the composite reverse osmosis membrane raw membrane with the polyamide functional layer.
The raw membrane obtained as described above is immersed in water to dissolve and remove the intermediate nanolayer, and preferably washed with water multiple times to obtain a high flux reverse osmosis membrane containing an intermediate nanofimary layer.
The inventor of the present invention believes that the hydrolysis of the ZIF-8 nanoparticles is inhibited under the condition of an alkaline aqueous solution, and thus the ZIF-8 nanoparticles can maintain a stable shape during interfacial polymerization, but the ZIF-8 nanoparticles can be completely hydrolyzed after being soaked in water for a certain period of time. The bottom of the polyamide layer dissolved with the ZIF-8 nano particles has nano-grade roughness, and a large number of wrinkled structures at the bottom increase the effective permeation area of the polyamide functional layer, so that the permeation flux in unit shadow area relative to the base membrane is increased, and the flux of the reverse osmosis membrane can be greatly improved on the premise of not influencing the desalination rate.
II. The invention relates to a high-flux reverse osmosis membrane containing an intermediate nano sacrificial layer
The high-flux reverse osmosis membrane containing the middle nano sacrificial layer obtained by the method provided by the invention has the advantages that the bottom of the polyamide functional layer has nano roughness, and the bottom has a corrugated structure. The high-flux reverse osmosis membrane prepared by the method has the advantages of thin thickness of the functional layer, good mechanical property, uniform distribution and large effective permeation area, and greatly improves the flux on the premise of not influencing the desalting performance.
III, application of high-flux reverse osmosis membrane containing middle nano sacrificial layer
The high flux reverse osmosis membrane containing an intermediate nano sacrificial layer according to the present invention may be used for fluid separation in water treatment applications, treatment of industrial or municipal wastewater, food processing industry and pharmaceutical industry.
IV, Membrane element and filtration System comprising the high flux reverse osmosis Membrane with intermediate Nanosacrifice layer of the invention
A membrane element according to the present invention comprising a high flux reverse osmosis membrane according to the present invention comprising an intermediate nano-sacrificial layer.
The filtration system according to the present invention comprises a high flux reverse osmosis membrane according to the present invention comprising an intermediate nano-sacrificial layer.
Examples
The present invention will be described in further detail with reference to specific examples, but the present invention is by no means limited to the following examples. It should be noted that the reagents and raw materials used in the examples of the present invention are commercially available conventional products unless otherwise specified.
The hydrophilicity was evaluated as follows for the base films prepared as follows.
Using the prepared base film, the water droplet contact angle was measured as follows: and (3) soaking the membrane sample in pure water for 24 hours, and airing at 20 ℃. The contact angle tester has the following model: germany KRUSS DSA30 research type contact angle measuring instrument. The membrane sample was laid flat on a test table, pure water was dropped onto the membrane with the needle of a contact angle measuring instrument, and the contact angle of the drop was recorded 10 seconds after the drop was dropped onto the membrane. The volume of each drop of pure water was about 3uL, five random points were selected for each sample and the data averaged.
The following is the manufacturer information of the substances specifically used in the examples.
