CN115487691A - Positively charged high-flux composite nanofiltration membrane for lithium extraction in salt lake and preparation method thereof - Google Patents
Positively charged high-flux composite nanofiltration membrane for lithium extraction in salt lake and preparation method thereof Download PDFInfo
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- CN115487691A CN115487691A CN202211332844.7A CN202211332844A CN115487691A CN 115487691 A CN115487691 A CN 115487691A CN 202211332844 A CN202211332844 A CN 202211332844A CN 115487691 A CN115487691 A CN 115487691A
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- 239000012528 membrane Substances 0.000 title claims abstract description 141
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000605 extraction Methods 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000243 solution Substances 0.000 claims abstract description 82
- 229920001661 Chitosan Polymers 0.000 claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 67
- 239000008346 aqueous phase Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 21
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000004907 flux Effects 0.000 claims abstract description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 210000004379 membrane Anatomy 0.000 claims description 48
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 210000002469 basement membrane Anatomy 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 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 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000010410 layer Substances 0.000 description 29
- 239000002585 base Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000108 ultra-filtration Methods 0.000 description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000000159 acid neutralizing agent Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of separation membrane composite materials, and discloses a positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes and a preparation method thereof. The preparation method of the composite nanofiltration membrane comprises the following steps: 1) Preparing quaternized chitosan modified mesoporous nano silicon dioxide; 2) Preparing an organic phase solution: dissolving acyl chloride monomer with at least two acyl chloride groups in a solvent to obtain an organic phase solution; 3) Preparing an aqueous solution: dissolving polyethyleneimine in water, adding a surfactant, an acid neutralizer and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing to obtain an aqueous phase solution; 4) Interfacial polymerization reaction: contacting a base membrane with the aqueous phase solution, removing the redundant aqueous phase solution on the surface of the base membrane, and contacting the base membrane with the organic phase solution to generate an interfacial polymerization reaction to obtain an intermediate membrane body; 5) And (3) post-treatment: and carrying out heat treatment on the intermediate film body to obtain the film. The composite nanofiltration membrane prepared by the invention has excellent divalent salt interception performance and high water flux.
Description
Technical Field
The invention relates to the technical field of separation membrane composite materials, in particular to a positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes and a preparation method thereof.
Background
Lithium is naturally present in pegmatite such as spodumene and lepidolite as solid lithite, and is present in salt lake brine, underground brine and seawater as lithium ions. At present, lithium extraction from salt lake brine is a main source of global lithium salt production, and a nanofiltration technology becomes a novel extraction technology aiming at salt lake mining with high magnesium-lithium ratio.
Nanofiltration is a membrane separation technology between ultrafiltration and reverse osmosis, and has the advantages of low operating pressure, high separation efficiency, low operating cost and the like. The preparation method of the composite nanofiltration membrane comprises the following steps: phase inversion, blending, charging and compounding. Among them, the most widely used and most effective method is the complex method. The composite method can involve two steps of preparing a base membrane and an ultrathin surface layer of the nanofiltration membrane. The nanofiltration membrane is mainly a phase inversion method, and the preparation method of the membrane surface layer is most commonly an interfacial polymerization method.
At present, the market mostly gives priority to negatively charged nanofiltration membranes, but with the increase of the complexity of the separation system and the improvement of the requirements on the membrane separation performance, such as the separation of multivalent cations and some small cationic molecules, the negatively charged nanofiltration membranes have poor effects, and therefore, positively charged nanofiltration membranes are more and more concerned by research. The positively charged nanofiltration membrane has the advantages of acid and alkali resistance, microbial pollution resistance and the like, and has greater advantages in the aspects of separating high-valence metal ions such as Mg2+, ca2+, and the like, purifying amino acid and cationic dye which are lower than isoelectric points and the like compared with the conventional nanofiltration membrane.
Chinese patent publication No. CN112755817 discloses a composite nanofiltration membrane with high performance, a preparation method and application thereof, the composite nanofiltration membrane comprises a porous ultrafiltration basement membrane and a polyamide selective separation layer arranged on the basement membrane, the polyamide selective separation layer is mainly formed by interfacial polymerization reaction of polyamine monomers and polybasic acyl chloride monomers under the regulation and control action of a surfactant, one of the adopted implementation modes is that polyethyleneimine and trimesoyl chloride are subjected to interfacial polymerization on a polyether sulfone ultrafiltration basement membrane, and the obtained polyamide separation layer is compact and influences the water flux of the nanofiltration membrane.
