CN114405292A - Novel composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof - Google Patents
Novel composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof Download PDFInfo
- Publication number
- CN114405292A CN114405292A CN202210198879.XA CN202210198879A CN114405292A CN 114405292 A CN114405292 A CN 114405292A CN 202210198879 A CN202210198879 A CN 202210198879A CN 114405292 A CN114405292 A CN 114405292A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- nanofiltration membrane
- novel composite
- composite nanofiltration
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 177
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 126
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 210000004379 membrane Anatomy 0.000 claims abstract description 67
- 239000012071 phase Substances 0.000 claims abstract description 55
- 238000002791 soaking Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- -1 titanium hydroxyl modified imidazole Chemical class 0.000 claims abstract description 19
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- 229960003506 piperazine hexahydrate Drugs 0.000 claims description 12
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 229960005141 piperazine Drugs 0.000 claims description 4
- RILPVBCCHVYIJF-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCN1CN(C)C=C1 RILPVBCCHVYIJF-UHFFFAOYSA-N 0.000 claims description 3
- SFPTVQNKTCPLAX-UHFFFAOYSA-N 3-ethyl-1-methyl-1,2-dihydroimidazol-1-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CC[NH+]1CN(C)C=C1 SFPTVQNKTCPLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 21
- 239000002351 wastewater Substances 0.000 abstract description 17
- 208000028659 discharge Diseases 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 56
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 36
- 239000002585 base Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- 239000004408 titanium dioxide Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 27
- 239000003921 oil Substances 0.000 description 24
- 239000011148 porous material Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 16
- 238000012695 Interfacial polymerization Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000001223 reverse osmosis Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 230000009881 electrostatic interaction Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002090 nanochannel Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- IXLWEDFOKSJYBD-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;methanesulfonate Chemical compound CS([O-])(=O)=O.CC[N+]=1C=CN(C)C=1 IXLWEDFOKSJYBD-UHFFFAOYSA-M 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012703 sol-gel precursor Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/263—Chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a novel composite nanofiltration membrane modified by ionic liquid, a preparation method and application thereof, belonging to the technical field of separation membrane composite materials. Firstly, dissolving a titanium source and imidazole ionic liquid in a solvent, and after the reaction is finished, carrying out freeze drying to obtain titanium hydroxyl modified imidazole ionic liquid; the molar ratio of the titanium source to the imidazole ionic liquid is 1: 0.5-1.5. And then dissolving an aqueous phase monomer in the titanium hydroxyl modified imidazole ionic liquid, and reacting to obtain an aqueous phase solution. And finally, soaking the basement membrane in the water phase solution, soaking the basement membrane in the oil phase solution to react to form a cross-linked layer, taking out and drying to obtain the novel composite nanofiltration membrane. The novel composite nanofiltration membrane can be applied to zero discharge treatment of high-salinity wastewater, and has high salt ion rejection rate and water permeation flux.
Description
Technical Field
The invention relates to the technical field of separation membrane composite materials, in particular to a novel composite nanofiltration membrane modified by ionic liquid and a preparation method and application thereof.
Background
The wastewater with the total salt content of at least 1 percent is called high-salinity wastewater, and most of the salt substances contained in the high-salinity wastewater are Cl-、SO4 2-、Na+、Ca2+And the like. The high-salt wastewater is mainly from chemical production, incomplete chemical reaction or by-products of chemical reaction, especially a large amount of high-COD and high-salt toxic wastewater generated in the production process of chemical products such as dyes, pesticides and the like. In the waste water treatment process, the concentration of soluble salts is increased by mineralization caused by the addition of a water treatment agent, acid and alkali and concentrated solution generated by recovery of most of 'light' water, so that the 'high salinity waste water' which is difficult to biochemically treat is formed. In addition, the high-salinity wastewater also comes from seawater desalination treatment, petroleum and natural gas refining, food processing plants and the like.
The high-salinity wastewater not only contains high-concentration inorganic salt, but also contains high-concentration organic matters, nitrogen, phosphorus and other substances, and the direct discharge can improve the water mineralization of rivers, bring serious pollution to soil, surface water and underground water and endanger the ecological environment. At present, the common treatment technologies for high-salinity wastewater include distillation desalination technologies (multiple-effect evaporation, multi-stage flash evaporation, compressed air distillation and membrane distillation), electrolysis technologies, ion exchange technologies, membrane separation technologies, biological treatment technologies and the like. Although the distillation desalination technology is applied earlier, the high-salinity wastewater is easy to scale on the wall of a heat transfer pipe due to boiling on a heating surface, frequent cleaning and strict scale prevention measures are required, the structure of distillation equipment is complex, and the operation energy consumption is too high, so that the industrial applicability of the technology is influenced. The longer the electrolysis technology is run, the more susceptible the electrode surface is to electrochemical corrosion, scaling, and the need to periodically clean or replace the electrode, which would otherwise affect the reaction efficiency. The ion exchange technology is frequently regenerated, consumes a large amount of acid and alkali, has high operation cost, generates a large amount of acid and alkali regeneration waste liquid which cannot be digested, and causes secondary pollution. The biological treatment technology for high-salinity wastewater treatment needs to domesticate specific species of strains for a long time, and has strict requirements on the operating environment, strict requirements on the control of operating parameters and poor environmental applicability of the strains, so the biological treatment technology for high-salinity wastewater is still in the research and discussion stage.
