CN115487693A - Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof - Google Patents
Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN115487693A CN115487693A CN202211213941.4A CN202211213941A CN115487693A CN 115487693 A CN115487693 A CN 115487693A CN 202211213941 A CN202211213941 A CN 202211213941A CN 115487693 A CN115487693 A CN 115487693A
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- 239000012528 membrane Substances 0.000 title claims abstract description 112
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 51
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 46
- 239000004952 Polyamide Substances 0.000 title claims abstract description 44
- 229920002647 polyamide Polymers 0.000 title claims abstract description 44
- 239000011159 matrix material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000013207 UiO-66 Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 17
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 10
- -1 zirconium ions Chemical class 0.000 claims description 9
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 8
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- YYGZWQNDFRCZIF-UHFFFAOYSA-N 2,5-bis(sulfanyl)terephthalic acid Chemical compound OC(=O)C1=CC(S)=C(C(O)=O)C=C1S YYGZWQNDFRCZIF-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- YHXKXVFQHWJYOD-UHFFFAOYSA-N 1-biphenyl-2-ylmethanamine Chemical compound NCC1=CC=CC=C1C1=CC=CC=C1 YHXKXVFQHWJYOD-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 51
- 230000007547 defect Effects 0.000 abstract description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000005501 phase interface Effects 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 abstract 4
- 210000002469 basement membrane Anatomy 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 230000004907 flux Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- ASYCOIGCAKHETJ-UHFFFAOYSA-J CC(=O)C.[Cl-].[Zr+4].[Cl-].[Cl-].[Cl-] Chemical compound CC(=O)C.[Cl-].[Zr+4].[Cl-].[Cl-].[Cl-] ASYCOIGCAKHETJ-UHFFFAOYSA-J 0.000 description 3
- 238000012863 analytical testing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HJLHTTJLVALHOP-UHFFFAOYSA-N hexane;hydron;chloride Chemical compound Cl.CCCCCC HJLHTTJLVALHOP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D61/027—Nanofiltration
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
Abstract
The invention relates to a polyamide/polyolefin mixed matrix nanofiltration membrane as well as preparation and application thereof, wherein the nanofiltration membrane consists of a Polyolefin (PE) porous support layer, a Polyamide (PA) active layer and in-situ grown and attached UIO-66 nanoparticles; the preparation process comprises the following steps: firstly, loading metal ions on a PE supporting layer, then carrying out interfacial polymerization to generate a PA compact skin layer, and finally soaking the membrane in an organic ligand machine solvent to synthesize UIO-66 nano particles in situ through back diffusion to prepare the mixed matrix nano-filtration membrane. The invention adopts the single-layer polyolefin porous basement membrane as the supporting layer, and can effectively reduce the thickness and the cost of the membrane. In addition, the in-situ method can avoid the problem of great reduction of the membrane performance caused by nanoparticle agglomeration and phase interface defects, and the preparation process is easy to regulate and control and operate, so that the method has good application prospects in the fields of water treatment, seawater desalination, sewage treatment and the like.
Description
(I) technical field
The invention relates to a polyamide/polyolefin mixed matrix nanofiltration membrane based on back diffusion in-situ growth UIO-66 and a preparation method thereof.
(II) background of the invention
With the rapid development of the science and technology level of human beings and the rapid increase of industrial production, the living standard of human beings is greatly improved. However, the problems of various environmental pollution and water resource shortage are brought along. The membrane technology has the advantages of high separation efficiency, simple operation, no pollution and the like, and has great application potential in the aspects of wastewater treatment, hard water softening, seawater desalination and the like. Nanofiltration membranes are popular as one of the membrane classes because of their selectivity for monovalent and multivalent ions, low operating pressures, and relatively low cost.
At present, polyamide (PA) nanofiltration membranes have good water permeability and salt rejection due to a polyamide active layer, and become the mainstream of the development of the current nanofiltration membranes. The traditional polyamide nanofiltration membrane consists of a bottom membrane supporting layer and a polyamide active layer. The nanofiltration membrane supporting layer is usually an ultrafiltration membrane, and the material of the nanofiltration membrane supporting layer is composed of polyester non-woven fabrics and ultrafiltration layers of polysulfone, polyethersulfone, polyvinylidene fluoride and the like. The existing ultrafiltration membrane is seriously dependent on foreign import, and has complex preparation and higher cost. A domestic Polyolefin (PE) has been widely used as a lithium battery separator. The thickness (5-50 um) and the aperture (10-70 nm) of the membrane are both suitable for a nanofiltration membrane to replace the traditional two-layer ultrafiltration membrane as a supporting layer, and the membrane is low in price and easy to obtain and is beneficial to large-scale continuous production. However, PA nanofiltration membranes still face difficulties in application, such as the "trade-off" effect between water permeability and salt rejection and membrane fouling problems during use. Therefore, in order to further improve the performance of PA nanofiltration membranes, the optimization of the nanofiltration membrane modification is the focus of current research. The MOFs nano-particles are introduced into the polyamide active layer, so that the water permeability and selectivity of the membrane can be greatly improved. However, the problems of nanoparticle agglomeration, easy phase interface defect and the like easily occur in the preparation process of the traditional MOFs mixed matrix nanofiltration membrane.
Disclosure of the invention
The invention aims to overcome the defects of the existing nanofiltration membrane and provides a polyamide/polyolefin mixed matrix nanofiltration membrane based on back diffusion in-situ growth UIO-66 and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a polyamide/polyolefin mixed matrix nanofiltration membrane comprises a polyolefin porous support layer, a polyamide active layer and UIO-66 nanoparticles growing and adhering in situ, and is prepared by the following method: firstly, loading metal zirconium ions on a polyolefin porous supporting layer, then carrying out interfacial polymerization to generate a compact polyamide active layer, and finally soaking the membrane in an organic ligand machine solvent to synthesize UIO-66 nano particles in situ through back diffusion to prepare the polyamide/polyolefin mixed matrix nano-filtration membrane.
The UIO-66 nano particle is prepared by self-assembly of a metal zirconium ion monomer and an organic ligand monomer, wherein the metal zirconium ion monomer is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate, and the organic ligand monomer is one or more of terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-di-mercapto terephthalic acid, 2-hydroxy terephthalic acid and 1,3, 5-benzene tricarboxylic acid.
The polyolefin porous supporting layer is prepared from one or more of polyethylene and polypropylene.
The invention also relates to a method for preparing the polyamide/polyolefin mixed matrix nanofiltration membrane, which comprises the following steps:
(1) Dipping a polyolefin porous supporting layer in a solution containing a metal zirconium ion monomer, and attaching metal salt ions to the surface of the polyolefin porous supporting layer; the metal zirconium ion monomer is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate;
(2) Dipping the membrane formed in the step (1) in an organic phase solution of acyl chloride monomer to form an organic phase liquid layer on the surface of the membrane; the acyl chloride monomer is one or more of isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl chloride and polybasic aromatic sulfonyl chloride;
(3) Contacting the membrane formed in the step (2) with an aqueous solution containing amine monomers, and forming a polyamide active layer on the surface of the PE supporting layer through an interfacial polymerization reaction to obtain the metal salt ion-doped initial nanofiltration membrane; the amine monomer is one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexanediamine, 1, 4-butanediamine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 1, 2-cyclohexanediamine, 4, 5-dichloro-o-phenylenediamine, diethylenetriamine and benzenetriamine;
(4) Carrying out in-situ growth UIO-66 on the initial nanofiltration membrane doped with metal salt ions formed in the step (3) in a solution containing an organic ligand, and cleaning to obtain the polyamide/polyolefin mixed matrix nanofiltration membrane; the organic ligand monomer is one or more of terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-di-mercapto terephthalic acid, 2-hydroxy terephthalic acid and 1,3, 5-benzene tricarboxylic acid.
Specifically, the step (1) is as follows: pouring organic phase solution containing metal zirconium ion monomer on the surface of the polyolefin porous support layer, wherein the contact time is 0.1-15 min, then pouring out and drying; the content of the metal zirconium ion in the organic phase solution is 0.005-0.1%, and the solvent is one or more of water, ether, acetone, dimethylformamide, ethanol and acetonitrile.
Specifically, the step (2) is as follows: covering a layer of organic phase solution of acyl chloride monomer on the surface of the membrane obtained in the step (1), pouring out after lasting for 0.1-15 min, wherein the mass fraction of the acyl chloride monomer in the organic phase solution is 0.01-1%, and the solvent is one or more of n-hexane, cyclohexane, toluene, benzene and ethyl acetate.
Specifically, the step (3) is as follows: covering a layer of aqueous phase solution containing amine monomers on the surface of the membrane obtained in the step (2), pouring the aqueous phase solution after the aqueous phase solution lasts for 0.1-15 min, carrying out heat treatment at 40-80 ℃ for 5-30 min, and then cleaning the membrane by using an organic solvent; the mass fraction of the amine monomer in the aqueous phase solution is 0.01-1%.
In the solution of the organic ligand in the step (4), the mass fraction of the organic ligand monomer is 0.005-0.1%, and the solvent is one or more of acetone, ethanol, acetonitrile and N, N-dimethylformamide.
Preferably, the reaction temperature of the step (4) is in the range of 25-50 ℃ (more preferably 25 ℃), and the reaction time is 12-48 h.
Preferably, the cleaning solvent in the step (4) is acetone.
The invention has the following beneficial effects: the polyamide/polyolefin mixed matrix nanofiltration membrane has the advantages of high flux and high rejection rate, simple and feasible preparation method, low cost and huge application potential in the aspects of wastewater treatment, hard water softening, seawater desalination and the like.
Description of the drawings
FIG. 1 shows the separation performance of the nanofiltration membrane (water flux and Na) 2 SO 4 Rejection rate);
FIG. 2 is a scanning electron microscope image of a PA/PE mixed matrix nanofiltration membrane based on back-diffusion in-situ growth of UIO-66;
FIG. 3 is a schematic view and an apparatus diagram of a membrane performance evaluation apparatus.
(V) detailed description of the preferred embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples:
the preparation environments of all the initial nanofiltration membranes in the examples were: the temperature is 25 ℃, the humidity is 40%, and the pressure is normal.
A PA/PE mixed matrix nanofiltration membrane based on reverse diffusion in-situ growth UIO-66 is composed of a PE membrane as a support layer and a polyamide layer containing UIO-66 nanoparticles as a functional layer. The preparation method comprises the following specific steps:
(1) And pouring the metal salt monomer solution on the surface of the PE membrane supporting layer for 4min, pouring out the solution and then airing. Wherein the metal salt monomer is zirconium chloride, the solvent is acetone, and the concentration of the zirconium chloride is 0.00625wt%.
(2) Covering a layer of organic phase solution on the surface of the PE membrane supporting layer obtained in the step (1) for 4min, and then pouring off. Wherein the monomer is trimesoyl chloride, the organic phase solvent is normal hexane, and the concentration of the trimesoyl chloride is 0.075wt%;
(3) Pouring the water phase solution on the surface of the PE membrane supporting layer for 1min, then pouring the solution, and carrying out heat treatment at 60 ℃ for 15min to obtain an initial nanofiltration membrane; wherein the monomer is piperazine. The mass fraction of the aqueous phase monomer was 0.1wt%, and the pH of the aqueous phase solution =10.
(4) Cleaning the membrane obtained in the step (3) with acetone, modifying the membrane with a solution containing an organic ligand at the temperature of 25 ℃/50 ℃ for 24h/48h to carry out in-situ growth of UIO-66, and cleaning to obtain a nanofiltration membrane in-situ growth of UIO-66; wherein the organic ligand is 2-amino terephthalic acid, the mass fraction is 0.00625wt%, the solvent is acetone, and the polyamide nanofiltration membrane is a circle with the diameter of 6 cm.
Example 1:
(1) The PE membrane support layer (shanghai new materials science & tech limited) was immersed in a zirconium chloride acetone solution (0.00625 wt%) for 4min, the solution was poured off and the membrane was air dried.
(2) Immersing the obtained membrane in 0.075wt% of benzene tricarbochloride n-hexane solution for 4min;
(3) Carrying out interfacial polymerization on the obtained membrane and 0.1wt% piperazine water solution for 1min to form a zirconium ion doped polyamide layer on the surface of the PE membrane supporting layer, carrying out heat treatment for 15min, and cleaning with an acetone solution;
(4) And (3) putting the obtained membrane into an acetone solution of 2-amino terephthalic acid to react for in-situ growth of UIO-66 at 25 ℃ for 24 hours, and cleaning the membrane by using acetone to obtain the nano-filtration membrane based on in-situ growth of UIO-66 nano particles.
Analytical testing of the nanofiltration membranes obtained in example 1:
the nanofiltration membrane prepared in this example was loaded into a membrane performance evaluation apparatus (hangzhou seif membrane separation technology ltd, model SA), see fig. 3, with experimental conditions: at normal temperature, 0.6MPa, pre-pressing 1h,1g/L of Na 2 SO 4 A salt solution; the experimental results are as follows: water flux: 6.6Lm -2 h -1 bar -1 ，Na 2 SO 4 The retention rate is as follows: and 75 percent.
Example 2:
(1) Immersing the PE membrane supporting layer in a zirconium chloride acetone solution (0.00625 wt%), pouring out the solution after immersing for 4min, and airing the membrane;
(2) Immersing the obtained film in 0.075wt% of benzene tricarboxychloride n-hexane solution for 4min, pouring the solution, and forming an organic phase liquid layer on the surface of the solution;
(3) Carrying out interfacial polymerization on the obtained membrane and 0.1wt% of piperazine water solution for 1min to form a zirconium ion doped polyamide layer on the surface of the PE membrane supporting layer, carrying out heat treatment for 15min, and cleaning with an acetone solution;
(4) And (3) placing the obtained membrane in an acetone solution of 2-amino terephthalic acid to carry out reaction at 25 ℃ for 48 hours to grow the UIO-66 in situ, and cleaning the membrane by using acetone to obtain the nanofiltration membrane based on the nano particles of the grown UIO-66 in situ, wherein a scanning electron microscope picture is shown in figure 2, wherein a nodular structure belonging to polyamide can be seen from the picture, and obvious particles exist on the surface of the membrane.
Analytical testing of the nanofiltration membranes obtained in example 2:
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 6.8Lm -2 h -1 bar -1 ，Na 2 SO 4 Retention rate: 77 percent.
Example 3:
(1) Immersing the PE membrane supporting layer in a zirconium chloride acetone solution (0.00625 wt%), pouring out the solution after immersing for 4min, and airing the membrane;
(2) Immersing the obtained film in 0.075wt% of benzene tricarboxychloride n-hexane solution for 4min, pouring the solution, and forming an organic phase liquid layer on the surface of the solution;
(3) Carrying out interfacial polymerization on the obtained membrane and 0.1wt% piperazine water solution for 1min to form a zirconium ion doped polyamide layer on the surface of the PE membrane supporting layer, carrying out heat treatment for 15min, and cleaning with an acetone solution;
(4) And (3) placing the obtained membrane in a 2-amino terephthalic acid acetone solution for reaction at 50 ℃ for 24 hours to grow the UIO-66 in situ, and cleaning the membrane by using acetone to obtain the nanofiltration membrane based on the in-situ grown UIO-66 nanoparticles.
Analytical testing of the nanofiltration membranes obtained in example 3:
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 7.8Lm -2 h -1 bar -1 ，Na 2 SO 4 Retention rate: and 47 percent.
Example 4 (comparative):
(1) Immersing a Polysulfone (PSF) membrane supporting layer in 0.2wt% piperazine water solution for 4min, and pouring out the solution to form a water-phase liquid layer on the surface of the solution;
(2) And (3) carrying out interfacial polymerization on the organic phase liquid layer and 0.1wt% of benzene trimethyl chloride n-hexane solution for 1min to form a polyamide layer on the surface of the polysulfone ultrafiltration membrane supporting layer, carrying out heat treatment for 15min, and then placing the polyamide layer into deionized water for storage.
The membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 3.3Lm -2 h -1 bar -1 ，Na 2 SO 4 Retention rate: 97 percent.
Separation Performance profiles of nanofiltration membranes for examples 1-4 (Water flux and Na) 2 SO 4 Rejection) see fig. 1, specific data see table 1:
table 1: water flux and Na of nanofiltration membrane in the embodiment of the invention 2 SO 4 Retention rate
| Examples | Pure water flux (Lm) -2 h -1 bar -1 ) | Na 2 SO 4 Retention (%) |
| Example 1 | 6.6 | 75 |
| Example 2 | 6.8 | 77 |
| Example 3 | 7.8 | 47 |
| Example 4 | 3.3 | 97 |
It can be seen that compared with the traditional polyamide nanofiltration membrane (example 4) using a polysulfone ultrafiltration membrane as a support layer, the water flux of the polyamide/polyolefin mixed matrix nanofiltration membrane (examples 1,2 and 3) prepared by the invention is significantly increased (by 2 times), and the rejection rate of salt is slightly reduced.
Claims (8)
1. A polyamide/polyolefin mixed matrix nanofiltration membrane comprises a polyolefin porous support layer, a polyamide active layer and in-situ grown and attached UIO-66 nanoparticles, and is prepared by the following method: firstly, loading metal zirconium ions on a polyolefin porous supporting layer, then carrying out interfacial polymerization to generate a compact polyamide active layer, and finally soaking the membrane in an organic ligand machine solvent to synthesize UIO-66 nano particles in situ through back diffusion to prepare the polyamide/polyolefin mixed matrix nano-filtration membrane.
2. The polyamide/polyolefin mixed matrix nanofiltration membrane according to claim 1, wherein: the UIO-66 nano particle is prepared by self-assembly of a metal zirconium ion monomer and an organic ligand monomer, wherein the metal zirconium ion monomer is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate, and the organic ligand monomer is one or more of terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-di-mercapto terephthalic acid, 2-hydroxy terephthalic acid and 1,3, 5-benzene tricarboxylic acid.
3. A method of preparing the polyamide/polyolefin mixed matrix nanofiltration membrane of claim 1, comprising:
(1) Soaking a polyolefin porous supporting layer in a solution containing a metal zirconium ion monomer, and attaching metal salt ions to the surface of the polyolefin porous supporting layer; the metal zirconium ion monomer is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate;
(2) Dipping the membrane formed in the step (1) in an organic phase solution of acyl chloride monomer to form an organic phase liquid layer on the surface of the membrane; the acyl chloride monomer is one or more of isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl chloride and polybasic aromatic sulfonyl chloride;
(3) Contacting the membrane formed in the step (2) with an aqueous solution containing amine monomers, and forming a polyamide active layer on the surface of the PE supporting layer through an interfacial polymerization reaction to obtain the metal salt ion-doped initial nanofiltration membrane; the amine monomer is one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexanediamine, 1, 4-butanediamine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 1, 2-cyclohexanediamine, 4, 5-dichloro-o-phenylenediamine, diethylenetriamine and benzenetriamine;
(4) Carrying out in-situ growth UIO-66 on the initial nanofiltration membrane doped with metal salt ions formed in the step (3) in a solution containing an organic ligand, and cleaning to obtain the polyamide/polyolefin mixed matrix nanofiltration membrane; the organic ligand monomer is one or more of terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-di-mercapto terephthalic acid, 2-hydroxy terephthalic acid and 1,3, 5-benzene tricarboxylic acid.
4. The method of claim 3, wherein said step (1) is: pouring organic phase solution containing metal zirconium ion monomer on the surface of the polyolefin porous support layer, wherein the contact time is 0.1-15 min, then pouring out and drying; the content of the metal zirconium ion in the organic phase solution is 0.005-0.1%, and the solvent is one or more of water, ether, acetone, dimethylformamide, ethanol and acetonitrile.
5. The method of claim 3, wherein the step (2) is: covering a layer of organic phase solution of acyl chloride monomer on the surface of the membrane obtained in the step (1), pouring out after the duration of 0.1-15 min, wherein the mass fraction of the acyl chloride monomer in the organic phase solution is 0.01-1%, and the solvent is one or more of n-hexane, cyclohexane, toluene, benzene and ethyl acetate.
6. The method of claim 3, wherein said step (3) is: covering a layer of aqueous phase solution containing amine monomers on the surface of the membrane obtained in the step (2), pouring the aqueous phase solution after the aqueous phase solution lasts for 0.1-15 min, carrying out heat treatment at 40-80 ℃ for 5-30 min, and then cleaning the membrane by using an organic solvent; the mass fraction of the amine monomer in the aqueous phase solution is 0.01-1%.
7. The method according to claim 3, wherein the mass fraction of the organic ligand monomer in the solution of the organic ligand in step (4) is 0.005-0.1%, and the solvent is one or more of acetone, ethanol, acetonitrile, and N, N-dimethylformamide.
8. The method of claim 3, wherein the reaction temperature of the step (4) is 25-50 ℃ and the reaction time is 12-48 h.
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