Chinese patent publication No. CN102794116 discloses a mesoporous silica microsphere-polymer nano composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane is obtained by forming an aromatic polymer functional skin layer loaded with mesoporous silica spheres on a porous support membrane. The mesoporous silica microspheres in the composite layer have a mesoporous structure, and are beneficial to the transmission of substances, so that the nanofiltration membrane has better permeability, hydrophilicity and pollution resistance, but the dispersibility of the mesoporous silica microspheres in the composite membrane is poor, the improvement of the silica microspheres on the performance of the nanofiltration membrane is influenced, and in addition, the mesoporous silica microspheres are dispersed in the separation layer of the nanofiltration membrane to reduce the pressure resistance of the separation layer of the nanofiltration membrane, so that the separation layer is broken.
Disclosure of Invention
The invention provides a positively charged high-flux composite nanofiltration membrane for lithium extraction in salt lakes, a preparation method and application thereof, aiming at overcoming the technical problems. The composite nanofiltration membrane prepared by the method has good hydrophilic property and pressure resistance, so that the water capacity of the composite nanofiltration membrane is improved, and the service life of the composite nanofiltration membrane is prolonged.
In order to realize the purpose, the invention adopts the following technical scheme:
the preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes comprises the following steps:
1) Preparing quaternized chitosan modified mesoporous nano silicon dioxide;
2) Preparing an organic phase solution: dissolving acyl chloride monomer with at least two acyl chloride groups in a solvent to obtain an organic phase solution;
3) Preparing an aqueous solution: dissolving polyethyleneimine in water, adding a surfactant, an acid neutralizer and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing to obtain an aqueous phase solution;
4) Interfacial polymerization reaction: contacting a base membrane with the aqueous phase solution, removing the redundant aqueous phase solution on the surface of the base membrane, and contacting the base membrane with the organic phase solution to generate an interfacial polymerization reaction to obtain an intermediate membrane body;
5) And (3) post-treatment: and carrying out heat treatment on the intermediate film body to obtain the film.
In the prior art, polyethyleneimine and trimesoyl chloride are conventionally used as reaction monomers and are subjected to interfacial polymerization reaction on the surface of an ultrafiltration base membrane, so that a positively charged separation layer is synthesized on the surface of the ultrafiltration base membrane, the separation layer has a high rejection rate on divalent cations due to positive charge, but polyethyleneimine belongs to a high molecular organic substance and contains more amino groups on molecules, and the amino groups react with the acyl chloride groups of the trimesoyl chloride to generate a compact separation layer, so that the water flux of the composite nanofiltration membrane is low. Also add mesoporous silica in the separating layer among the prior art, because there is the infiltration passageway in hydrophilic group and the inside on mesoporous silica surface to improve the water flux of compound nanofiltration membrane (see background art for details, this is no longer described), but the further problem that exists is: (1) The mesoporous silica is easy to agglomerate and cannot be well and uniformly dispersed in a separation layer of the composite nanofiltration membrane, a smooth permeation channel is difficult to form in the separation layer, and the improvement of the mesoporous silica on the water permeation flux of the nanofiltration membrane is influenced; (2) After the mesoporous silica is added into the separation layer of the nanofiltration membrane, the pressure resistance of the separation layer is influenced, and the separation layer of the nanofiltration membrane is easy to crack under the action of water body pressure, so that the service life of the composite nanofiltration membrane is influenced. In order to solve the technical problems, the modified mesoporous silica particles are added into the composite nanofiltration membrane separation layer, so that mesoporous silica is uniformly dispersed in the nanofiltration membrane separation, the compressive strength of the nanofiltration membrane separation layer is improved, and the service life of the composite nanofiltration membrane is prolonged.
Preferably, the acid chloride monomer in the step 2) is at least one of trimesoyl chloride and pyromellitic chloride.
Preferably, the mass concentration of the acyl chloride monomer in the organic phase solution in the step 2) is 0.01-1%.
Preferably, the molecular weight of the polyethyleneimine in the step 3) is 10000-25000Da; the mass concentration of the polyethyleneimine in the aqueous phase solution is 0.1-2%.
Preferably, the mass concentration of the quaternized chitosan modified mesoporous nano-silica in the aqueous phase solution in the step 3) is 0.05-0.5%.