The membrane separation technology is a novel separation technology for separating, purifying and concentrating target substances by utilizing the difference of selective permeability of membranes to each component in a mixture. Among them, nanofiltration membranes and reverse osmosis membranes are the most effective and most commonly used desalination technologies, but if the TDS of the wastewater is higher than 30000mg/L, membrane fouling, scaling and the like are easy to occur by using reverse osmosis membranes (RO), and the membrane flux is reduced. The nanofiltration membrane (NF) is called loose reverse osmosis, and is currently most commonly a polymer nano-membrane (organic membrane) prepared by an interfacial polymerization method, and has a nano-scale pore diameter between the pore diameters of a reverse osmosis membrane and an ultrafiltration membrane, and because the pore diameter is large, the removal rate and the separation performance of salts are not good, so in order to improve the permeation flux and the separation performance of the polymer nano-membrane (organic membrane), many researches in recent years report that certain nano-particles or porous materials, such as aluminum oxide (Al) are added in the preparation process of the polymer nanofiltration membrane (organic membrane), and the nano-particles or the porous materials are used for improving the permeation flux and the separation performance of the polymer nano-membrane (organic membrane), and the research reports are carried out2O3) Titanium dioxide (TiO)2) Silicon dioxide (SiO)2) However, these inorganic porous materials have limited dispersibility and poor compatibility with organic membrane materials, and thus the separation performance of the nanofiltration membrane is not improved.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of limited dispersibility, poor compatibility with organic membrane materials and low separation performance in the prior art.
In order to solve the technical problems, the invention provides a novel composite nanofiltration membrane modified by ionic liquid and a preparation method and application thereof. Since the initial film generation can affect the diffusion of the subsequent reaction monomer, the reaction has self-inhibition property, so that the film prepared by the interfacial polymerization method has smaller thickness and is beneficial to the transmission.
The first purpose of the invention is to provide a preparation method of a novel composite nanofiltration membrane, which comprises the following steps,
s1, dissolving a titanium source and the imidazole ionic liquid in a solvent, and after the reaction is finished, freeze-drying to obtain the titanium hydroxyl modified imidazole ionic liquid; the molar ratio of the titanium source to the imidazole ionic liquid is 1: 0.5-1.5;
s2, dissolving an aqueous phase monomer in the imidazole ionic liquid modified by the titanium hydroxide radical in the step S1, and reacting to obtain an aqueous phase solution; the water phase monomer is a piperazine compound;
s3, soaking the bottom membrane in the water phase solution obtained in the step S2, soaking the bottom membrane in the oil phase solution for reaction to form a cross-linked layer, taking out and drying to obtain the novel composite nanofiltration membrane; the oil phase solution is obtained by dissolving acyl chloride monomers in an organic solvent.
In one embodiment of the present invention, in the S1 step, the solvent is isopropanol.
In one embodiment of the present invention, in the step S1, the titanium source is isopropyl titanate.
In one embodiment of the present invention, in step S1, the imidazole based ionic liquid is 1-ethyl-3-methylimidazole methane sulfonate ionic liquid and/or 1-ethyl-3-methylimidazole trifluoroacetate ionic liquid.
In one embodiment of the present invention, in the S2 step, the piperazine-based compound is piperazine hexahydrate.
In one embodiment of the present invention, in the step of S2, the concentration of the aqueous phase monomer is 1.0 to 3.0 wt%; the concentration of the titanium hydroxyl modified imidazole ionic liquid is 0.3-0.5 wt%.
In one embodiment of the present invention, in the step of S3, the concentration of the acid chloride-based monomer is 0.01 to 0.2 wt%; the acyl chloride monomer is trimesoyl chloride.
In an embodiment of the present invention, in step S3, the base film is a polyethersulfone-based film.
In one embodiment of the present invention, in step S3, the soaking time in the aqueous phase is 8-12 min; soaking in oil phase for 3-7 min.
In one embodiment of the present invention, in the step S3, the drying temperature is 328-338K; the drying time is 3-7 min.
The second purpose of the invention is to provide a novel composite nanofiltration membrane prepared by the method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the novel composite nanofiltration membrane firstly utilizes ionic liquid to react with titanium dioxide (TiO)2) The nano particles are subjected to surface grafting, and then the modified titanium dioxide material with higher permeability is introduced in an interfacial polymerization mode, namely the obtained titanium dioxide particles loaded with ionic liquid are added to an organic selective layer of the polymer nanofiltration membrane in the interfacial polymerization process, so that the titanium dioxide (TiO) is improved2) The dispersibility of the nano particles and the compatibility with the organic film material ensure that the space of the prepared film is uniformly distributed, thus eliminating the formation of non-selective diffusion channels and reducing the generation of surface defects of the film. And because of the hydrophilicity of the ionic liquid, the doped ionic liquid modified titanium dioxide can provide an additional water channel for the polymer nano-membrane (organic membrane), so that the permeation and separation performance of the composite hybrid nanofiltration membrane (ionic liquid modified nanofiltration membrane material) is further improved, the composite hybrid nanofiltration membrane is used for treating high-salt wastewater, and the composite hybrid nanofiltration membrane has high pure water flux, high rejection rate on salt and high separation performance on different salts.
