CN116407956A - Polyamide nano composite membrane with high charge distribution pore canal and preparation method thereof - Google Patents
Polyamide nano composite membrane with high charge distribution pore canal and preparation method thereof Download PDFInfo
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- CN116407956A CN116407956A CN202310383538.4A CN202310383538A CN116407956A CN 116407956 A CN116407956 A CN 116407956A CN 202310383538 A CN202310383538 A CN 202310383538A CN 116407956 A CN116407956 A CN 116407956A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 143
- 239000012528 membrane Substances 0.000 title claims abstract description 143
- 229920002647 polyamide Polymers 0.000 title claims abstract description 143
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 80
- 238000009826 distribution Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000011148 porous material Substances 0.000 title claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 154
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 50
- 150000001412 amines Chemical class 0.000 claims abstract description 50
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 50
- 239000008346 aqueous phase Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000012621 metal-organic framework Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 19
- 238000012695 Interfacial polymerization Methods 0.000 claims description 18
- 229920002492 poly(sulfone) Polymers 0.000 claims description 17
- -1 3-propyl Chemical group 0.000 claims description 16
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 9
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 7
- HPLFXTUAVXJDPJ-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-triethylazanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC(O)CCl HPLFXTUAVXJDPJ-UHFFFAOYSA-M 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 238000000861 blow drying Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 6
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 4
- IFNWESYYDINUHV-UHFFFAOYSA-N 2,6-dimethylpiperazine Chemical compound CC1CNCC(C)N1 IFNWESYYDINUHV-UHFFFAOYSA-N 0.000 claims description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- AASBQTIDAQOQAV-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarbonyl chloride Chemical compound ClC(=O)C1C(C(Cl)=O)C(C(Cl)=O)C1C(Cl)=O AASBQTIDAQOQAV-UHFFFAOYSA-N 0.000 claims description 2
- FEUMMORSWUHIPB-UHFFFAOYSA-N cyclohexane-1,2,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C1CC(C(Cl)=O)C(C(Cl)=O)CC1C(Cl)=O FEUMMORSWUHIPB-UHFFFAOYSA-N 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims 4
- DEHHUEQBGIZXJN-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarbonyl chloride Chemical compound ClC(=O)C1CC(C(Cl)=O)C(C(Cl)=O)C1C(Cl)=O DEHHUEQBGIZXJN-UHFFFAOYSA-N 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 25
- 239000002105 nanoparticle Substances 0.000 abstract description 16
- 230000004048 modification Effects 0.000 abstract description 5
- 239000004941 mixed matrix membrane Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 96
- 239000002585 base Substances 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 19
- 239000012085 test solution Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- 238000002791 soaking Methods 0.000 description 14
- 239000002352 surface water Substances 0.000 description 14
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- 229920006130 high-performance polyamide Polymers 0.000 description 13
- 239000011734 sodium Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of preparation of mixed matrix membrane separation materials, and discloses a polyamide nano composite membrane with high charge distribution pore channels and a preparation method thereof. The composite membrane is formed by compounding an ultrafiltration base membrane and a polyamide compact layer hybridized with a charged nano porous metal organic frame, wherein the polyamide compact layer hybridized with the charged nano porous metal organic frame is aqueous phase amine and UIO-66-NH 2 The mixed solution of the base derivative and the organic acyl chloride solution are polymerized on the surface interface of the ultrafiltration base membrane. The invention uses the method of UIO-66-NH 2 The surface of the nano particle is modified by ionization modification with different degrees, and the modified UIO-66-NH 2 The nano particles can not only be uniformly dispersedThe microstructure and the charge of the formed polyamide compact layer are coordinated among polyamide high molecular chain segments, and the inherent nano pores of the polyamide compact layer can provide additional water molecule transmission channels.
Description
Technical Field
The invention belongs to the technical field of preparation of mixed matrix membrane separation materials, and particularly relates to a polyamide nano composite membrane with high charge distribution pore channels and a preparation method thereof.
Background
Aiming at the heavy demands of energy conservation, emission reduction, traditional industry transformation upgrading and the like, the improvement of ion separation technology has important significance for sustainable development of chemical industrial processes such as energy conversion and storage, environmental pollution and detection, clean industrial production, resource recycling and the like. The nanofiltration separation technology taking the polyamide composite membrane as the core has the advantages of good single/multivalent ion selectivity and low process energy consumption, and can be used in chemical processes such as lithium extraction in salt lakes, brine refining (chlor-alkali industry), recycling of high-salt wastewater, recovery of waste acid (alkali) liquid, flow batteries, salt difference energy power generation and the like. However, the existing polyamide nano-membrane has wide pore diameter distribution reaction, strong surface electronegativity and similar ion (such as Cl) to physical and chemical parameters - /SO 4 2- 、Li + /Mg 2+ ) The separation precision of the catalyst is lower, and the permeability of the catalyst needs to be further improved to reduce the energy consumption and investment cost of the process. Thus, in light of the tremendous demands of the water, resource and energy fields for ion separation technology, it is necessary to develop membrane materials for fine screening of ions.