Preferably, the material of the base membrane in the step 4) is one of polysulfone, polyethersulfone, polyvinylidene fluoride and polyacrylonitrile.
Preferably, the base membrane in step 4) is a hollow fiber membrane, a flat sheet membrane or a tubular membrane.
Preferably, the preparation method of the quaternized chitosan modified mesoporous nano-silica in the step 1) comprises the following steps:
a) Taking mesoporous silica and an epoxy silane coupling agent as raw materials, and grafting the epoxy silane coupling agent on the surface of mesoporous silica nanoparticles to obtain coupling agent modified mesoporous silica nanoparticles;
b) The epoxy group grafted on the coupling agent modified mesoporous silica nano particle and the amino group on the quaternary ammonium salt chitosan are subjected to ring-opening reaction, and the molecular weight of the quaternary ammonium salt chitosan is 1500-2000Da;
c) And performing post-treatment to obtain the quaternized chitosan modified mesoporous nano silicon dioxide.
The method for modifying the mesoporous nano-silica comprises the steps of grafting an epoxy coupling agent on the surface of the mesoporous silica to load an epoxy group on the surface of the mesoporous silica, and then utilizing the epoxy group to perform an open loop reaction with an amino group on the surface of quaternary ammonium salt chitosan, so that the quaternary ammonium salt chitosan is grafted on the surface of mesoporous silica particles. Meanwhile, the quaternary ammonium salt chitosan is positively charged and dispersed in the nanofiltration membrane separation layer, so that the charge on the surface of the composite nanofiltration membrane is not reduced, and the high interception performance of divalent cations can be kept.
On the other hand, quaternary ammonium salt chitosan is grafted on the surfaces of the mesoporous silica particles to form a dendritic wrapped core structure, and the quaternary ammonium salt chitosan is uniformly inserted into a separation layer of the nanofiltration membrane to form a skeleton reinforcing structure, so that the compressive strength of the composite nanofiltration membrane separation layer is enhanced, and the service life of the composite nanofiltration membrane is prolonged. Through further research, the dendritic wrapped core structure formed inside the separation layer is related to the molecular weight of quaternary ammonium salt chitosan, when the molecular weight of the chitosan is smaller than the range required by the invention, the molecular chain of the quaternary ammonium salt chitosan is too short, a framework structure cannot be formed in the nanofiltration membrane separation layer, when the molecular weight of the chitosan is smaller than the range required by the invention, the molecular chain of the quaternary ammonium salt chitosan is too long, the molecular chain of the quaternary ammonium salt chitosan cannot be fully extended, and a framework reinforcing structure is difficult to form, and the invention enables the composite nanofiltration membrane separation layer to have good compression resistance by controlling the molecular weight of the quaternary ammonium salt chitosan to be 1500-2000 Da.
The positively charged high-flux composite nanofiltration membrane for lithium extraction in salt lakes is prepared by the method.
The application of the positively charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes is disclosed, and the composite nanofiltration membrane is applied to the fields of hard water softening, seawater desalination or lithium extraction from salt lakes.
The beneficial technical effects of the invention are as follows:
1) Under the action of electrostatic repulsion, the mesoporous silicon dioxide can be uniformly dispersed in an aqueous phase solution and further uniformly dispersed in the nanofiltration membrane separation, a smooth permeation channel is formed in a separation layer of the composite nanofiltration membrane, and the water flux of the composite nanofiltration membrane is improved;
2) The quaternary ammonium salt chitosan is positively charged and dispersed in the nanofiltration membrane separation layer, so that the charge quantity on the surface of the composite nanofiltration membrane is not reduced, and the high interception performance on divalent cations can be maintained;
3) Quaternary ammonium salt chitosan is grafted on the surfaces of the mesoporous silica particles to form a dendritic wrapped core structure, and the quaternary ammonium salt chitosan is uniformly inserted into a separation layer of the nanofiltration membrane to form a skeleton reinforcing structure, so that the compressive strength of the composite nanofiltration membrane separation layer is enhanced, and the service life of the composite nanofiltration membrane is prolonged.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Furthermore, the embodiments of the present invention described in the following description are generally only a part of the embodiments of the present invention, and not all of the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or those prepared by a conventional method of the open literature by those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all methods known to those skilled in the art.