(2) The mechanism of separating pollutants by the novel composite nanofiltration membrane comprises pore size screening, adsorption, electrostatic interaction and functional interaction, wherein the process is pore size expansion-electrostatic adsorption-functional interaction (repulsive force and attractive force). The sieving of contaminants is achieved by nanochannels of the nanomembrane, and electrostatic interactions and functional interactions are influenced by the valence ratio and ionic hydration diameter of the contaminants.
(3) The novel composite nanofiltration membrane has strong and unique interaction (strong covalent bonding) among the layers, which promotes the integrity of the membrane and stabilizes the pore structure of the membrane. The presence of oxygen-containing functional groups in the ionic liquid introduced into the nanofiltration membrane can enhance the interaction (e.g., electrostatic interaction) between the nanofiltration membrane and molecules such as water, ions, and contaminants.
(4) The novel composite nanofiltration membrane disclosed by the invention evaluates the Pore Size Distribution (PSD) of the nanofiltration membrane by using a Density Functional Theory (DFT) model, has specific pore size, has excellent water permeability and selectivity, and has water flux of 70L/m, and the pore size distribution is concentrated between 0.3nm and 0.7nm2H.bar, the salt rejection rate can reach more than 90%. Change of water flux value, type and addition amount of ionic liquid, and titanium dioxide (TiO)2) The addition amount of the ionic liquid and the titanium dioxide is related, and a nanofiltration membrane material with the optimal performance can be prepared by using a proper ionic liquid and titanium dioxide addition amount.
(5) The novel composite nanofiltration membrane can be applied to zero discharge treatment of high-salinity wastewater, the salt ion rejection rate of the novel composite nanofiltration membrane is higher than that of a common nanofiltration membrane material due to the special membrane surface charge and the special membrane pore size of the novel composite nanofiltration membrane, the water permeation flux is higher, and the technology for realizing salt separation through selective filtration of the nanofiltration membrane material can be popularized in the field of high-salinity wastewater recycling.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
fig. 1 is a diagram showing a pore size distribution of nanofiltration membrane materials of examples 1 and 5 and comparative example 3 of the present invention.
Figure 2 is a graph of pure water flux at different pressures for nanofiltration membrane materials of examples 1-6 of the present invention.
Fig. 3 is a graph of pure water flux at different pressures for nanofiltration membrane materials of example 1 and comparative examples 1-3 of the present invention.
Figure 4 is a graph of the rejection rate of the nanofiltration membrane material of examples 1 to 6 of the invention and comparative examples 1 to 3 for NaCl solutions of different concentrations.
Fig. 5 is a graph of the separation performance of the nanofiltration membrane materials of examples 1 and 6 of the present invention on different salt solutions.
FIG. 6 is a graph of pure water flux and NaCl rejection for different runs of nanofiltration membrane material of example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
firstly, imidazole ionic liquid 1-ethyl-3-methylimidazole methane sulfonate ionic liquid [ Emim ] is synthesized and prepared]CH3SO3Then isopropyl titanate (TTIP) as a sol-gel precursor is mixed with isopropanol (C)3H7OH) were mixed, an ionic liquid [ Emim ] was added to the mixture]CH3SO3Then dropwise adding water to carry out hydrolytic condensation to prepare ionic liquid modified titanium dioxide, and finally preparing the nanofiltration membrane by adopting an interfacial polymerization method, wherein the method specifically comprises the following three steps:
(1) imidazole ionic liquid [ Emim]CH3SO3Synthesis of (2)
Brominating 1-ethyl-3-methylimidazole (26g, 0.136mol) and methanesulfonic acid (13g, 0.136mol) in 30mL of CCI4Mixing, stirring for 0.5h at room temperature, slowly dropwise adding 2.3g of hydrogen peroxide (30%, 0.068mol) into the reaction system, and stirring for 3h at room temperature after the dropwise addition of 30% of hydrogen peroxide is finishedAfter the reaction is finished, separating by using a separating funnel, washing the water phase by using dichloromethane, and carrying out rotary evaporation on the water phase to obtain the 1-ethyl-3-methylimidazolium methanesulfonate ionic liquid [ Emim]CH3SO3。
(2) Imidazole ionic liquid [ Emim]CH3SO3Preparation of modified titanium dioxide materials
Adding isopropyl titanate (10g, 0.035mol) into isopropanol (42g, 0.7mol), stirring and mixing, then adding imidazole ionic liquid [ Emim ] into the mixture]CH3SO3(7.22g, 0.035mol) for 15min, adding a small amount of deionized water into the mixed solution, continuing stirring for 1h, and after the reaction is finished, freeze-drying to obtain the imidazole ionic liquid [ Emim]CH3SO3Modifying the titanium dioxide material.
(3) Preparation of ionic liquid modified nanofiltration membrane
Step 1: firstly, 0.4 percent of imidazole ionic liquid [ Emim ] with mass concentration is added into a piperazine hexahydrate aqueous solution with mass concentration of 2 percent]CH3SO3Modifying titanium dioxide powder, carrying out ultrasonic dispersion for 1h, and then cooling to room temperature to obtain an aqueous phase mixture for later use.
Step 2: taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
Step 3: pouring off the water phase, removing the excessive water on the membrane surface, pouring the n-hexane solution of 0.1 wt% of trimesoyl chloride in the oil phase solution on the membrane surface, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer, namely the imidazole ionic liquid [ Emim%]CH3SO3The modified titanium dioxide powder is embedded in the crosslinked layer.
Step 4: and (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Example 2
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
(1) imidazole ionic liquid [ Emim]CH3SO3The specific procedure of (1) was the same as in example 1.