At present, the research generally considers that the ion sieving performance of the polyamide nano-film is mainly controlled by the synergy of size sieving, charge repulsion and dielectric repulsion. The stacking pores (aggregation pores) and the network pores formed by the polyamide polymer chain segments provide physical size selectivity, and the two pore size structures are closely related to the molecular structure of the interfacial polymerization monomer and the interfacial polymerization process. Therefore, the novel reaction monomer structure is designed at the molecular level or the interfacial polymerization process is regulated and controlled so as to narrow the pore size distribution of the polyamide separation layer, strengthen the size screening effect and further improve the ion screening precision of the polyamide nanofiltration membrane. For example, the design ratio in patent CN108452689A The traditional alicyclic acyl chloride monomer with smaller molecular conformation and flexibility is used for preparing the full aliphatic polyamide nanofiltration membrane with smaller average pore diameter, the NaCl interception rate is kept below 16 percent, and meanwhile, the Na is kept below 16 percent 2 SO 4 The retention rate is maintained above 99.5%, and the excellent Cl is shown - /SO 4 2- Selectivity. But the improvement of structural compactness inevitably leads to a limited improvement of the permeate flux. Methods such as constructing an intermediate layer, regulating and controlling the diffusion rate of the aqueous phase monomer, regulating and controlling the interfacial distribution of the aqueous phase monomer and the like have been studied to promote the spatial order of interfacial polymerization reaction, thereby narrowing the pore size distribution of the separation layer. For example, in patent CN113262642a and CN112755817a, a single-molecule network layer self-assembled at the water-oil interface with a surfactant (such as sodium dodecyl sulfonate and a phosphodiester compound) is used to regulate the ordered diffusion of amine monomers to prepare a polyamide nanofiltration membrane with uniform structure. The retention rate of divalent cations of the polyamide nanofiltration membranes with narrower pore size distribution is more than 98.5 percent, the retention rate of monovalent cations is less than 35 percent, and the water flux can be kept at 16Lm -2 h -1 bar -1 The above. However, the stability and contamination resistance of these surface-wrinkled and ultra-thin separation layers in practical long-term applications is challenging.
The polyamide separation layer surface typically contains a plurality of ionizable charged groups (e.g., -COOH and-NH 2 ) These charged groups may electrostatically interact with ions to cause a charge repulsion phenomenon. Therefore, strengthening the charge rejection is another strategy to effectively increase the ion selectivity of polyamide nanofiltration membranes. More charged groups are introduced into the separation layer by screening water phase/oil phase monomers, so that the charge density of the membrane is improved; or the molecules with charged groups are constructed on the surface of the polyamide separation layer through surface modification (such as chemical grafting, chemical crosslinking, secondary interfacial polymerization, free radical reaction and the like) so as to improve the positive charge density of the surface of the membrane. For example, patent CN113694740a prepares a polyamide membrane with high positive charge density inside the separation layer by interfacial polymerization using ionized quaternary ammonium salt as an aqueous monomer. These polyamino monomers diffuse at a rate and reactivity that affect the final prepared polymer as compared to conventional PIP monomersPermeability of the amide separation layer. The CN112844046a patent grafts a polyfunctional amine compound (e.g., polyethyleneimine, polyvinylamine, polyacrylamide) to the surface of the primary layer of the polyamide membrane by a secondary interfacial polymerization reaction to increase the charge density of the surface of the separation layer. The additional charge layer introduced by the surface modification method, while significantly improving ion selectivity, increases film thickness and crosslink density, resulting in a sacrifice in permeability.
At present, although a great deal of research focuses on the advantages of nano porous filler with inherent pore diameter in breaking through the permeability-selectivity of a polyamide membrane, the research of designing the charged nano porous filler and combining the synergistic effect of pore diameter screening and charge repulsion to prepare the polyamide nano composite membrane with high charge distribution pore channels for ion fine screening is not reported. In addition, how to improve the dispersibility and compatibility of the nano porous filler in the polyamide polymer chain segment has been a key challenge in the field of preparing defect-free polyamide nanocomposite films.
Disclosure of Invention
In order to overcome the problems existing in the related art, the disclosed embodiments of the present invention provide a polyamide nanocomposite membrane with high charge distribution channels and a method for preparing the same, and specifically design in-situ preparation of charged nanoporous metal-organic frameworks (MOFs) with no defects, high permeability, and high ion selectivity (Mg) 2+ /Li + 、SO 4 2- /Cl - ) A metal organic framework based mixed matrix membrane.
The technical scheme is as follows: the polyamide nano composite membrane with the high charge distribution pore canal is formed by compounding an ultrafiltration base membrane and a polyamide compact layer hybridized with a charged nano porous metal organic frame MOFs, and the molecular structural formula of the polyamide nano composite membrane with the high charge distribution pore canal is as follows:
In one embodiment, the polyamide compact layer hybridized by the charged nano porous metal organic frameworks MOFs is formed by polymerizing an aqueous-phase amine solution and an oil-phase organic acyl chloride solution on the surface interface of the ultrafiltration base membrane.
In one embodiment, the ultrafiltration base membrane comprises a porous supporting layer, wherein the porous supporting layer is a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane or a polyacrylonitrile ultrafiltration membrane prepared by phase inversion on the surface of a non-woven fabric; the aqueous amine solution is UIO-66-NH with organic amine and high charge density 2 Mixed solutions of the base derivatives;
the porous supporting layer is immersed in aqueous amine solution and oil phase organic acyl chloride solution successively, and the porous supporting layer is subjected to interfacial polymerization to form the polyamide compact layer hybridized with MOFs of the charged nano porous metal organic frame.
In one embodiment, the charged UIO-66-NH 2 The radical derivative is quaternary ammonium, imidazole or sulfonic acid modified UIO-66-NH 2 At least one of the group derivatives; preparation of quaternary ammonium, imidazole or sulfonic acid group modified UIO-66-NH 2 The modifying agent required by the radical derivative is at least one of 1, 3-propyl sultone, 1, 4-butane sultone, 2, 3-epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride, O-methyl acryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride, 4-imidazole formaldehyde and 2-imidazole formaldehyde.
In one embodiment, the organic amine monomer in the aqueous amine solution is two or more-NH-, -NH- 2 C which is connected with alicyclic saturated hydrocarbon or replaces the original aliphatic or aromatic hydrocarbon; the organic amine monomer is one or more of piperazine, tri (2-aminoethyl) amine, m-phenylenediamine, polyethyleneimine, 2, 5-dimethylpiperazine, (1R, 2R) - (-) -1, 2-cyclohexanediamine, 2, 6-dimethylpiperazine and 1, 4-cyclohexanediamine; the organic solvent for preparing the aqueous amine solution is at least one of cyclohexane, n-hexane, n-heptane and ISOPAR-G, ISOPAR-E, ISOPAR-H.