The following examples are representative, relatively representative, test recordings of recordings made during the course of research and development of the protocol of the present invention, but are not intended to be exhaustive and do not limit the scope of the invention.
The quaternized chitosan used in the specific embodiment of the invention is O-2-hydroxypropyl trimethyl ammonium chloride chitosan with a molecular formula of NH 2 -CS-CH 2 OCH 2 CH(OH)CH 2 N + Me 3 Cl - 。
Example 1
The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes comprises the following steps:
1) Preparing the quaternized chitosan modified mesoporous nano-silica:
a) Adding 0.2g of mesoporous nano-silica into 20mL of toluene, performing ultrasonic dispersion for 30min, then adding 0.05g of gamma-glycidoxypropyltrimethoxysilane (KH-560), reacting for 6h at 70 ℃, performing centrifugal separation, and drying to obtain coupling agent modified mesoporous nano-silica;
b) Adding quaternized chitosan with molecular weight of 2000Da into deionized water, stirring and dissolving to prepare a quaternized chitosan solution with mass concentration of 0.6%, dropwise adding a hydrochloric acid solution to adjust pH to 5, adding the coupling agent modified mesoporous nano-silica into the quaternized chitosan solution, stirring at normal temperature for 12h, standing for 5h, adjusting the pH of the solution to be neutral, centrifuging, washing with water, and drying to obtain quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving a trimesoyl chloride monomer in a normal hexane solvent to prepare a trimesoyl chloride solution with the mass concentration of 0.8%;
3) Preparing an aqueous solution: dissolving polyethyleneimine with the molecular weight of 20000Da in water, adding a surfactant sodium dodecyl sulfate, an acid neutralizing agent triethylamine and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing by ultrasonic oscillation to obtain an aqueous phase solution, wherein the mass concentration of the polyethyleneimine in the aqueous phase solution is 1.5%, the mass concentration of the sodium dodecyl sulfate is 0.05%, the mass concentration of the triethylamine is 0.5%, and the concentration of the quaternized chitosan modified mesoporous nano-silica is 0.3%;
4) Interfacial polymerization reaction: soaking a polyether sulfone ultrafiltration flat plate base membrane in an aqueous phase solution for 2min, removing redundant aqueous phase solution on the surface of the base membrane, and soaking the base membrane in an organic phase solution for interfacial polymerization for 50s to obtain an intermediate membrane body;
5) And (3) post-treatment: and (3) placing the intermediate film body in an oven to perform thermosetting crosslinking for 15min at the temperature of 60 ℃ to obtain the film.
Comparative example 1
The difference between the comparative example 1 and the example 1 is that no quaternized chitosan modified mesoporous nano-silica is added to the aqueous phase solution.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the quaternized chitosan modified mesoporous nano-silica in the aqueous phase solution is replaced by the common nano-silica.
A cross-flow experimental device is adopted to test the ion interception performance and the pure water flux of the composite nanofiltration membrane, the test condition is that the environmental temperature is 25 ℃, the test pressure is 0.3MPa, and the test concentrations of magnesium sulfate, magnesium chloride and calcium chloride are 2000ppm.
Compared with the nanofiltration membrane performance test of the comparative example, the embodiment can obtain that the pure water flux of the nanofiltration membrane is obviously improved by doping the quaternized chitosan modified mesoporous nano-silica into the nanofiltration membrane, and the divalent cation interception effect is slightly improved.