(2) Imidazole ionic liquid [ Emim]CH3SO3The preparation of the modified titanium dioxide material was carried out in the same manner as in example 1.
(3) Preparation of ionic liquid modified nanofiltration membrane
Step 1: firstly, 0.3 percent of imidazole ionic liquid [ Emim ] is added into a piperazine hexahydrate aqueous solution with the mass concentration of 2 percent]CH3SO3Modifying titanium dioxide powder, carrying out ultrasonic dispersion for 1h, and then cooling to room temperature to obtain an aqueous phase mixture for later use.
Step 2: taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
Step 3: pouring off the water phase, removing the excessive water on the membrane surface, pouring the n-hexane solution of 0.1 wt% of trimesoyl chloride in the oil phase solution on the membrane surface, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer, namely the imidazole ionic liquid [ Emim%]CH3SO3The modified titanium dioxide powder is embedded in the crosslinked layer.
Step 4: and (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Example 3
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
(1) imidazole ionic liquid [ Emim]CH3SO3The specific procedure of (1) was the same as in example 1.
(2) Imidazole ionic liquid [ Emim]CH3SO3Preparation of modified titanium dioxide materials, in particularThe procedure is as in example 1.
(3) Preparation of ionic liquid modified nanofiltration membrane
Step 1: firstly, 0.5 percent of imidazole ionic liquid [ Emim ] with mass concentration is added into a piperazine hexahydrate aqueous solution with mass concentration of 2 percent]CH3SO3Modifying titanium dioxide powder, carrying out ultrasonic dispersion for 1h, and then cooling to room temperature to obtain an aqueous phase mixture for later use.
Step 2: taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
Step 3: pouring off the water phase, removing the excessive water on the membrane surface, pouring the n-hexane solution of 0.1 wt% of trimesoyl chloride in the oil phase solution on the membrane surface, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer, namely the imidazole ionic liquid [ Emim%]CH3SO3The modified titanium dioxide powder is embedded in the crosslinked layer.
Step 4: and (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Example 4
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
(1) imidazole ionic liquid [ Emim]CH3SO3The specific procedure of (1) was the same as in example 1.
(2) Imidazole ionic liquid [ Emim]CH3SO3Preparation of modified titanium dioxide materials
Adding isopropyl titanate (10g, 0.035mol) into isopropanol (42g, 0.7mol), stirring and mixing, then adding imidazole ionic liquid [ Emim ] into the mixture]CH3SO3(3.61g, 0.0175mol) stirring and mixing for 15min, then adding a small amount of deionized water into the mixed solution, continuing stirring and reacting for 1h, and after the reaction is finished, freeze-drying to obtain the imidazole ionic liquid [ Emim [ ]]CH3SO3Modifying the titanium dioxide material.
(3) The specific steps of the preparation of the ionic liquid modified nanofiltration membrane are the same as those in example 1.
Example 5
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
(1) imidazole ionic liquid [ Emim]CH3SO3The specific procedure of (1) was the same as in example 1.
(2) Imidazole ionic liquid [ Emim]CH3SO3Preparation of modified titanium dioxide materials
Adding isopropyl titanate (10g, 0.035mol) into isopropanol (42g, 0.7mol), stirring and mixing, then adding imidazole ionic liquid [ Emim ] into the mixture]CH3SO3(10.83g, 0.0525mol) stirring and mixing for 15min, then adding a small amount of deionized water into the mixed solution, continuing stirring and reacting for 1h, and after the reaction is finished, freeze-drying to obtain the imidazole ionic liquid [ Emim [ ]]CH3SO3Modifying the titanium dioxide material.
(3) The specific steps of the preparation of the ionic liquid modified nanofiltration membrane are the same as those in example 1.
Example 6
A novel composite nanofiltration membrane modified by ionic liquid and a preparation method thereof specifically comprise the following steps:
(1) imidazole ionic liquid [ Emim]CF3Synthesis of COO
Brominating 1-ethyl-3-methylimidazole (26g, 0.136mol) and trifluoroacetic acid (15.5g, 0.136mol) in 30mL of CCI4Mixing, stirring at room temperature for 0.5h, slowly dropwise adding 2.3g of hydrogen peroxide (30%, 0.068mol) into the reaction system, after the dropwise addition of the 30% of hydrogen peroxide is finished, continuously stirring at room temperature for 3h, after the reaction is finished, separating by using a separating funnel, washing an aqueous phase by using dichloromethane, and carrying out rotary evaporation on the aqueous phase to obtain the 1-ethyl-3-methylimidazole trifluoroacetate ionic liquid [ Emim]CF3COO。
(2) ImidazolesIonic liquid [ Emim]CF3Preparation of COO modified titanium dioxide material
Adding isopropyl titanate (10g, 0.035mol) into isopropanol (42g, 0.7mol), stirring and mixing, then adding imidazole ionic liquid [ Emim ] into the mixture]CF3COO (7.846g, 0.035mol) is stirred and mixed for 15min, then a small amount of deionized water is added into the mixed solution, the mixture is stirred and reacted for 1h, and after the reaction is finished, the mixture is frozen and dried to obtain the imidazole ionic liquid [ Emim]CF3And COO modifies the titanium dioxide material.