Polysulfone, chemical reagents of the national drug group Ltd
Attapulgite, chemical reagents of national drug group Ltd
N, N-dimethylformamide, chemical reagents of national drug group Ltd
Polyvinylpyrrolidone, national pharmaceutical group chemical reagents Co., Ltd
Zn(NO3)2·6H2O，Sigma-Aldrich
Methanol, chemical reagents of national drug group, Ltd
2-methylimidazole, Alfa-Aesar
Dopamine hydrochloride, Alfa-Aesar
Tromethamine, Alfa-Aesar
P-phenylenediamine, BASF
Trimesoyl chloride, BASF
Isopar G, Isopar G, chemical reagents of national drug group Co., Ltd
Example 1
Preparation of polysulfone-based membranes
(1) Dispersing 1 wt% attapulgite in 40 wt% N, N-dimethylformamide DMF under ultrasonic condition, ultrasonically treating for 3 hr with 300W ultrasonic cleaning machine, vacuum filtering with microfiltration membrane with pore diameter of 0.2 μm, and removing impurities to obtain DMF filtrate;
(2) under the stirring state, adding 1 wt% of polyvinylpyrrolidone into the filtrate, stirring at a stirring speed of 60r/min to uniformly disperse the polyvinylpyrrolidone in the filtrate, maintaining the stirring speed, heating to 90 ℃, adding 18 wt% of polysulfone and 40 wt% of DMF, and stirring for 4 hours to obtain a casting solution;
(3) carrying out vacuum defoaming treatment on the casting solution under-80 kPa, filtering, cooling to room temperature, uniformly coating the casting solution on a PP non-woven fabric substrate by adopting a scraper system, and feeding the PP non-woven fabric substrate into a coagulating bath, wherein the coagulating bath is 1.0 wt% of DMF (dimethyl formamide) aqueous solution, the temperature is 20 ℃, and the coagulating treatment time is 30 s; then placing the membrane in deionized water, adjusting the temperature to 20 ℃, and rinsing for 200 seconds to obtain the polysulfone basal membrane modified by the attapulgite; the measurement shows that the water drop contact angle of the polysulfone-based membrane modified by the attapulgite is 56 degrees; the thickness is 5.5-6mil (1mil ═ 0.0254 mm).
Preparation of modified polysulfone-based membrane loaded with dopamine/ZIF-8 nano layer
(1) Under the normal temperature environment, the mixture is stirred to contain 0.1mol of Zn (NO)3)2·6H2Quickly pouring the mixed solution of 40mL of methanol and 20mL of water of O into 40mL of methanol solution containing 0.4mol of 2-methylimidazole, and stirring for 1h to obtain milky white dispersion liquid; adding 50mg of dopamine hydrochloride and 10ml of 0.1mol of tromethamine buffer (pH 8.5), and stirring at normal temperature for 5h to obtain a dark gray suspension;
(2) immersing the polysulfone-based membrane modified by attapulgite in the suspension, and standing for 12h at room temperature to enable the dopamine/ZIF-8 nano particles to grow on the surface of the polysulfone-based membrane. Taking out, repeatedly washing with distilled water and methanol, and drying at 60 deg.C for 0.5 hr to obtain single-growth basement membrane; and repeating the growth process to obtain the polysulfone basal membrane with secondary growth of dopamine/ZIF-8.
Preparation of functional polyamide layers
(1) Soaking a polysulfone-based membrane subjected to secondary growth of dopamine/ZIF-8 in an aqueous solution containing 2 wt% of m-phenylenediamine and 0.5 wt% of sodium hydroxide for 100 seconds to enable the aqueous solution to permeate into holes of a ZIF-8 nano layer;
(2) and (3) filtering excessive aqueous phase solution, immersing the membrane into n-hexane organic phase solution containing 0.1 wt% of phthaloyl chloride for reaction for 20 seconds, discharging the organic phase solution after the reaction is finished, and drying the membrane in a vacuum oven at 90 ℃ for 5 minutes to prepare a composite reverse osmosis primary membrane which is cut into two halves, namely M1-RO1 and M1-RO 2.
Removing intermediate sodiumPreparation of reverse osmosis membrane of rice sacrificial layer
And (3) immersing the M1-RO2 reverse osmosis membrane into pure water for 30min, washing with the pure water for 3-5 times, and dissolving the ZIF-8 nano particles to obtain the required reverse osmosis membrane RO-M1.
Example 2
Polysulfone-based membranes were prepared in the same manner as described in example 1.