Example 2
The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from the salt lake comprises the following steps:
1) Preparing the quaternized chitosan modified mesoporous nano-silica:
a) Adding 0.2g of mesoporous nano-silica into 20mL of toluene, performing ultrasonic dispersion for 30min, then adding 0.05g of gamma-glycidoxypropyltrimethoxysilane (KH-560), reacting for 6h at 70 ℃, performing centrifugal separation, and drying to obtain coupling agent modified mesoporous nano-silica;
b) Adding quaternized chitosan with the molecular weight of 1500Da into deionized water, stirring and dissolving to prepare a quaternized chitosan solution with the mass concentration of 0.6%, dropwise adding a hydrochloric acid solution to adjust the pH value to 5, adding the coupling agent modified mesoporous nano-silica into the quaternized chitosan solution, stirring at normal temperature for 12h, standing for 5h, adjusting the pH value of the solution to be neutral, centrifuging, washing with water, and drying to obtain quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving a trimesoyl chloride monomer in a normal hexane solvent to prepare a trimesoyl chloride solution with the mass concentration of 0.05%;
3) Preparing an aqueous solution: dissolving polyethyleneimine with the molecular weight of 12000Da in water, adding surfactant lauryl sodium sulfate, acid neutralizing agent triethylamine and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing by ultrasonic oscillation to obtain an aqueous phase solution, wherein the mass concentration of the polyethyleneimine in the aqueous phase solution is 0.3%, the mass concentration of the lauryl sodium sulfate is 0.05%, the mass concentration of the triethylamine is 0.5%, and the concentration of the quaternized chitosan modified mesoporous nano-silica is 0.08%;
4) Interfacial polymerization: firstly soaking a polyether sulfone ultrafiltration flat base membrane in an aqueous phase solution for 2min, then removing redundant aqueous phase solution on the surface of the base membrane, and then soaking the base membrane in an organic phase solution for interfacial polymerization for 50s to obtain an intermediate membrane body;
5) And (3) post-treatment: and (3) placing the intermediate film body in an oven to carry out thermosetting crosslinking for 15min at the temperature of 60 ℃ to obtain the film.
Comparative example 3
Comparative example 3 differs from example 2 in that the quaternized chitosan was replaced with a quaternized chitosan with a molecular weight of 1200 Da.
Comparative example 4
Comparative example 4 differs from example 2 in that the quaternized chitosan was replaced with a quaternized chitosan with a molecular weight of 2500 Da. A cross-flow experimental device is adopted to test the ion rejection performance of the composite nanofiltration membrane, under the test conditions that the environmental temperature is 25 ℃, the test pressure is 0.5MPa, and the test solution is 2000ppm magnesium sulfate, the composite nanofiltration membrane is stably operated for 30min, and then the change of the rejection rate of the nanofiltration membrane on the magnesium sulfate is tested after the composite nanofiltration membrane is respectively operated for 5 days, 10 days, 20 days, 30 days and 50 days.
| 5D | 10D | 30D | 50D | |
| Example 2 | 99.1％ | 99.0％ | 99.0％ | 98.8％ |
| Comparative example 3 | 98.5％ | 98.2％ | 97.5％ | 95.6％ |
| Comparative example 4 | 99.3％ | 98.6％ | 96.2％ | 93.1％ |
According to the test results, the composite nanofiltration membrane in the example 2 still maintains high magnesium sulfate rejection performance after running for 50D, while the nanofiltration membranes in the comparative examples 3 and 4 have no obvious short-term change in magnesium sulfate rejection performance, but have obvious reduction in magnesium sulfate rejection performance after long-term running for 50D.
Example 3
The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes comprises the following steps:
1) Preparing the quaternized chitosan modified mesoporous nano-silica:
a) Adding 0.2g of mesoporous nano-silica into 20mL of toluene, performing ultrasonic dispersion for 30min, then adding 0.05g of gamma-glycidoxypropyltrimethoxysilane (KH-560), reacting for 6h at 70 ℃, performing centrifugal separation, and drying to obtain coupling agent modified mesoporous nano-silica;
b) Adding quaternized chitosan with molecular weight of 2000Da into deionized water, stirring and dissolving to prepare a quaternized chitosan solution with mass concentration of 0.6%, dropwise adding a hydrochloric acid solution to adjust pH to 5, adding the coupling agent modified mesoporous nano-silica into the quaternized chitosan solution, stirring at normal temperature for 12h, standing for 5h, adjusting the pH of the solution to be neutral, centrifuging, washing with water, and drying to obtain quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving a trimesoyl chloride monomer in a normal hexane solvent to prepare a trimesoyl chloride solution with the mass concentration of 0.5 percent;
3) Preparing an aqueous solution: dissolving polyethyleneimine with the molecular weight of 20000Da in water, adding surfactant lauryl sodium sulfate, acid neutralizing agent triethylamine and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing by ultrasonic oscillation to obtain an aqueous phase solution, wherein the mass concentration of the polyethyleneimine in the aqueous phase solution is 1.0%, the mass concentration of the lauryl sodium sulfate is 0.05%, the mass concentration of the triethylamine is 0.5%, and the concentration of the quaternized chitosan modified mesoporous nano-silica is 0.2%;
4) Interfacial polymerization reaction: firstly soaking a polyether sulfone ultrafiltration flat base membrane in an aqueous phase solution for 2min, then removing redundant aqueous phase solution on the surface of the base membrane, and then soaking the base membrane in an organic phase solution for interfacial polymerization for 50s to obtain an intermediate membrane body;
5) And (3) post-treatment: and (3) placing the intermediate film body in an oven to carry out thermosetting crosslinking for 15min at the temperature of 60 ℃ to obtain the film.