(3) Preparation of ionic liquid modified nanofiltration membrane
Step 1: firstly, 0.4 percent of imidazole ionic liquid [ Emim ] with mass concentration is added into a piperazine hexahydrate aqueous solution with mass concentration of 2 percent]CF3And modifying titanium dioxide powder with COO, ultrasonically dispersing for 1h, and cooling to room temperature to obtain an aqueous phase mixture for later use.
Step 2: taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
Step 3: pouring off the water phase, removing the excessive water on the membrane surface, pouring the n-hexane solution of 0.1 wt% of trimesoyl chloride in the oil phase solution on the membrane surface, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer, namely the imidazole ionic liquid [ Emim%]CF3The COO-modified titanium dioxide powder is embedded in the crosslinked layer.
Step 4: and (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Comparative example 1
(1) Firstly, adding unmodified titanium dioxide powder into a piperazine hexahydrate aqueous solution with the mass concentration of 2%, ultrasonically dispersing for 1h, and then cooling to room temperature to obtain an aqueous phase mixture for later use.
(2) Taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
(3) And pouring the water phase, removing the excessive water on the surface of the membrane, pouring 0.1 wt% of trimesoyl chloride n-hexane solution of the oil phase solution onto the surface of the membrane, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer in which unmodified titanium dioxide powder is embedded.
(4) And (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Comparative example 2
(1) Firstly, adding unmodified titanium dioxide powder with the mass concentration of 0.4% into piperazine hexahydrate aqueous solution with the mass concentration of 2%, ultrasonically dispersing for 1h, and then cooling to room temperature to obtain an aqueous phase mixture for later use.
(2) Taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring the water phase mixture on the surface of the base film, and soaking for 10 min.
(3) And pouring the water phase, removing the excessive water on the surface of the membrane, pouring 0.1 wt% of trimesoyl chloride n-hexane solution of the oil phase solution onto the surface of the membrane, reacting for 5min, and allowing the oil phase solution and the water phase mixture to react with each other to form a cross-linked layer in which unmodified titanium dioxide powder is embedded.
(4) And (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Comparative example 3
Preparing an ultrafiltration basement membrane by polyether sulfone (PES), and then carrying out interfacial polymerization on the surface of the basement membrane by using a piperazine hexahydrate (PIP) aqueous solution with the mass concentration of 2% and a trimesoyl chloride n-hexane solution with the mass concentration of 0.1% to form a polyamide cross-linked layer as a nanofiltration selection layer.
Step 1: taking a polyether sulfone (PES) base film with a proper size as a base film, soaking the base film in deionized water for pretreatment, placing the base film in an interfacial polymerization mold, removing redundant water on the surface of the film, pouring a piperazine hexahydrate (PIP) aqueous solution with the mass concentration of 2% on the surface of the base film, and soaking for 10 min.
Step 2: and pouring the water phase, removing the excessive water on the surface of the membrane, pouring the n-hexane solution of 0.1 wt% of trimesoyl chloride in the oil phase solution onto the surface of the membrane, and reacting for 5min to form a cross-linked layer by the mutual reaction of the oil phase solution and the water phase mixture.
Step 3: and (4) pouring out the surface oil phase, putting the membrane into an oven, drying for 5min at 333K, taking out the membrane, and storing in water.
Test example 1
The novel composite nanofiltration membranes prepared in examples 1 to 6 and the nanofiltration membrane materials prepared in comparative examples 1 to 3 were evaluated for Pore Size Distribution (PSD), and the membrane materials were evaluated for salt/water permeability, and the permeability, the permeation flux, and the rejection rate of inorganic salts are important parameters characterizing the separation performance of the nanofiltration membranes, and the specific evaluation parameters were as follows:
(1) pore Size Distribution (PSD) of various nanofiltration membrane materials
The Pore Size Distribution (PSD) of the nanofiltration membrane is evaluated by using a Density Functional Theory (DFT) model and solute transfer simulation, and the result is shown in figure 1, the pore size distribution of the ionic liquid modified nanofiltration membrane material prepared by the invention is concentrated between 0.3nm and 0.7nm, and the ionic liquid modified nanofiltration membrane material prepared by the invention is also proved to have high water flux and salt rejection rate from the aspect of pore size distribution because the radius of hydrated ions of most salt ions is more than 0.65nm and the diameter of water molecules is 0.28 nm. Also, as can be seen from fig. 1, the pore size distribution of the blank nanofiltration membrane is concentrated between 0.4nm and 0.8nm, and the pore size distribution of the nanofiltration membrane material prepared in example 5 is slightly smaller than that of example 1, so that it is further illustrated that too much ionic liquid is added during the preparation process of the novel nanofiltration membrane to block part of the channels, thereby affecting the water flux of the prepared novel nanofiltration membrane.
(2) Pure water flux of ionic liquid modified nanofiltration membrane under different pressures
Through a reverse osmosis device, adopting cross flow filtrationAnd testing the pure water flux of the ionic liquid modified nanofiltration membrane under different pressures, wherein the testing temperature is room temperature. The pure water flux of the ionic liquid modified nanofiltration membrane under different pressures is shown in figures 2-3, and the results show that the water flux of the ionic liquid modified nanofiltration membrane material prepared by the invention can reach 70L/m2H.bar or more. Comparing examples 1-6 in fig. 2, it can be seen that the nanofiltration membrane materials modified by different amounts of ionic liquid and titanium dioxide, and the nanofiltration membrane materials modified by different types of ionic liquid have higher pure water flux, and thus it can be inferred that the appropriate range of the molar ratio of the added ionic liquid to the titanium dioxide in the preparation process of the ionic liquid modified nanofiltration membrane material prepared by the present invention is 0.5-1.5: 1, Ionic liquid-titanium dioxide (IL-TiO)2) The proper range of the mass ratio concentration of the whole additive is 0.3-0.5%.