Preparation of modified polysulfone-based membrane loaded with dopamine/ZIF-8 nano layer
(1) Under the normal temperature environment, the mixture is stirred to contain 0.13mol of Zn (NO)3)2·6H2Quickly pouring the mixed solution of 40mL of methanol and 20mL of water of O into 40mL of methanol solution containing 0.45mol of 2-methylimidazole, and stirring for 1h to obtain milky white dispersion liquid; adding 50mg of dopamine hydrochloride and 10ml of 0.1mol of tromethamine buffer (pH 8.5), and stirring at normal temperature for 5h to obtain a dark gray suspension;
(2) immersing the polysulfone-based membrane modified by attapulgite in the suspension, and standing for 12h at room temperature to enable the dopamine/ZIF-8 nano particles to grow on the surface of the polysulfone-based membrane. Taking out, repeatedly washing with distilled water and methanol, and drying at 60 deg.C for 0.5 hr to obtain single-growth basement membrane; and repeating the growth process to obtain the polysulfone basal membrane with dopamine/ZIF-8 growing for three times.
Preparation of functional polyamide layers
(1) Soaking a polysulfone-based membrane grown three times by dopamine/ZIF-8 in an aqueous solution containing 2 wt% of m-phenylenediamine and 0.5 wt% of sodium hydroxide for 100 seconds to enable the aqueous solution to permeate into holes of a ZIF-8 nano layer;
(2) and (3) filtering excessive aqueous phase solution, immersing the membrane into n-hexane organic phase solution containing 0.1 wt% of phthaloyl chloride for reaction for 20 seconds, discharging the organic phase solution after the reaction is finished, and drying the membrane in a vacuum oven at 90 ℃ for 5 minutes to prepare a composite reverse osmosis primary membrane which is cut into two halves, namely M2-RO1 and M2-RO 2.
Preparation of reverse osmosis membrane containing middle nano sacrificial layer
And (3) immersing the M2-RO2 reverse osmosis membrane into pure water for 30min, washing with the pure water for 3-5 times, and dissolving the ZIF-8 nano particles to obtain the required reverse osmosis membrane RO-M2.
Testing
The membrane was tested by cutting the membrane M1-RO1, RO-M1, M2-RO1, and RO-M2, and 2 commercially available reverse osmosis membranes (designated as RO-1 and RO-2, respectively) from yoton technologies co, each membrane was cut into three test membranes each having an area of 3.4cm × 3.4cm, and the test membranes were placed on a cross-flow test bench under the conditions of 2000ppm of aqueous sodium chloride solution, 150Psi operating pressure, raw water temperature of 25 ℃, pH 7, and each test time of 30 min. The average values of salt rejection and flux obtained from each set of membrane tests were recorded and the results are shown in table 1. Table 1 shows the test data of the reverse osmosis membranes M1-RO1 and M2-RO1 containing the middle nano-layer, the reverse osmosis membranes RO-M1 and RO-M2 without the middle nano-layer (i.e., containing the middle nano sacrificial layer), and the reverse osmosis membranes RO-1 and RO-2 for Timewton commercial use, and it can be seen from Table 1 that the reverse osmosis membranes prepared by the method of the present invention can effectively improve the permeation flux without changing the desalting performance, and the flux of the reverse osmosis membranes after the middle nano-layer is removed (i.e., containing the middle nano sacrificial layer) is higher.
TABLE 1
The specific modes of the present invention are disclosed in the above embodiments, but the above embodiments are merely examples and are not to be construed as limiting. Various modifications obvious to those skilled in the art are certainly included within the scope of the present invention.
Industrial applicability
The preparation method of the high-flux reverse osmosis membrane containing the middle nano sacrificial layer has the advantages of low cost and simple operation, and can provide the high-flux reverse osmosis membrane. The high-flux reverse osmosis membrane containing the middle nano sacrificial layer has the advantages of thin thickness of the functional layer, good mechanical property, uniform distribution and large effective permeation area, and greatly improves the flux on the premise of not influencing the desalting performance. Therefore, the method is useful for water treatment, treatment of industrial or municipal wastewater, food processing and pharmaceutical industry.
Claims (28)
1. A method of making a high flux reverse osmosis membrane, said method comprising the steps of:
(1) preparing a polymer solution dispersed with an inorganic silicate nano material as a membrane casting solution, coating the membrane casting solution on a support material, and then soaking the membrane casting solution in a coagulating bath to obtain a base membrane;
(2) preparing a dopamine/ZIF-8 suspension, immersing the basement membrane obtained in the step (1) into the suspension, and allowing dopamine/ZIF-8 to grow on the surface of the basement membrane to obtain a modified basement membrane with a dopamine/ZIF-8 intermediate nano layer;
(3) immersing the modified base membrane obtained in the step (2) into a water phase solution and an organic phase solution for interfacial polymerization to prepare a polyamide functional layer, so as to obtain the composite reverse osmosis membrane raw membrane with the polyamide functional layer;
(4) and (4) immersing the primary membrane obtained in the step (3) in water, and dissolving to remove the middle nano layer to obtain the high-flux reverse osmosis membrane.
2. The production method according to claim 1, wherein the support material is a nonwoven fabric, wherein the polymer solution contains a polymer and a solvent, the polymer being at least one of polysulfone, polyethersulfone, polyphenylsulfone, polyvinylidene fluoride, polyvinyl chloride, cellulose and derivatives thereof, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polyimide, polyethylene, and the solvent being at least one of N, N-dimethylformamide DMF, N-dimethylpyrrolidone, N-dimethylacetamide, dimethyl sulfoxide, N-hexane, cyclohexane, N-heptane, isoparaffin solvent Isopar G, chloroform, toluene, benzene, methanol, propanol; the coagulation bath is a water bath.
3. The production method according to claim 1 or 2, wherein the concentration of the polymer in the casting solution is 10 wt% to 25 wt%.
4. The production method according to claim 1 or 2, wherein the inorganic silicate nanomaterial is an aqueous magnesium-rich aluminosilicate having a concentration of 0.5 wt% to 5 wt% in the casting solution.
5. The preparation method according to claim 4, wherein the inorganic silicate nano-material is attapulgite.
6. The production method according to claim 1 or 2, wherein an active hydrophilic stabilizer is added to the dope solution at a concentration of 0.5 wt% to 5 wt% in the dope solution.
7. The method of claim 6, wherein the active hydrophilic stabilizer is polyvinylpyrrolidone.
8. The production method according to claim 1 or 2, wherein DMF is added in the coagulation bath.
9. The preparation method according to claim 1 or 2, wherein in the step (2), the dopamine/ZIF-8 suspension is prepared by:
(a) adding Zn (NO)3)2·6H2Adding the mixed solution of water and alcohol of O into the alcoholic solution of 2-methylimidazole, and uniformly mixing to obtain a dispersion liquid;
(b) adding dopamine hydrochloride and tromethamine Tris-HCl buffer solution into the dispersion liquid obtained in the step (a) to obtain the dopamine/ZIF-8 suspension liquid.
10. The production method according to claim 9, wherein the alcohol is methanol.
11. The production method according to claim 9, wherein the growing and rinsing are performed once or repeatedly performed a plurality of times.
12. The production method according to claim 9, wherein the Zn (NO)3)2·6H2The concentration of O in the mixed solution of water and alcohol is 1.0mol/L to 2.5mol/L, and the concentration of the 2-methylimidazole in the alcohol solution is 5mol/L to 15 mol/L.
13. The production method according to claim 9, wherein the Zn (NO)3)2·6H2The volume concentration of the mixed solution of water and alcohol of O in the dopamine/ZIF-8 suspension is 50-70 vol%.
14. The preparation method according to claim 9, wherein the volume concentration of the alcohol solution of 2-methylimidazole in the dopamine/ZIF-8 suspension is 30 to 60 vol%.
15. The preparation method of claim 9, wherein the concentration of dopamine hydrochloride in the dopamine/ZIF-8 suspension is from 0.40g/L to 0.60 g/L.