Example 4
The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from the salt lake comprises the following steps:
1) Preparing the quaternized chitosan modified mesoporous nano-silica:
a) Adding 0.2g of mesoporous nano-silica into 20mL of toluene, performing ultrasonic dispersion for 30min, then adding 0.05g of gamma-glycidoxypropyltrimethoxysilane (KH-560), reacting for 6h at 70 ℃, performing centrifugal separation, and drying to obtain coupling agent modified mesoporous nano-silica;
b) Adding quaternized chitosan with the molecular weight of 2000Da into deionized water, stirring and dissolving to prepare a quaternized chitosan solution with the mass concentration of 0.6%, dropwise adding a hydrochloric acid solution to adjust the pH value to 5, adding the coupling agent modified mesoporous nano-silica into the quaternized chitosan solution, stirring at normal temperature for 12h, standing for 5h, adjusting the pH value of the solution to be neutral, centrifuging, washing with water, and drying to obtain quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving a trimesoyl chloride monomer in a normal hexane solvent to prepare a trimesoyl chloride solution with the mass concentration of 0.01 percent;
3) Preparing an aqueous solution: dissolving polyethyleneimine with the molecular weight of 20000Da in water, adding a surfactant of sodium dodecyl sulfate, an acid neutralizing agent of triethylamine and quaternized chitosan modified mesoporous nano-silica, and dispersing uniformly by ultrasonic oscillation to obtain an aqueous phase solution, wherein the mass concentration of the polyethyleneimine in the aqueous phase solution is 0.1%, the mass concentration of the sodium dodecyl sulfate is 0.05%, the mass concentration of the triethylamine is 0.5%, and the concentration of the quaternized chitosan modified mesoporous nano-silica is 0.05%;
4) Interfacial polymerization: soaking a polyether sulfone ultrafiltration flat plate base membrane in an aqueous phase solution for 2min, removing redundant aqueous phase solution on the surface of the base membrane, and soaking the base membrane in an organic phase solution for interfacial polymerization for 50s to obtain an intermediate membrane body;
5) And (3) post-treatment: and (3) placing the intermediate film body in an oven to carry out thermosetting crosslinking for 15min at the temperature of 60 ℃ to obtain the film.
Example 5
The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from salt lakes comprises the following steps:
1) Preparing the quaternized chitosan modified mesoporous nano-silica:
a) Adding 0.2g of mesoporous nano-silica into 20mL of toluene, performing ultrasonic dispersion for 30min, then adding 0.05g of gamma-glycidoxypropyltrimethoxysilane (KH-560), reacting for 6h at 70 ℃, performing centrifugal separation, and drying to obtain coupling agent modified mesoporous nano-silica;
b) Adding quaternized chitosan with the molecular weight of 2000Da into deionized water, stirring and dissolving to prepare a quaternized chitosan solution with the mass concentration of 0.6%, dropwise adding a hydrochloric acid solution to adjust the pH value to 5, adding the coupling agent modified mesoporous nano-silica into the quaternized chitosan solution, stirring at normal temperature for 12h, standing for 5h, adjusting the pH value of the solution to be neutral, centrifuging, washing with water, and drying to obtain quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving a trimesoyl chloride monomer in a normal hexane solvent to prepare a trimesoyl chloride solution with the mass concentration of 1%;
3) Preparing an aqueous solution: dissolving polyethyleneimine with the molecular weight of 25000Da in water, adding surfactant lauryl sodium sulfate, acid neutralizing agent triethylamine and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing by ultrasonic oscillation to obtain an aqueous phase solution, wherein the mass concentration of the polyethyleneimine in the aqueous phase solution is 2%, the mass concentration of the lauryl sodium sulfate is 0.05%, the mass concentration of the triethylamine is 0.5%, and the concentration of the quaternized chitosan modified mesoporous nano-silica is 0.5%;
4) Interfacial polymerization: firstly soaking a polyether sulfone ultrafiltration flat base membrane in an aqueous phase solution for 2min, then removing redundant aqueous phase solution on the surface of the base membrane, and then soaking the base membrane in an organic phase solution for interfacial polymerization for 50s to obtain an intermediate membrane body;
5) And (3) post-treatment: and (3) placing the intermediate film body in an oven to carry out thermosetting crosslinking for 15min at the temperature of 60 ℃ to obtain the film.