Comparing example 1 with comparative examples 1-3 in FIG. 3, it can be seen that the imidazole-based ionic liquid [ Emim]CH3SO3Compared with a nanofiltration membrane material prepared by modifying titanium dioxide and then preparing the nanofiltration membrane material only by adopting imidazole ionic liquid [ Emim]CH3SO3The pure water flux of the modified nanofiltration membrane material is larger, and further shows that the addition of titanium dioxide can provide an additional water channel for the prepared novel nanofiltration membrane material.
(3) Rejection rate of ionic liquid modified nanofiltration membrane on salt solution
The rejection rate of the ionic liquid modified nanofiltration membrane to NaCl solutions with different concentrations is tested by adopting a reverse osmosis device and cross-flow filtration, and the data is recorded after the rejection rate is relatively stable by pre-pressing for a period of time at room temperature and 1bar pressure. As shown in fig. 4, as can be seen from comparative examples 1 to 6, the rejection rate (> 90%) of NaCl solution of various ionic liquid modified nanofiltration membrane materials prepared by the present invention is higher, which further illustrates that the suitable range of the molar ratio of the added ionic liquid to titanium dioxide is 0.5 to 1.5 in the preparation process of the ionic liquid modified nanofiltration membrane material prepared by the present invention: 1, Ionic liquid-titanium dioxide (IL-TiO)2) The proper range of the mass ratio concentration of the whole additive is 0.3-0.5%.
Also, from the results, it is clear that when imidazole is usedIonic liquid like [ Emim ]]CH3SO3When the addition amount is too much, the agglomeration of particles, uneven particle dispersion, uneven charge distribution and other reasons can be caused, the surface defect of the membrane is caused, and the separation performance of the membrane is influenced; similarly, when the imidazole ionic liquid [ Emim]CH3SO3When the amount is too small, the membrane separation performance is affected by changes in the pore diameter of the membrane, a decrease in the electrostatic adsorption force on the membrane surface, and the like.
From the results, it is understood that the difference in the kind of the ionic liquid does not largely affect the separation performance of the membrane, and thus it can be said that the ionic liquid according to the present invention is not limited to the two kinds of ionic liquids disclosed in the present invention, and is also applicable to other hydrophilic ionic liquids.
Comparing the data of example 1 and comparative examples 1-3, it can be seen that the imidazole ionic liquid [ Emim]CH3SO3The nanofiltration membrane material prepared after modifying titanium dioxide has a much higher NaCl rejection rate than the nanofiltration membrane material prepared by unmodified titanium dioxide because of [ Emim]CH3SO3The ionic liquid has fixed positively charged imidazole group, so that the imidazole ionic liquid [ Emim]CH3SO3The nanofiltration membrane prepared after modifying titanium dioxide has positive electricity and repels Na+The NaCl in the solution is trapped, and the modified nanofiltration membrane material has the characteristic of charge, so that the nanofiltration membrane material has high desalting performance under very low pressure. And through imidazole ionic liquid [ Emim]CH3SO3Ionic liquid [ Emim ] in nanofiltration membrane material prepared after modifying titanium dioxide]CH3SO3Due to the embedding, the ionic liquid forms an ion nano channel effect due to microphase separation, so that the pore channel distribution of the nanofiltration membrane material modified by the ionic liquid is more concentrated on intercepting various salt ions.
(4) Separation performance of ionic liquid modified nanofiltration membrane on different salt solutions
The ionic liquid-modified nanofiltration membrane materials prepared in examples 1 and 6 were tested for different salt solutions (0.1mol/L NaCl, MgCl) at a pressure of 1bar by means of a reverse osmosis unit using cross-flow filtration2、CaCl2Solution) separation performance. Is implemented by the method in FIG. 5The results in example 1 show that imidazole-based ionic liquids [ Emim]CH3SO3MgCl pair of nanofiltration membrane material prepared after modifying titanium dioxide2The retention rate of the catalyst is 98.2 percent, and the catalyst is applied to CaCl2The retention rate of (A) was 97.8%, the retention rate of NaCl was 96.1%, and the respective salt ions were Mg in the order of radius of hydrated ion2+(0.86nm)＞Ca2+(0.82nm)＞Na+(0.72nm), the nano-filtration membrane material modified by the ionic liquid has smaller pore channel distribution, is more beneficial to intercepting salt ions with larger hydrated ion radius, and the electrostatic repulsion effect of the membrane material on divalent salt ions is larger than that of monovalent salt ions, so that the membrane can realize MgCl effect2Has better interception effect. Therefore, electrostatic interaction and functional interaction of the ionic liquid modified nanofiltration membrane material and various salt ions are influenced by the valence ratio of pollutants and the ionic hydration diameter, and the ionic liquid modified nanofiltration membrane material has different ionic retention rates due to different charge intensities of electrolyte salt ions, has different selectivity of the membrane to different ions and different ion passing ratios in a multi-element system containing ions with different valence states.