16. The preparation method according to claim 9, wherein the tromethamine Tris-HCl buffer pH is in the range of 7.5 to 9.2.
17. The production method according to claim 1 or 2, wherein the aqueous phase solution contains an aqueous phase monomer and water; the organic phase solution contains an organic phase monomer and a solvent.
18. The production method according to claim 17, wherein the aqueous-phase monomer is at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-toluenediamine, m-toluenediamine, o-toluenediamine, and biphenyldiamine.
19. The production method according to claim 17, wherein the concentration of the aqueous-phase monomer in the aqueous-phase solution is 0.5 wt% to 5 wt%.
20. The production method according to claim 17, wherein the organic phase monomer is at least one of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 4' -biphenyldicarbonyl chloride, trimesoyl chloride.
21. The method of claim 17, wherein the solvent is at least one of n-hexane, cyclohexane, n-heptane, Isopar G, an isoparaffin solvent.
22. The production method according to claim 17, wherein the concentration of the organic-phase monomer in the organic-phase solution is 0.005 wt% to 3 wt%.
23. A high flux reverse osmosis membrane made according to the method of any one of claims 1-22.
24. The high flux reverse osmosis membrane of claim 23 wherein the polyamide functional layer has a base with nano-scale roughness and a corrugated structure.
25. Use of a high flux reverse osmosis membrane according to claim 23 or 24 in water treatment applications, food processing, pharmaceutical industry.
26. Use of a high flux reverse osmosis membrane according to claim 25 wherein said water treatment application comprises the treatment of industrial or municipal wastewater.
27. A membrane element comprising a high flux reverse osmosis membrane according to claim 23 or 24.
28. A filtration system comprising a membrane element according to claim 27.
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| CN110433673B (en) * | 2019-07-08 | 2021-02-12 | 淮阴师范学院 | Quaternary ammonium salt functionalized polysulfone-nano attapulgite hybrid anion-exchange membrane and preparation method thereof |
| CN110711499B (en) * | 2019-08-21 | 2021-09-10 | 江苏大学 | PVDF/UiO-66-NH2Preparation method and application of imprinted composite membrane |
| CN111330460B (en) * | 2019-11-28 | 2021-04-23 | 青岛科技大学 | Method for modifying polysulfone nanofiltration membrane by using DNA/ZIF-8 and obtained membrane |
| CN111001318B (en) * | 2019-12-16 | 2022-04-08 | 绍兴市俱和环保科技有限公司 | Hybrid composite forward osmosis membrane assisted by dopamine and modified and preparation method thereof |
| CN111686596B (en) * | 2020-06-19 | 2022-07-12 | 万华化学（宁波）有限公司 | Preparation method and application of oil-water separation membrane |
| CN111921387B (en) * | 2020-07-16 | 2022-03-29 | 浙江工业大学 | Preparation method of polydopamine modified imidazolyl nanoparticle composite nanofiltration membrane |
| CN112316753B (en) * | 2020-09-22 | 2022-04-19 | 宁波方太厨具有限公司 | Preparation method of high-flux loose hollow fiber nanofiltration membrane |
| CN112221355B (en) * | 2020-09-24 | 2022-06-14 | 德蓝水技术股份有限公司 | High-flux hollow fiber desalting membrane and preparation method thereof |
| CN112999898B (en) * | 2021-02-08 | 2023-02-03 | 青岛科技大学 | High-flux nanofiltration membrane capable of realizing monovalent/divalent ion selective separation and preparation method thereof |
| CN113318616B (en) * | 2021-06-30 | 2022-05-31 | 西安建筑科技大学 | rGO/ZIF-8 composite nano material as middle layer modified nanofiltration membrane and preparation method thereof |
| CN114177786B (en) * | 2021-11-01 | 2022-12-30 | 深圳市惠康水务集团有限公司 | Preparation method of multilayer polyamide composite reverse osmosis membrane |
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