Comparative example 5
The comparative example 5 is a composite nanofiltration membrane with high performance disclosed in chinese patent publication No. CN112755817 (nanofiltration membrane obtained by interfacial polymerization reaction of polyethyleneimine and trimesoyl chloride monomer in example 13). The composite nanofiltration membrane prepared in the embodiment 4 of the invention is tested according to the test conditions of the comparative example 5 (the test environment temperature is 25 ℃, the test pressure is 4bar, and the salt concentration is 20 mmol/L), and the test results are as follows:
the contrast results show that the rejection performance of the composite nanofiltration membrane on divalent salt and the pure water flux of the composite nanofiltration membrane are higher than those of the composite nanofiltration membrane in the comparative example 5, and the composite nanofiltration membrane provided by the invention has excellent rejection performance on divalent ions and water flux. In addition, the rejection rate of the composite nanofiltration membrane prepared by the invention to lithium chloride can reach 21.6%, and the rejection rate to magnesium chloride is as high as 98.2%, so that the composite nanofiltration membrane has a good separation effect on magnesium and lithium ions.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the appended claims.
Claims (9)
1. The preparation method of the positively charged high-flux composite nanofiltration membrane for extracting lithium from the salt lake is characterized by comprising the following steps of:
1) Preparing quaternized chitosan modified mesoporous nano-silica;
2) Preparing an organic phase solution: dissolving acyl chloride monomers with at least two acyl chloride groups in a solvent to obtain an organic phase solution;
3) Preparing an aqueous solution: dissolving polyethyleneimine in water, adding a surfactant, an acid neutralizer and quaternized chitosan modified mesoporous nano-silica, and uniformly dispersing to obtain an aqueous phase solution;
4) Interfacial polymerization reaction: contacting a base membrane with the aqueous phase solution, removing the redundant aqueous phase solution on the surface of the base membrane, and contacting the base membrane with the organic phase solution to generate an interfacial polymerization reaction to obtain an intermediate membrane body;
5) And (3) post-treatment: and carrying out heat treatment on the intermediate film body to obtain the film.
2. The method for preparing the positively-charged high-flux composite nanofiltration membrane for lithium extraction from the salt lake according to claim 1, wherein the acid chloride monomer in the step 2) is at least one of trimesoyl chloride and pyromellitic chloride.
3. The preparation method of the positively charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein the mass concentration of the acid chloride monomer in the organic phase solution in the step 2) is 0.01-1%.
4. The preparation method of the positively-charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein in the step 3), the molecular weight of the polyethyleneimine is 10000-25000Da;
the mass concentration of the polyethyleneimine in the aqueous phase solution is 0.1-2%.
5. The preparation method of the positively charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein the mass concentration of the quaternized chitosan modified mesoporous nano-silica in the aqueous phase solution in the step 3) is 0.05-0.5%.
6. The preparation method of the positively charged high flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein the material of the basement membrane in the step 4) is one of polysulfone, polyethersulfone, polyvinylidene fluoride and polyacrylonitrile.
7. The preparation method of the positively-charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein the base membrane in the step 4) is a hollow fiber membrane, a flat membrane or a tubular membrane.
8. The preparation method of the positively charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes according to claim 1, wherein the preparation method of the quaternized chitosan modified mesoporous nano-silica in the step 1) comprises the following steps:
taking mesoporous silica and an epoxy silane coupling agent as raw materials, and grafting the epoxy silane coupling agent on the surface of mesoporous silica nanoparticles to obtain coupling agent modified mesoporous silica nanoparticles;
the epoxy group grafted on the coupling agent modified mesoporous silica nano particle and the amino group on the quaternized chitosan are subjected to ring opening reaction, and the molecular weight of the quaternized chitosan is 1500-2000Da;
and performing post-treatment to obtain the quaternized chitosan modified mesoporous nano silicon dioxide.
9. A positively charged high-flux composite nanofiltration membrane for lithium extraction from salt lakes, which is characterized by being prepared by the method as claimed in any one of claims 1 to 9.
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