Similarly, from the results of example 6 in fig. 5, it can be seen that, although the type of ionic liquid was changed, the performance of the hydrophilic ionic liquid was similar in the treatment of high-salt wastewater, and further, it is explained that the ionic liquid according to the present invention is not limited to the two ionic liquids disclosed in the present invention, and is also applicable to other hydrophilic ionic liquids.
(5) Operation stability of ionic liquid modified nanofiltration membrane
The change of the pure water flux and the change of the NaCl rejection of the ionic liquid modified nanofiltration membrane material prepared in example 1 of the present invention under long-term operation were studied, and the results are shown in fig. 6, where the pure water flux of the ionic liquid modified nanofiltration membrane material shows a small fluctuation with time, but the whole is relatively stable, and the attenuation of the water flux is small. However, the rejection rate of the ionic liquid modified nanofiltration membrane material to the NaCl has a stable operation stage, the rejection rate of the ionic liquid modified nanofiltration membrane material to the NaCl is gradually increased in the early operation stage (0 ═ 10h), after the operation is stable, the change is not large, the stability is about 96%, and after 150h of uninterrupted filtration, the filtration performance of the ionic liquid modified nanofiltration membrane material still maintains a very good state, which indicates that the ionic liquid modified nanofiltration membrane material has good operation stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a novel composite nanofiltration membrane is characterized by comprising the following steps,
s1, dissolving a titanium source and the imidazole ionic liquid in a solvent, and after the reaction is finished, freeze-drying to obtain the titanium hydroxyl modified imidazole ionic liquid; the molar ratio of the titanium source to the imidazole ionic liquid is 1: 0.5-1.5;
s2, dissolving an aqueous phase monomer in the imidazole ionic liquid modified by the titanium hydroxide radical in the step S1, and reacting to obtain an aqueous phase solution; the water phase monomer is a piperazine compound;
s3, soaking the bottom membrane in the water phase solution obtained in the step S2, soaking the bottom membrane in the oil phase solution for reaction to form a cross-linked layer, taking out and drying to obtain the novel composite nanofiltration membrane; the oil phase solution is obtained by dissolving acyl chloride monomers in an organic solvent.
2. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S1, the titanium source is isopropyl titanate.
3. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S1, the imidazole-based ionic liquid is 1-ethyl-3-methylimidazole methane sulfonate ionic liquid and/or 1-ethyl-3-methylimidazole trifluoroacetate ionic liquid.
4. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S2, the piperazine compound is piperazine hexahydrate.
5. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S2, the concentration of the aqueous phase monomer is 1.0-3.0 wt%; the concentration of the titanium hydroxyl modified imidazole ionic liquid is 0.3-0.5 wt%.
6. The method for preparing the novel composite nanofiltration membrane according to claim 1, wherein in the step S3, the concentration of the acyl chloride monomer is 0.01-0.2 wt%; the acyl chloride monomer is trimesoyl chloride.
7. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S3, the basement membrane is a polyethersulfone membrane.
8. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S3, the soaking time in the aqueous phase is 8-12 min; soaking in oil phase for 3-7 min.
9. The method for preparing a novel composite nanofiltration membrane according to claim 1, wherein in the step S3, the drying temperature is 328-338K; the drying time is 3-7 min.
10. A novel composite nanofiltration membrane prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210198879.XA CN114405292B (en) | 2022-03-01 | 2022-03-01 | Composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210198879.XA CN114405292B (en) | 2022-03-01 | 2022-03-01 | Composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114405292A true CN114405292A (en) | 2022-04-29 |
| CN114405292B CN114405292B (en) | 2023-10-27 |
Family
ID=81261048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210198879.XA Active CN114405292B (en) | 2022-03-01 | 2022-03-01 | Composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114405292B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| US20100297531A1 (en) * | 2009-05-21 | 2010-11-25 | Battelle Memorial Institute | Immobilized fluid membranes for gas separation |
| CN102600819A (en) * | 2012-02-29 | 2012-07-25 | 上海师范大学 | Porous titanium dioxide photocatalyst film and preparation method thereof |
| CN103170260A (en) * | 2013-04-18 | 2013-06-26 | 河北麦森钛白粉有限公司 | Modified nanometer titanium dioxide based preparation process of hollow ultrafiltration membrane fiber |
| CN104492282A (en) * | 2014-12-24 | 2015-04-08 | 福州大学 | Ionic liquid modified TiO2 nanoparticle/PVDF composite micro-porous membrane and preparation method thereof |
| CN105879907A (en) * | 2016-03-02 | 2016-08-24 | 中国科学院兰州化学物理研究所 | Immobilized ionic-liquid catalyst and application thereof to synthesizing ester lubricating oil |
| CN106115777A (en) * | 2016-06-15 | 2016-11-16 | 南开大学 | The preparation method of a kind of titanium dioxide ultrathin nanometer page and the application in lithium ion battery thereof |
| CN107583469A (en) * | 2017-11-01 | 2018-01-16 | 天津工业大学 | The preparation method of polyamide composite nanofiltration membrane containing amino modified nano-particle |