In one embodiment, the organic acyl chloride monomer in the oil phase organic acyl chloride solution is one or more of trimesoyl chloride, 1,2,3, 4-cyclobutane tetra-formyl chloride, 1,2,4, 5-cyclohexanetetraformyl chloride, 1,3, 5-cyclohexanetetraacyl chloride and 1,2,3, 4-cyclopentanetetraacyl chloride, wherein three or more-COCl are connected on saturated hydrocarbon or aromatic hydrocarbon.
The invention also aims to provide a preparation method of the polyamide nano composite membrane with the high charge distribution pore canal, which designs UIO-66-NH modified by different charge groups through a post-modification strategy 2 The nano porous filler, the soluble charged nano porous filler is uniformly dispersed among polyamide macromolecule chain segments to cooperatively form the microstructure and the charge of the polyamide separation layer, and the method specifically comprises the following steps:
S1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 0.05-4wt%, and then dissolving 0.005-2wt% of UIO-66-NH with high charge density 2 Adding the base derivative, 0-2.3wt% of triethylamine and 0-4.6wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtain a water phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 1-10min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.01-0.4wt% of polybasic acyl chloride, 0-1wt% of tributyl phosphate and 0-1wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization for 10-100S to form a polyamide separation layer, and pouring out the rest organic acyl chloride solution after the reaction is finished;
s4, placing the film obtained in the step S3 in an oven at 60-100 ℃ for thermal crosslinking for 1-10min, and taking out to obtain the polyamide nano composite film with the high charge distribution pore canal.
In one embodiment, in step S1, a high charge density UIO-66-NH 2 The preparation of the base derivative comprises the following steps: adding proper amount of UIO-66-NH into methanol 2 Stirring, ultrasonic treating, adding small molecule of sulfonate, epoxy quaternary ammonium salt or imidazole aldehyde, reacting at 40-80deg.C for 4-12 hr, centrifuging, washing, and freeze drying to obtain charged UIO-66-NH 2 A base derivative;
the charged UIO-66-NH 2 The structure of the base derivative is as follows:
in one embodiment, the charged UIO-66-NH 2 In the preparation of the base derivative, the small molecule of the sultone is one of 1, 3-propyl sultone and 1, 4-butane sultone;
the epoxy quaternary ammonium salt small molecule is one of 2,3 epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride and O-methacryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride;
the imidazole aldehyde small molecule is one of 4-imidazole formaldehyde and 2-imidazole formaldehyde.
By combining all the technical schemes, the invention has the advantages and positive effects that:
the invention discloses a polyamide nano composite membrane with high charge distribution pore canal and a preparation method thereof, the composite membrane is formed by compounding an ultrafiltration base membrane and a polyamide compact layer hybridized with a charged nano porous Metal Organic Frameworks (MOFs), wherein the polyamide compact layer hybridized with the charged nano porous Metal Organic Frameworks (MOFs) is aqueous amine and UIO-66-NH with high charge density 2 The mixed solution of the base derivative and the organic acyl chloride solution are polymerized on the surface interface of the ultrafiltration base membrane, and the charged UIO-66-NH 2 The radical derivative is quaternary ammonium, imidazole or sulfonic acid modified UIO-66-NH 2 And (3) a base derivative. The invention designs the UIO-66-NH modified by quaternary ammonium, imidazole and sulfonic acid groups through a post-modification strategy 2 The base derivative and the soluble charged nano porous filler can be uniformly dispersed among polyamide high molecular chain segments to coordinate the microstructure and the charge of the formed polyamide compact layer so as to prepare the polyamide nano composite membrane with high charge distribution pore channels. The composite membrane prepared by the invention has high ion selectivity and permeability, and can be applied to lithium extraction in salt lakes, brine refining (chlor-alkali industry), high-salt wastewater reclamation, waste acid (alkali) liquid recovery, flow batteries and salt differenceCan generate electricity and other chemical fields.
The invention provides a charge nano porous filler with controllable charge density (UIO-66-NH with high charge density) 2 Base derivative), a method for preparing the polyamide nano composite membrane with high charge distribution pore canal in situ. The invention designs UIO-66-NH modified by different charged groups through a post-modification strategy 2 The nano porous filler and the soluble charged nano porous filler can be uniformly dispersed among polyamide high molecular chain segments to coordinate the microstructure and the charge of the formed polyamide separation layer. The method utilizes abundant charged groups and inherent pore size advantages in the nano porous organic framework to regulate and control the charge density and pore size distribution of the polyamide separation layer. In addition, the method can combine the advantages of rich charged groups, pore channel regularity and ion size screening property of MOFs with the advantages of softness and processability of a high polymer matrix, and can theoretically greatly improve the ion selectivity and permeability of the traditional polymer nano-film.
The invention utilizes UIO-66-NH 2 -NH in organic framework structures 2 The groups are modified in different degrees on the molecular scale through a post-modification strategy, and quaternary ammonium, imidazole or sulfonic acid groups are introduced into UIO-66-NH 2 In the framework structure, the dispersibility and the solubility of the colloidal solution in the aqueous amine solution are improved, and finally, a stable colloidal solution is formed. Modified UIO-66-NH during interfacial polymerization 2 The nano filler not only affects the distribution and diffusion of the aqueous phase amine monomer on the surface of the basement membrane, but also occupies an interface reaction site, thereby causing the polyamide macromolecule chain segment to surround the three-dimensional nanometer UIO-66-NH 2 The frame structure is formed to increase the formation of polyamide segment stacking holes. In addition, due to the charged nano UIO-66-NH 2 The ordered pore canal and the charged group in the framework structure increase the order and the charge of the pore canal of the polyamide nanometer film. Thus, the prepared polyamide nanocomposite membrane with high charge distribution channels has increased channel order, charge density and porosity, resulting in a significant enhancement of ion sieving performance.
The invention uses the method of UIO-66-NH 2 The surface of the nano particle is modified by ionization modification with different degreesPreparation of UIO-66-NH with surfaces enriched with quaternary ammonium, imidazole or sulphonic acid ionic groups 2 Nanoparticles, i.e. charged nanoporous fillers. Modified UIO-66-NH 2 The nano particles can be stably and uniformly dispersed in the aqueous phase solution, can be stably present in the polyamide high molecular chain segment through interfacial polymerization, so that the charge density of the polyamide compact layer is improved, and the nano particles are porous materials and can remarkably improve the water flux.
The invention was carried out under simulated drinking water conditions (at 2000ppm NaCl/Na) 2 SO 4 /MgCl 2 LiCl 145 psi) test of the prepared mixed matrix membrane, the prepared high positive charge density UIO-66-NH 2 MgCl of nanoparticle hybridized polyamide nanocomposite film 2 The retention rate is 96.2-98.5%, the retention rate of LiCl is 18.8-40.1%, and the water flux is 229.1-386.3 L.m -2 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the Prepared UIO-66-NH with high negative charge density 2 Na of nanoparticle hybridized polyamide nanocomposite membrane 2 SO 4 The retention rate is 96.5-99.3%, the NaCl retention rate is 16.3-39.5%, and the water flux is 302.8-420.6 L.m -2 ·h -1 . Osmotic flux and ion selectivity (Mg 2+ /Li + 、SO 4 2- /Cl - ) The selectivity is superior to the ion-selective composite membrane reported at present, which shows that the membrane preparation method has obvious technical progress.
The sulfonate, aldehyde imidazole and epoxy quaternary ammonium salt micromolecules used for modification in the invention have the advantages of simple structure, low cost, easy obtainment and the like, and the modification method is simple and is convenient for popularization in industrial application. The modified UIO-66-NH of the invention 2 The nano particles can be uniformly dispersed among polyamide high molecular chain segments to coordinate the microstructure and charge of the formed polyamide compact layer, and the inherent nano pores of the nano particles can provide additional water molecule transmission channels.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure;
FIG. 1 is a flow chart of a preparation method of a polyamide nanocomposite film with high charge distribution channels according to an embodiment of the present invention;
FIG. 2 is a surface topography of a polyamide nanocomposite membrane with high charge distribution channels prepared according to an embodiment of the present invention;
FIG. 3 is a schematic illustration of a quaternary ammonium group modified UIO-66-NH designed and synthesized in accordance with example 3 of the present invention 2 A topography of the nanoparticle;
fig. 4 is a schematic view of charge density of the composite films prepared in comparative example 1, example 4 and example 11 provided in examples of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Embodiment 1 of the invention provides a polyamide nanocomposite membrane with high charge distribution pore channels, which is formed by compositing an ultrafiltration base membrane and a high charge density nano porous Metal Organic Frameworks (MOFs) hybridized polyamide compact layer, wherein the high charge density nano porous Metal Organic Frameworks (MOFs) hybridized polyamide compact layer is formed by polymerizing an aqueous phase amine mixed solution and an oil phase organic acyl chloride solution on the surface interface of the ultrafiltration base membrane, and the aqueous phase amine mixed solution is UIO-66-NH with high charge density and organic amine 2 Mixed solutions of the base derivatives; said high charge density UIO-66-NH 2 The derivative is UIO-66-NH modified by quaternary ammonium, imidazole or sulfonic acid group 2 At least one of the group derivatives.
In the embodiment of the invention, the organic amine is at least one of m-phenylenediamine, piperazine, polyethyleneimine, tri (2-aminoethyl) amine, 2, 5-dimethylpiperazine, (1R, 2R) - (-) -1, 2-cyclohexanediamine, 2, 6-dimethylpiperazine and 1, 4-cyclohexanediamine.
In an embodiment of the invention, the preparation of quaternary ammonium, imidazole or sulfonic acid group modified UIO-66-NH 2 The modifying agent required by the radical derivative is at least one of 1, 3-propyl sultone, 1, 4-butane sultone, 2, 3-epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride, O-methyl acryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride, 4-imidazole formaldehyde and 2-imidazole formaldehyde.
In the embodiment of the invention, the organic acyl chloride is at least one of trimesoyl chloride, 1,2,3, 4-cyclobutanetetra-formyl chloride, 1,2,4, 5-cyclohexanedicarbonyl chloride, 1,3, 5-cyclohexanediacyl chloride and 1,2,3, 4-cyclopenta-tetra-acyl chloride. The organic solvent is at least one of cyclohexane, n-hexane, n-heptane, and ISOPAR-G, ISOPAR-E, ISOPAR-H.
In the embodiment of the invention, the ultrafiltration base membrane comprises a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane or a polyacrylonitrile ultrafiltration membrane.
As shown in fig. 1, the preparation method of the polyamide nanocomposite film with high charge distribution pore channels provided by the embodiment of the invention comprises the following steps:
s1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 0.05-4wt%, and then dissolving 0.005-2wt% of UIO-66-NH with high charge density 2 Adding the base derivative, 0-2.3wt% of triethylamine and 0-4.6wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtain a water phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 1-10min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.01-0.4wt% of polybasic acyl chloride, 0-1wt% of tributyl phosphate and 0-1wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization for 10-100S to form a polyamide separation layer, and pouring out the rest organic acyl chloride solution after the reaction is finished;
S4, placing the film obtained in the step S3 in an oven at 60-100 ℃ for thermal crosslinking for 1-10min, and taking out to obtain the polyamide nanocomposite film with the high charge distribution pore channels (FIG. 2 is a surface topography diagram of the polyamide nanocomposite film with the high charge distribution pore channels prepared by the embodiment of the invention).
Example 2 the polyamide nanocomposite membrane with high charge distribution channels provided in the example of the present invention has the following structural formula:
wherein R is a molecule with a charged group.
The polyamide nano composite membrane with the high charge distribution pore canal consists of non-woven fabrics, a porous supporting layer and charged UIO-66-NH 2 The porous support layer is a polysulfone ultrafiltration membrane prepared by phase inversion on the surface of non-woven fabrics; containing UIO-66-NH 2 The polyamide compact layer of the base derivative is prepared by sequentially dipping a porous supporting layer in an aqueous phase amine solution and an oil phase organic acyl chloride solution and carrying out interfacial polymerization, wherein the aqueous phase amine solution contains UIO-66-NH with high charge density 2 And (3) a base derivative.
The organic amine monomer in the aqueous amine solution is two or more than two of "-NH-, -NH 2 "attached to alicyclic saturated hydrocarbon or substituted for original aliphatic or aromatic C", and further, the optional organic amine monomer in the invention is one or more of piperazine, tri (2-aminoethyl) amine, m-phenylenediamine, polyethylenimine, 2, 5-dimethylpiperazine, (1R, 2R) - (-) -1, 2-cyclohexanediamine, 2, 6-dimethylpiperazine, and 1, 4-cyclohexanediamine.
The oil phase organic acyl chloride solution contains three or more "-COCl" connected to saturated hydrocarbon or aromatic hydrocarbon, and the acyl chloride monomer selected by the invention is one or more of trimesoyl chloride, 1,2,3, 4-cyclobutane tetra-formyl chloride, 1,2,4, 5-cyclohexane tetra-formyl chloride, 1,3, 5-cyclohexane tri-acyl chloride and 1,2,3, 4-cyclopentanetetraacyl chloride.
In an embodiment of the present invention, a method for preparing a polyamide nanocomposite film having a high charge distribution channel is provided, including the steps of:
(1) Preparing an aqueous phase solution: UIO-66-NH 2 Dissolving the base derivative and polyamine in pure water, and then adding triethylamine and camphorsulfonic acid as additives; generally, UIO-66-NH 2 The mass concentration of the base derivative and the polyamine is 0.005-2wt% and 0.05-4wt%, and the mass concentration of the triethylamine and the camphorsulfonic acid is 0-2.3wt% and 0-4.6wt%;
(2) And (3) preparing the oil phase solution: dissolving polybasic acyl chloride in an organic solvent, and then adding tributyl phosphate and acetone as additives, wherein the mass concentration of polybasic acyl chloride, tributyl phosphate and acetone is 0.01-0.4wt%,0-1wt% and 0-1wt% respectively; the oil phase monomer solvent is one or more of cyclohexane, n-hexane, n-heptane and ISOPAR-G, ISOPAR-E, ISOPAR-H.
(3) Preparation of high-performance polyamide nano composite membrane: the ultrafiltration porous supporting layer adopts 1% sodium hydroxide or 1.5% NaHCO 3 Soaking in aqueous solution for 30min, washing with ultrapure water, drying, immersing the ultrafiltration porous support layer in the aqueous amine solution for 1-10min, removing surface water drops, and immersing in the polyacyl chloride solution for 10-100s to form a polyamide compact layer; taking out, and placing in a vacuum drying oven for heat treatment at 60-100deg.C for 1-10 min; preferably, the pore size of the porous support layer is in the range of 10-40nm.
In the embodiment of the invention, UIO-66-NH 2 The preparation method of the nano-particles comprises the following steps: according to ZrCl 4 : 2-amino terephthalic acid: water: n, N-Dimethylformamide (DMF) was 1:1:162:741, after stirring and ultrasonic treatment, the solution was poured into a reaction kettle and heated at 120 ℃ for 24 hours. After centrifugation at 10000rpm for 30min, the sediment was collected, first washed 3 times with methanol and then 3 times with water. Finally, obtaining the UIO-66-NH with the particle size of about 30-50nm 2 And (3) nanoparticles.
Charged UIO-66-NH 2 The preparation method of the base derivative comprises the following steps: adding proper amount of UIO-66-NH into methanol 2 Stirring, ultrasonic treating, and directingAdding sulfonate, epoxy quaternary ammonium salt or imidazole aldehyde micromolecule, reacting for 4-12h at 40-80 ℃, centrifuging, washing, freeze drying the product to obtain charged UIO-66-NH 2 And (3) a base derivative.
Charged UIO-66-NH 2 The structural formula of the base derivative is as follows:
the sulfonate lactone small molecules are as follows: 1, 3-propyl sultone and 1, 4-butane sultone.
The epoxy quaternary ammonium salt micromolecules are as follows: 2, 3-epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride, O-methacryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride.
The imidazole aldehyde small molecule is as follows: 4-imidazole formaldehyde and 2-imidazole formaldehyde.
Comparative example 1 a prior art hybrid matrix composite membrane preparation method comprises the steps of: (1) preparation of aqueous phase solution: configuration of 0.02w/v% UIO-66-NH 2 And 1.0w/v% PIP aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of polyamide nanocomposite film: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, the prepared mixed matrix composite membranes were continuously filtered for 1 hour at 145psi operating pressure, respectively, and the performance of the composite membranes was tested, and the results are shown in table 1.
Comparative example 2 the preparation method of the prior art mixed matrix composite membrane comprises the steps of:
(1) Preparing an aqueous phase solution: configuration of 0.02w/v% UIO-66-NH 2 And 0.8w/v% PIP aqueous solution;
(2) Preparation of oil phase solution: preparing a cyclohexane solution of 0.1w/v% of 1,2,3, 4-cyclopentatetraoyl chloride and 1w/v% of acetone;
(3) Preparation of polyamide nanocomposite film: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 20s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm Na 2 SO 4 And an aqueous NaCl solution as a test solution, and the prepared mixed matrix composite membranes were continuously filtered for 1 hour at an operating pressure of 145psi, respectively, and the properties of the composite membranes were tested, and the results are shown in Table 1.
preparation of quaternary ammonium group-rich UIO-66-NH on surface 2 Nanoparticles: 1.414g of UIO-66-NH 2 (Mw= 2828.95) dispersing in 60ml methanol solution by ultrasonic, adding 0.67g2, 3-epoxypropyl trimethyl ammonium chloride dropwise under stirring, reacting at 50 ℃ for 6 hours, washing the product by methanol, centrifuging, freeze drying to obtain the 2, 3-epoxypropyl trimethyl ammonium chloride modified UIO-66-NH 2 The derivative (fig. 3) has the structure:
(1) Preparing an aqueous phase solution: preparation of 0.02w/v% 2, 3-epoxypropyltrimethylammonium chloride modified UIO-66-NH 2 1.0w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking a polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the n-hexane solution of 0.1w/v% trimesoyl chloride in the step (2) for 30s, forming a polyamide compact layer, and then placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes having high charge distribution channels were continuously filtered for 1 hour, respectively, under an operating pressure of 145psi, and the properties of the composite membranes were tested, and the results are shown in table 1.
(1) Preparing an aqueous phase solution: preparation of 0.1w/v% 2, 3-epoxypropyltrimethylammonium chloride modified UIO-66-NH 2 Derivatives (same as in example 3), 1.0w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, the prepared mixed matrix composite membranes were continuously filtered for 1 hour at 145psi operating pressure, respectively, and the performance of the composite membranes was tested, and the results are shown in table 1.
(1) Preparing an aqueous phase solution: preparing 0.08w/v% of ethylene 2, 3-epoxypropyl trimethyl ammonium chloride modified UIO-66-NH 2 A derivative (same as in example 3), 1.0w/v% aqueous solution of hyperbranched polyethyleneimine (PEI-70000);
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes having high charge distribution channels were continuously filtered for 1 hour, respectively, under an operating pressure of 145psi, and the properties of the composite membranes were tested, and the results are shown in table 1.
(1) Preparing an aqueous phase solution: preparing 0.08w/v% of ethylene 2, 3-epoxypropyl trimethyl ammonium chloride modified UIO-66-NH 2 Derivatives (same as in example 3), 1.0w/v% aqueous solution of tris (2-aminoethyl) amine;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes having high charge distribution channels were continuously filtered for 1 hour, respectively, under an operating pressure of 145psi, and the properties of the composite membranes were tested, and the results are shown in table 1.
preparation of UIO-66-NH with imidazole group-rich surface 2 Nanoparticles: 1.414g of UIO-66-NH 2 (mw= 2828.95) was dispersed in 30ml of a methanol solution by ultrasonic wave, 0.38g of 2-imidazole formaldehyde was added dropwise with stirring, and reacted at 50 ℃ for 6 hours, followed byAnd removing the solvent, neutralizing the mixture by using HCl, washing, centrifuging, and freeze-drying to obtain a product with the structure:
(1) Preparing an aqueous phase solution: UIO-66-NH configured with 0.02w/v% imidazolyl 2 1.0w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes having high charge distribution channels were continuously filtered for 1 hour, respectively, under an operating pressure of 145psi, and the properties of the composite membranes were tested, and the results are shown in table 1.
(1) Preparing an aqueous phase solution: UIO-66-NH configured with 0.08w/v% imidazolyl 2 Derivatives (same as in example 5), 1.0w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, the prepared solution having an operating pressure of 145psiThe polyamide nano composite membranes with high charge distribution pore channels were continuously filtered for 1 hour, and the performance of the composite membranes was tested, and the results are shown in table 1.
(1) Preparing an aqueous phase solution: UIO-66-NH configured with 0.08w/v% imidazolyl 2 Derivatives (same as in example 5), 1.0w/v% aqueous solution of tris (2-aminoethyl) amine;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 5 min.
With 2000ppm MgCl 2 And LiCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes having high charge distribution channels were continuously filtered for 1 hour, respectively, under an operating pressure of 145psi, and the properties of the composite membranes were tested, and the results are shown in table 1.
preparation of UIO-66-NH having sulfonic acid group-rich surface 2 Nanoparticles: 1.0g of UIO-66-NH 2 (Mw= 2828.95) dispersing in 30ml methanol solution by ultrasonic, adding 0.54g1, 3-propyl sultone dropwise under stirring, reacting at 50 ℃ for 12 hours, washing the product by methanol, centrifuging, freeze drying to obtain sulfonic acid group modified UIO-66-NH 2 The derivative has the structure:
(1) Preparing an aqueous phase solution: configuration of 0.02w/v% 1, 3-propylsultone modified UIO-66-NH 2 Derivatives, 0.8w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing 0.1w/v% of a normal hexane solution of trimesoyl chloride;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 20s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 2 min.
With 2000ppm Na 2 SO 4 And NaCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes with high charge distribution channels were continuously filtered for 1 hour at an operating pressure of 145psi, respectively, and the performance of the composite membranes was tested, and the results are shown in Table 1.
(1) Preparing an aqueous phase solution: configuration of 0.08w/v% 1, 3-propylsultone modified UIO-66-NH 2 Derivatives (same as in example 10), 0.8w/v% piperazine aqueous solution;
(2) Preparation of oil phase solution: preparing an n-hexane solution of 0.1w/v% trimesoyl chloride, 0.1w/v% tributyl phosphate and 1w/v% acetone;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 30s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 2 min.
With 2000ppm Na 2 SO 4 And NaCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes with high charge distribution channels were continuously filtered for 1 hour at an operating pressure of 145psi, respectively, and the performance of the composite membranes was tested, and the results are shown in Table 1.
(1) Preparing an aqueous phase solution: configuration of 0.04w/v%1, 3-propylsultone modified UIO-66-NH 2 Derivatives (same as in example 10), 1.0w/v% piperazine in water;
(2) Preparation of oil phase solution: preparing a cyclohexane solution of 0.1w/v% of 1,2,3, 4-cyclopentatetraoyl chloride and 1w/v% of acetone;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 20s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 2 min.
With 2000ppm Na 2 SO 4 And NaCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes with high charge distribution channels were continuously filtered for 1 hour at an operating pressure of 145psi, respectively, and the performance of the composite membranes was tested, and the results are shown in Table 1.
Embodiment 13 the present embodiment provides a method for preparing a polyamide nanocomposite film having high charge distribution channels, comprising the steps of:
(1) Preparing aqueous amine solution: configuration of 0.08w/v%1, 3-propylsultone modified UIO-66-NH 2 Derivatives (same as in example 10), 1.0w/v% piperazine in water;
(2) Preparation of oil phase solution: preparing a cyclohexane solution of 0.1w/v% of 1,2,3, 4-cyclopentatetraoyl chloride and 1w/v% of acetone;
(3) Preparation of high-performance polyamide nano composite membrane: soaking the polysulfone ultrafiltration membrane in ultrapure water, washing, drying, immersing in the aqueous phase solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 20s to form a polyamide compact layer, and then, placing at 60 ℃ for heat treatment for 2 min.
With 2000ppm Na 2 SO 4 And NaCl aqueous solution as a test solution, and the prepared polyamide nanocomposite membranes with high charge distribution channels were continuously filtered for 1 hour at an operating pressure of 145psi, respectively, and the performance of the composite membranes was tested, and the results are shown in Table 1.
TABLE 1 ion sieving Properties of high Performance Polyamide nanocomposite films prepared according to the invention
In the examples of the present invention, single salt solution test conditions: 2000ppm MgCl 2 Or LiCl or Na 2 SO 4 Or NaCl water solution is used as a test solution, and the prepared polyamide membrane is continuously filtered for 1h under 145psi operation pressure and 25 ℃ to test the performance;
b MgCl 2 +licl test conditions: 1866ppm MgCl 2 The prepared polyamide film was pre-pressed for 0.5h at a working pressure of 145psi at 25℃with a +134ppm LiCl mixed brine solution as a test solution, and tested for Li + /Mg 2+ Selectivity (1);
c Na 2 SO 4 +nacl test conditions: 1000ppm Na 2 SO 4 The prepared polyamide film was pre-pressed for 0.5h at 25℃under 145psi operating pressure with a +1000ppm NaCl mixed brine solution as a test solution, and tested for Cl - /SO 4 2- Selectivity.
In the examples of the present invention, fig. 4 is a schematic view of charge density of the composite films prepared in comparative example 1, example 4 and example 11 provided in the examples of the present invention.
Example 14 As another possible embodiment of the present invention, a method for preparing a polyamide nanocomposite membrane with high charge distribution channels is provided, in which UIO-66-NH modified by different charged groups is designed by a post-modification strategy 2 The nano porous filler, the soluble charged nano porous filler is uniformly dispersed among polyamide macromolecule chain segments to cooperatively form the microstructure and the charge of the polyamide separation layer, and the method specifically comprises the following steps:
s1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 0.05%, and then preparing 0.005% of UIO-66-NH with high charge density 2 Adding the base derivative, 1.0wt% of triethylamine and 2.0wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtainTo an aqueous phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 1min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.01wt% of polybasic acyl chloride, 0.2wt% of tributyl phosphate and 0.2wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization for 10S to form a polyamide separation layer, and pouring out the residual organic acyl chloride solution after the reaction is finished;
And S4, placing the film obtained in the step S3 in a baking oven at 60 ℃ for thermal crosslinking for 1min, and taking out to obtain the polyamide nano composite film with the high charge distribution pore canal.
Example 15 As another possible embodiment of the present invention, a method for preparing a polyamide nanocomposite membrane with high charge distribution channels is provided, in which UIO-66-NH modified by different charged groups is designed by post-modification strategy 2 The nano porous filler, the soluble charged nano porous filler is uniformly dispersed among polyamide macromolecule chain segments to cooperatively form the microstructure and the charge of the polyamide separation layer, and the method specifically comprises the following steps:
s1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 2.055wt%, and then preparing 1.0wt% of UIO-66-NH with high charge density 2 Adding the base derivative, 1.15wt% of triethylamine and 2.3wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtain a water phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 5min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.2wt% of polybasic acyl chloride, 0.5wt% of tributyl phosphate and 0.5wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization for 55S to form a polyamide separation layer, and pouring out the residual organic acyl chloride solution after the reaction is finished;
S4, placing the film obtained in the step S3 in an oven at 80 ℃ for thermal crosslinking for 5min, and taking out to obtain the polyamide nano composite film with high charge distribution pore channels
Example 16 As another possible embodiment of the present invention, a method for preparing a polyamide nanocomposite membrane with high charge distribution channels is provided, in which UIO-66-NH modified by different charged groups is designed by a post-modification strategy 2 The nano porous filler, the soluble charged nano porous filler is uniformly dispersed among polyamide macromolecule chain segments to cooperatively form the microstructure and the charge of the polyamide separation layer, and the method specifically comprises the following steps:
s1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 4wt%, and then dissolving 2wt% of UIO-66-NH with high charge density 2 Adding the base derivative, 2.3wt% of triethylamine and 4.6wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtain a water phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 10min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.4wt% of polybasic acyl chloride, 1wt% of tributyl phosphate and 1wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization reaction for 100S to form a polyamide separation layer, and pouring out the residual organic acyl chloride solution after the reaction is finished;
And S4, placing the film obtained in the step S3 in a baking oven at 100 ℃ for thermal crosslinking for 10min, and taking out to obtain the polyamide nano composite film with the high charge distribution pore canal.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and in part, not described or illustrated in any particular embodiment, reference is made to the related descriptions of other embodiments.
While the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The polyamide nano composite membrane with the high charge distribution pore canal is characterized by being formed by compounding an ultrafiltration base membrane and a polyamide compact layer hybridized with MOFs of a charged nano porous metal organic frame, wherein the molecular structural formula is as follows:
2. the polyamide nanocomposite membrane with high charge distribution pore channels according to claim 1, wherein the polyamide dense layer hybridized by the charged nanoporous metal organic frameworks MOFs is formed by polymerizing an aqueous amine solution and an oil phase organic acid chloride solution on the surface interface of the ultrafiltration base membrane.
3. The polyamide nanocomposite membrane with high charge distribution channels according to claim 2, wherein the ultrafiltration base membrane comprises a porous support layer, the porous support layer being a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane or a polyacrylonitrile ultrafiltration membrane prepared by surface phase inversion of a nonwoven fabric; the aqueous amine solution is UIO-66-NH with organic amine and high charge density 2 Mixed solutions of the base derivatives;
the porous supporting layer is immersed in aqueous amine solution and oil phase organic acyl chloride solution successively, and the porous supporting layer is subjected to interfacial polymerization to form the polyamide compact layer hybridized with MOFs of the charged nano porous metal organic frame.
4. The polyamide nanocomposite membrane with high charge distribution channels according to claim 2, wherein the charged UIO-66-NH 2 The radical derivative is quaternary ammonium imidazole or sulfonic acid group modified UIO-66-NH 2 At least one of the group derivatives; preparation of quaternary ammonium, imidazole or sulfonic acid group modified UIO-66-NH 2 The required modifying agent for the radical derivative is 1, 3-propylsulfonic acidAt least one of lactone, 1, 4-butane sultone, 2, 3-epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride, O-methacryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride, 4-imidazole formaldehyde and 2-imidazole formaldehyde.
5. The polyamide nanocomposite membrane with high charge distribution channels according to claim 2, wherein the organic amine monomer in the aqueous amine solution is two or more of-NH-, -NH 2 C which is connected with alicyclic saturated hydrocarbon or replaces the original aliphatic or aromatic hydrocarbon; the organic amine monomer is one or more of piperazine, tri (2-aminoethyl) amine, m-phenylenediamine, polyethyleneimine, 2, 5-dimethylpiperazine, (1R, 2R) - (-) -1, 2-cyclohexanediamine, 2, 6-dimethylpiperazine and 1, 4-cyclohexanediamine.
6. The polyamide nanocomposite membrane with high charge distribution channels according to claim 5, wherein the organic solvent used to prepare the aqueous amine solution is at least one of cyclohexane, n-hexane, n-heptane, ISOPAR-G, ISOPAR-E, ISOPAR-H.
7. The polyamide nanocomposite membrane with high charge distribution channels according to claim 2, wherein the organic acid chloride monomer in the oil phase organic acid chloride solution is one or more of three or more-coci-linked to saturated hydrocarbon or aromatic hydrocarbon, and the organic acid chloride monomer is trimesoyl chloride, 1,2,3, 4-cyclobutanetetra-carbonyl chloride, 1,2,4, 5-cyclohexanetetracarbonyl chloride, 1,3, 5-cyclohexanetetracarbonyl chloride, and 1,2,3, 4-cyclopentanetetracarbonyl chloride.
8. A preparation method of a polyamide nano composite membrane is characterized in that the method is used for preparing the polyamide nano composite membrane with a pore canal with high charge distribution according to any one of claims 1-7, and UIO-66-NH modified by different charged groups is designed by a post-modification strategy 2 Nanoporous fillers, solubleThe charged nano porous filler is uniformly dispersed among polyamide polymer chain segments to cooperatively form the microstructure and the charge of the polyamide separation layer, and specifically comprises the following steps:
s1, dissolving organic amine in water to prepare an organic amine solution with the mass concentration of 0.05-4wt%, and then dissolving 0.005-2wt% of UIO-66-NH with high charge density 2 Adding the base derivative, 0-2.3wt% of triethylamine and 0-4.6wt% of camphorsulfonic acid into an organic amine solution, fully stirring, and performing ultrasonic dispersion to obtain a water phase solution;
s2, immersing the ultrafiltration base membrane in the aqueous phase solution in the step S1, taking out after immersing for 1-10min, and blow-drying or roll-drying the residual aqueous phase solution on the surface of the ultrafiltration base membrane by using an air knife or a rubber roll;
s3, preparing an organic acyl chloride solution by adopting 0.01-0.4wt% of polybasic acyl chloride, 0-1wt% of tributyl phosphate and 0-1wt% of acetone, immersing the upper surface of the membrane obtained in the step S2 in the organic acyl chloride solution, performing interfacial polymerization for 10-100S to form a polyamide separation layer, and pouring out the rest organic acyl chloride solution after the reaction is finished;
S4, placing the film obtained in the step S3 in an oven at 60-100 ℃ for thermal crosslinking for 1-10min, and taking out to obtain the polyamide nano composite film with the high charge distribution pore canal.
9. The method of preparing a polyamide nanocomposite film according to claim 7, wherein in step S1, UIO-66-NH of high charge density 2 The preparation of the base derivative comprises the following steps: adding proper amount of UIO-66-NH into methanol 2 Stirring, ultrasonic treating, adding small molecule of sulfonate, epoxy quaternary ammonium salt or imidazole aldehyde, reacting at 40-80deg.C for 4-12 hr, centrifuging, washing, and freeze drying to obtain charged UIO-66-NH 2 A base derivative;
the charged UIO-66-NH 2 The structure of the base derivative is as follows:
10. the method for preparing a polyamide nanocomposite film according to claim 9, wherein the charged UIO-66-NH 2 In the preparation of the base derivative, the small molecule of the sultone is one of 1, 3-propyl sultone and 1, 4-butane sultone;
the epoxy quaternary ammonium salt small molecule is one of 2,3 epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, dodecyl dimethyl epoxypropyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride and O-methacryloyl-oxyethyl dimethyl epoxypropyl ammonium chloride;
The imidazole aldehyde small molecule is one of 4-imidazole formaldehyde and 2-imidazole formaldehyde.
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| CN117427509A (en) * | 2023-12-20 | 2024-01-23 | 河南师范大学 | Self-assembled dendritic macromolecule polyamide nano-film for efficient separation of lithium and magnesium and preparation method thereof |
| CN117547974A (en) * | 2024-01-12 | 2024-02-13 | 河南师范大学 | Polyaiperazine amide nanofiltration membrane with high acid-base stability and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117427509A (en) * | 2023-12-20 | 2024-01-23 | 河南师范大学 | Self-assembled dendritic macromolecule polyamide nano-film for efficient separation of lithium and magnesium and preparation method thereof |
| CN117427509B (en) * | 2023-12-20 | 2024-04-05 | 河南师范大学 | Self-assembled dendritic macromolecule polyamide nano-film for efficient separation of lithium and magnesium and preparation method thereof |
| CN117547974A (en) * | 2024-01-12 | 2024-02-13 | 河南师范大学 | Polyaiperazine amide nanofiltration membrane with high acid-base stability and preparation method thereof |
| CN117547974B (en) * | 2024-01-12 | 2024-04-12 | 河南师范大学 | Polyaiperazine amide nanofiltration membrane with high acid-base stability and preparation method thereof |
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