| CN111068527A (en) * | 2019-12-23 | 2020-04-28 | 哈尔滨工业大学（深圳） | Preparation method of polyamide composite nanofiltration membrane for removing heavy metal pollutants |
| CN113893711A (en) * | 2021-10-15 | 2022-01-07 | 中国石油大学(华东) | High-flux reverse osmosis composite membrane and preparation method thereof |
-
2022
- 2022-03-01 CN CN202210198879.XA patent/CN114405292B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| US20100297531A1 (en) * | 2009-05-21 | 2010-11-25 | Battelle Memorial Institute | Immobilized fluid membranes for gas separation |
| CN102600819A (en) * | 2012-02-29 | 2012-07-25 | 上海师范大学 | Porous titanium dioxide photocatalyst film and preparation method thereof |
| CN103170260A (en) * | 2013-04-18 | 2013-06-26 | 河北麦森钛白粉有限公司 | Modified nanometer titanium dioxide based preparation process of hollow ultrafiltration membrane fiber |
| CN104492282A (en) * | 2014-12-24 | 2015-04-08 | 福州大学 | Ionic liquid modified TiO2 nanoparticle/PVDF composite micro-porous membrane and preparation method thereof |
| CN105879907A (en) * | 2016-03-02 | 2016-08-24 | 中国科学院兰州化学物理研究所 | Immobilized ionic-liquid catalyst and application thereof to synthesizing ester lubricating oil |
| CN106115777A (en) * | 2016-06-15 | 2016-11-16 | 南开大学 | The preparation method of a kind of titanium dioxide ultrathin nanometer page and the application in lithium ion battery thereof |
| CN107583469A (en) * | 2017-11-01 | 2018-01-16 | 天津工业大学 | The preparation method of polyamide composite nanofiltration membrane containing amino modified nano-particle |
| CN111068527A (en) * | 2019-12-23 | 2020-04-28 | 哈尔滨工业大学（深圳） | Preparation method of polyamide composite nanofiltration membrane for removing heavy metal pollutants |
| CN113893711A (en) * | 2021-10-15 | 2022-01-07 | 中国石油大学(华东) | High-flux reverse osmosis composite membrane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENGMEI SHI ET AL: "Preparation and characterization of PVDF/TiO2 hybrid membranes with ionic liquid modified nano-TiO2 particles", 《JOURNALOFMEMBRANESCIENCE》 * |
| FENGMEI SHI ET AL: "Preparation and characterization of PVDF/TiO2 hybrid membranes with ionic liquid modified nano-TiO2 particles", 《JOURNALOFMEMBRANESCIENCE》, vol. 427, 15 June 2013 (2013-06-15), pages 259 - 269 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114405292B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Recent advances of loose nanofiltration membranes for dye/salt separation | |
| Kheirieh et al. | Application and modification of polysulfone membranes | |
| Li et al. | Thermally reduced nanoporous graphene oxide membrane for desalination | |
| Gholami et al. | Impact of a new functionalization of multiwalled carbon nanotubes on antifouling and permeability of PVDF nanocomposite membranes for dye wastewater treatment | |
| Cui et al. | Emerging graphitic carbon nitride-based membranes for water purification | |
| Kang et al. | Application and modification of poly (vinylidene fluoride)(PVDF) membranes–a review | |
| Wang et al. | Designing high-performance nanofiltration membranes for high-salinity separation of sulfate and chloride in the chlor-alkali process | |
| Ma et al. | Water-stable metal–organic framework UiO-66 for performance enhancement of forward osmosis membranes | |
| Zhang et al. | Improving the hydrostability of ZIF-8 membrane by biomolecule towards enhanced nanofiltration performance for dye removal | |
| Boricha et al. | Preparation of N, O-carboxymethyl chitosan/cellulose acetate blend nanofiltration membrane and testing its performance in treating industrial wastewater | |
| Lee et al. | Performance, limitation, and opportunities of acid-resistant nanofiltration membranes for industrial wastewater treatment | |
| Kumari et al. | Recent advances in application of the graphene-based membrane for water purification | |
| Rahighi et al. | Two-dimensional materials in enhancement of membrane-based lithium recovery from metallic-ions-rich wastewaters: A review | |
| Vatanpour et al. | Polyvinyl alcohol-based separation membranes: a comprehensive review on fabrication techniques, applications and future prospective | |
| Zhang et al. | High-performance TFNC membrane with adsorption assisted for removal of Pb (II) and other contaminants | |
| Giwa et al. | Polymers for membrane filtration in water purification | |
| Xu et al. | Synthetic polymer materials for forward osmosis (FO) membranes and FO applications: a review | |
| Arjmandi et al. | Exploring the use of cheap natural raw materials to reduce the internal concentration polarization in thin-film composite forward osmosis membranes | |
| Yang et al. | Triethanolamine-based zwitterionic polyester thin-film composite nanofiltration membranes with excellent fouling-resistance for efficient dye and antibiotic separation | |
| Luo et al. | Cleanable natural-sugar-alcohol-based polyester membrane for highly efficient molecular separation | |
| Shi et al. | Advancements in material selection and application research for mixed matrix membranes in water treatment | |
| Shi et al. | Metal-organic framework membranes with varying metal ions for enhanced water and wastewater treatment: A critical review | |
| Li et al. | Construction of PDA-PEI/ZIF-L@ PE tight ultra-filtration (TUF) membranes on porous polyethylene (PE) substrates for efficient dye/salt separation | |
| Li et al. | Antifouling and chemical-resistant nanofiltration membrane modulated by a functionalized MWCNT interlayer for efficient dye/salt separation at high salinity | |
| Kumar et al. | Emerging trends in membrane-based wastewater treatment: electrospun nanofibers and reticular porous adsorbents as key components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |