CN117619153A - Preparation method of polyamide composite membrane and application of composite membrane - Google Patents
Preparation method of polyamide composite membrane and application of composite membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000004952 Polyamide Substances 0.000 title claims abstract description 29
- 229920002647 polyamide Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 56
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 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 28
- 229920002873 Polyethylenimine Polymers 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- 239000004695 Polyether sulfone Substances 0.000 claims description 17
- 229920006393 polyether sulfone Polymers 0.000 claims description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- IZQAUUVBKYXMET-UHFFFAOYSA-N 2-bromoethanamine Chemical compound NCCBr IZQAUUVBKYXMET-UHFFFAOYSA-N 0.000 claims description 7
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 7
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000108 ultra-filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 12
- 238000001728 nano-filtration Methods 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- 238000000926 separation method Methods 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000009295 crossflow filtration Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of preparation of polyamide composite membranes, and relates to a preparation method of a polyamide composite membrane and application of the composite membrane. The polyamide composite membrane with good selectivity and permeability is prepared by synthesizing a triamino quaternary ammonium salt monomer to participate in PEI/TMC interfacial polymerization process, and magnesium ions and lithium ions in water can be efficiently separated. The novel polyamide composite nanofiltration membrane prepared by the invention has compact and flat surface morphology, and the thickness of the PA layer is smaller. Excellent and stable membrane flux and rejection are exhibited in long-term filtration experiments.
Description
Technical Field
The invention relates to the technical field of preparation of polyamide composite membranes, and relates to a preparation method of a polyamide composite membrane and application of the composite membrane, in particular to application in magnesium-lithium separation.
Background
Lithium (Li) is a very strategically non-renewable resource, and as the lightest metal, it exhibits excellent properties such as high electrochemical activity, large specific heat capacity, high redox potential, low thermal expansion, etc., which makes it widely used in the leading edge fields of medicine, aerospace, batteries, etc. Along with the explosive growth of the demand for lithium ion batteries in recent years in the electric vehicles and energy storage industries, a drastic increase in Li consumption is caused. And the Li available for recycling is mainly distributed in the salt lake and accounts for nearly 70% of the global recoverable Li. In order to alleviate the shortage of Li resources, it is necessary to extract Li from salt lake brine containing a mixture of various ions through multi-step separation. Wherein magnesium isAnd Li->Since the ions have similar hydration radii and are difficult to separate, magnesium lithium ions (Mg 2+ /Li + ) The separation is a key ring for obtaining high-purity Li resources. In summary, there is an urgent need for an advanced material to efficiently separate Mg 2+ /Li + And (3) a mixture.
The pressure-driven nanofiltration membrane technology becomes Mg due to the advantages of low energy consumption, high separation efficiency and the like 2+ /Li + The technology with the most application prospect is separated. Due to Mg 2+ And Li (lithium) + Is very similar, so the charge characteristics of nanofiltration membranes are very similar for Mg 2+ /Li + The separation plays a key role. In other words, positively charged nanofiltration membranes favor Mg 2+ /Li + Thus polyamide Thin Film Composite Membrane (TFCM) vs. Mg prepared from Polyethylenimine (PEI) with a large number of positively charged amino groups by an Interfacial Polymerization (IP) process 2+ /Li + The separation shows relatively good selectivity, but there is still a problem that the selectivity and the permeability cannot be considered.
Chemical modification of the Polyamide (PA) layer of the TFCM may improve both the permeability and selectivity of the membrane to some extent. The addition of quaternary ammonium salt monomer during IP thus adjusts the free volume, charge characteristics and surface properties of the membrane, thereby allowing the membrane to be improved in both permeability and selectivity. The small molecular quaternary ammonium salt monomer with amine groups and the macromolecular polymer PEI jointly participate in the IP process, so that the interfacial reaction activity can be improved, the acyl chloride groups of TMC can react more fully, and the synthetic structure is more compact and compact, and has no defect of a PA layer. The selectivity of the membrane is expected to be further improved, and the high-purity Li is extracted with high efficiency.
Disclosure of Invention
The invention aims to overcome the technical problems mentioned in the background, and the polyamide composite membrane with good selectivity and permeability is prepared by synthesizing a triamino quaternary ammonium salt monomer to participate in PEI/TMC interfacial polymerization process, so that magnesium ions and lithium ions in water can be efficiently separated.
The first technical scheme of the invention is as follows: the synthesis of the triamino quaternary ammonium salt monomer comprises the following steps:
(1) Mixing 3, 5-diamino-1, 2, 4-triazole (DAT) and 2-bromoethylamine in a molar ratio of 1:1-3 thoroughly in dimethylformamide;
(2) Stirring and reacting in a water bath at constant temperature to obtain light green liquid, transferring, adding acetonitrile, and precipitating to obtain green oily matter;
(3) Separating the upper suspension, adding DMF, dissolving completely, adding acetonitrile, separating white floccule precipitate, centrifuging at high speed after ultrasound, pouring the upper suspension, transferring the residual white solid, and vacuum drying to obtain triamino quaternary ammonium salt monomer (DAT-NH) 2 ) Powder, prepared by the following reaction; :
the second technical scheme of the invention is as follows: the preparation of the polyamide composite membrane comprises the following steps:
(1) Mixing Polyethyleneimine (PEI) and DAT-NH with the mass concentration ratio of 5-10:1 2 Sodium Dodecyl Sulfate (SDS), na 2 CO 3 Sequentially adding a container with deionized water, and performing ultrasonic treatment until the deionized water is completely dissolved to obtain a water phase solution for later use;
(2) Adding 0.1-0.5wt% of trimesoyl chloride (TMC) into a container with normal hexane, and carrying out ultrasonic treatment until the trimesoyl chloride is completely dissolved to obtain an organic phase solution;
(3) Pouring the aqueous phase solution into a container, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the container for soaking for 5 minutes;
(4) After the PES film is extracted, the redundant liquid is sucked up;
(5) And fixing the polymer on a customized interfacial polymerization mold, adding an organic phase solution for full reaction, and drying to obtain the DAT/PEI-TMC polyamide composite film.
Further, the Polyethyleneimine (PEI) and DAT-NH in the step (1) 2 Mass concentration ratio is 6-8:1.
further, the mass concentration of trimesoyl chloride (TMC) in the step (2) is 0.3%.
The third technical scheme of the invention is as follows: the DAT/PEI-TMC polyamide composite membrane prepared by the method is used for efficiently separating magnesium ions and lithium ions in water.
The invention has the advantages that:
the invention provides a novel triamino quaternary ammonium salt monomer which participates in PEI/TMC interfacial polymerization process to prepare a polyamide composite membrane with good selectivity and permeability. Mg at an operating pressure of 6bar 2+ /Li + The separation factor is up to 40.3, and the permeation flux is up to 8.6LMH/bar. And exhibits good long-term stability while maintaining excellent separation performance. The method has excellent application value for efficiently extracting the high-purity Li.
The prepared novel polyamide composite nanofiltration membrane has compact and flat surface morphology, and the thickness of the PA layer is small. Excellent and stable membrane flux and rejection are exhibited in long-term filtration experiments.
Drawings
FIG. 1 is a graph of the morphology characterization of a DAT/PEI-TMC composite film;
(a) SEM images of film surface morphology;
(b) AFM image of film surface topography;
(c) TEM image of film cross-sectional morphology.
FIG. 2 is the pure water flux of the DAT/PEI-TMC composite membrane at different operating pressures.
FIG. 3 shows membrane permeabilities and separation factors for DAT/PEI-TMC composite membranes treating magnesium lithium ion mixed solutions at different operating pressures.
FIG. 4 is a graph showing performance of a DAT/PEI-TMC composite film over 120 hours of operation.
FIG. 5 is a schematic diagram of membrane structure and Mg2+/Li+ separation process.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific embodiments.
Example 1
(1) 8.4744g of 3, 5-diamino-1, 2, 4-triazole (DAT), 17.5386g of 2-bromoethylamine, 90mL of Dimethylformamide (DMF) were added to a 150mL flask and mixed;
(2) Placing the flask into a water bath kettle, stirring at the constant temperature of 45 ℃ in the water bath at 500r/min for reaction for 24 hours to obtain light green liquid, transferring the light green liquid into a 500mL beaker, adding 180mL acetonitrile, and precipitating green oily matter;
(3) Taking out the beaker from the water bath, separating the upper suspension by a pipetting gun, adding 10mL of DMF, adding 180mL of acetonitrile after complete dissolution, separating white floccule precipitate, putting into a high-speed centrifuge for rotation after ultrasonic treatment for 3 times, pouring out the upper suspension, transferring the residual white solid to a vacuum drying oven for drying at 40 ℃ for 2 hours, and obtaining the triamino quaternary ammonium salt monomer (DAT-NH) 2 ) And (3) powder.
(4) 0.46wt% of Polyethyleneimine (PEI), 0.04wt% of DAT-NH 2 0.1wt% Sodium Dodecyl Sulfate (SDS), 0.1wt% Na 2 CO 3 Sequentially adding a blue mouth bottle with deionized water, carrying out ultrasonic treatment until the blue mouth bottle is completely dissolved to obtain aqueous phase solution, and wrapping the bottle with tinfoil for standby;
(5) Adding 0.3wt% of trimesic chloride (TMC) into a blue mouth bottle with n-hexane, and carrying out ultrasonic treatment until the trimesic chloride is completely dissolved to obtain an organic phase solution;
(6) Pouring the aqueous phase solution into a culture dish, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the culture dish for soaking for 5 minutes;
(7) After the PES film is extracted, two pieces of filter paper are used for covering, the PES film is paved on a smooth glass plate, the PES film is lightly rolled by a roller, and redundant liquid is absorbed;
(8) Fixing the membrane on a customized Interfacial Polymerization (IP) mould, adding an organic phase solution for reaction for 1min, then placing the membrane in a 60 ℃ oven for further reaction for 30min to obtain a DAT/PEI-TMC composite membrane, and soaking the DAT/PEI-TMC composite membrane in deionized water for later use.
(9) The selectivity and permeability of the DAT/PEI-TMC polyamide composite membrane was evaluated using a cross-flow filtration device.
Example 2
(1) 8.4744g of 3, 5-diamino-1, 2, 4-triazole (DAT), 17.5386g of 2-bromoethylamine, 90mL of Dimethylformamide (DMF) were added to a 150mL flask and mixed;
(2) Placing the flask into a water bath kettle, stirring at the constant temperature of 45 ℃ in the water bath at 500r/min for reaction for 24 hours to obtain light green liquid, transferring the light green liquid into a 500mL beaker, adding 180mL acetonitrile, and precipitating green oily matter;
(3) Taking out the beaker from the water bath, separating the upper suspension by a pipetting gun, adding 10mL of DMF, adding 180mL of acetonitrile after complete dissolution, separating white floccule precipitate, putting into a high-speed centrifuge for rotation after ultrasonic treatment for 3 times, pouring out the upper suspension, transferring the residual white solid to a vacuum drying oven for drying at 40 ℃ for 2 hours, and obtaining the triamino quaternary ammonium salt monomer (DAT-NH) 2 ) And (3) powder.
(4) 0.45wt% of Polyethyleneimine (PEI), 0.05wt% of DAT-NH 2 0.1wt% Sodium Dodecyl Sulfate (SDS), 0.1wt% Na 2 CO 3 Sequentially adding a blue mouth bottle with deionized water, carrying out ultrasonic treatment until the blue mouth bottle is completely dissolved to obtain aqueous phase solution, and wrapping the bottle with tinfoil for standby;
(5) Adding 0.3wt% of trimesic chloride (TMC) into a blue mouth bottle with n-hexane, and carrying out ultrasonic treatment until the trimesic chloride is completely dissolved to obtain an organic phase solution;
(6) Pouring the aqueous phase solution into a culture dish, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the culture dish for soaking for 5 minutes;
(7) After the PES film is extracted, two pieces of filter paper are used for covering, the PES film is paved on a smooth glass plate, the PES film is lightly rolled by a roller, and redundant liquid is absorbed;
(8) Fixing the membrane on a customized Interfacial Polymerization (IP) mould, adding an organic phase solution for reaction for 1min, then placing the membrane in a 60 ℃ oven for further reaction for 30min to obtain a DAT/PEI-TMC composite membrane, and soaking the DAT/PEI-TMC composite membrane in deionized water for later use.
(9) The selectivity and permeability of the DAT/PEI-TMC polyamide composite membrane was evaluated using a cross-flow filtration device.
Example 3
(1) 8.4744g of 3, 5-diamino-1, 2, 4-triazole (DAT), 17.5386g of 2-bromoethylamine, 90mL of Dimethylformamide (DMF) were added to a 150mL flask and mixed;
(2) Placing the flask into a water bath kettle, stirring at the constant temperature of 45 ℃ in the water bath at 500r/min for reaction for 24 hours to obtain light green liquid, transferring the light green liquid into a 500mL beaker, adding 180mL acetonitrile, and precipitating green oily matter;
(3) Taking out the beaker from the water bath, separating the upper suspension by a pipetting gun, adding 10mL of DMF, adding 180mL of acetonitrile after complete dissolution, separating white floccule precipitate, putting into a high-speed centrifuge for rotation after ultrasonic treatment for 3 times, pouring out the upper suspension, transferring the residual white solid to a vacuum drying oven for drying at 40 ℃ for 2 hours, and obtaining the triamino quaternary ammonium salt monomer (DAT-NH) 2 ) And (3) powder.
(4) 0.44wt% of Polyethyleneimine (PEI), 0.06wt% of DAT-NH 2 0.1wt% Sodium Dodecyl Sulfate (SDS), 0.1wt% Na 2 CO 3 Sequentially adding a blue mouth bottle with deionized water, carrying out ultrasonic treatment until the blue mouth bottle is completely dissolved to obtain aqueous phase solution, and wrapping the bottle with tinfoil for standby;
(5) Adding 0.3wt% of trimesic chloride (TMC) into a blue mouth bottle with n-hexane, and carrying out ultrasonic treatment until the trimesic chloride is completely dissolved to obtain an organic phase solution;
(6) Pouring the aqueous phase solution into a culture dish, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the culture dish for soaking for 5 minutes;
(7) After the PES film is extracted, two pieces of filter paper are used for covering, the PES film is paved on a smooth glass plate, the PES film is lightly rolled by a roller, and redundant liquid is absorbed;
(8) Fixing the membrane on a customized Interfacial Polymerization (IP) mould, adding an organic phase solution for reaction for 1min, then placing the membrane in a 60 ℃ oven for further reaction for 30min to obtain a DAT/PEI-TMC composite membrane, and soaking the DAT/PEI-TMC composite membrane in deionized water for later use.
(9) The selectivity and permeability of the DAT/PEI-TMC polyamide composite membrane was evaluated using a cross-flow filtration device.
Example 4
(1) 8.4744g of 3, 5-diamino-1, 2, 4-triazole (DAT), 17.5386g of 2-bromoethylamine, 90mL of Dimethylformamide (DMF) were added to a 150mL flask and mixed;
(2) Placing the flask into a water bath kettle, stirring at the constant temperature of 45 ℃ in the water bath at 500r/min for reaction for 24 hours to obtain light green liquid, transferring the light green liquid into a 500mL beaker, adding 180mL acetonitrile, and precipitating green oily matter;
(3) Taking out the beaker from the water bath, separating the upper suspension by a pipetting gun, adding 10mL of DMF, adding 180mL of acetonitrile after complete dissolution, separating white floccule precipitate, putting into a high-speed centrifuge for rotation after ultrasonic treatment for 3 times, pouring out the upper suspension, transferring the residual white solid to a vacuum drying oven for drying at 40 ℃ for 2 hours, and obtaining the triamino quaternary ammonium salt monomer (DAT-NH) 2 ) And (3) powder.
(4) 0.42wt% of Polyethyleneimine (PEI), 0.08wt% of DAT-NH 2 0.1wt% Sodium Dodecyl Sulfate (SDS), 0.1wt% Na 2 CO 3 Sequentially adding a blue mouth bottle with deionized water, carrying out ultrasonic treatment until the blue mouth bottle is completely dissolved to obtain aqueous phase solution, and wrapping the bottle with tinfoil for standby;
(5) Adding 0.3wt% of trimesic chloride (TMC) into a blue mouth bottle with n-hexane, and carrying out ultrasonic treatment until the trimesic chloride is completely dissolved to obtain an organic phase solution;
(6) Pouring the aqueous phase solution into a culture dish, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the culture dish for soaking for 5 minutes;
(7) After the PES film is extracted, two pieces of filter paper are used for covering, the PES film is paved on a smooth glass plate, the PES film is lightly rolled by a roller, and redundant liquid is absorbed;
(8) Fixing the membrane on a customized Interfacial Polymerization (IP) mould, adding an organic phase solution for reaction for 1min, then placing the membrane in a 60 ℃ oven for further reaction for 30min to obtain a DAT/PEI-TMC composite membrane, and soaking the DAT/PEI-TMC composite membrane in deionized water for later use.
(9) The selectivity and permeability of the DAT/PEI-TMC polyamide composite membrane was evaluated using a cross-flow filtration device.
Example 5
(1) 8.4744g of 3, 5-diamino-1, 2, 4-triazole (DAT), 17.5386g of 2-bromoethylamine, 90mL of Dimethylformamide (DMF) were added to a 150mL flask and mixed;
(2) Placing the flask into a water bath kettle, stirring at the constant temperature of 45 ℃ in the water bath at 500r/min for reaction for 24 hours to obtain light green liquid, transferring the light green liquid into a 500mL beaker, adding 180mL acetonitrile, and precipitating green oily matter;
(3) Taking out the beaker from the water bath, separating the upper suspension by a pipetting gun, adding 10mL of DMF, adding 180mL of acetonitrile after complete dissolution, separating white floccule precipitate, putting into a high-speed centrifuge for rotation after ultrasonic treatment for 3 times, pouring out the upper suspension, transferring the residual white solid to a vacuum drying oven for drying at 40 ℃ for 2 hours, and obtaining the triamino quaternary ammonium salt monomer (DAT-NH) 2 ) And (3) powder.
(4) 0.38wt% of Polyethyleneimine (PEI), 0.12wt% of DAT-NH 2 0.1wt% Sodium Dodecyl Sulfate (SDS), 0.1wt% Na 2 CO 3 Sequentially adding a blue mouth bottle with deionized water, carrying out ultrasonic treatment until the blue mouth bottle is completely dissolved to obtain aqueous phase solution, and wrapping the bottle with tinfoil for standby;
(5) Adding 0.3wt% of trimesic chloride (TMC) into a blue mouth bottle with n-hexane, and carrying out ultrasonic treatment until the trimesic chloride is completely dissolved to obtain an organic phase solution;
(6) Pouring the aqueous phase solution into a culture dish, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the culture dish for soaking for 5 minutes;
(7) After the PES film is extracted, two pieces of filter paper are used for covering, the PES film is paved on a smooth glass plate, the PES film is lightly rolled by a roller, and redundant liquid is absorbed;
(8) Fixing the membrane on a customized Interfacial Polymerization (IP) mould, adding an organic phase solution for reaction for 1min, then placing the membrane in a 60 ℃ oven for further reaction for 30min to obtain a DAT/PEI-TMC composite membrane, and soaking the DAT/PEI-TMC composite membrane in deionized water for later use.
(9) The selectivity and permeability of the DAT/PEI-TMC polyamide composite membrane was evaluated using a cross-flow filtration device.
In summary, as shown in fig. 1 to 4, the novel polyamide composite nanofiltration membrane prepared by the research has a relatively compact and flat surface morphology, and the PA layer thickness is relatively small. Excellent and stable membrane flux and rejection are exhibited in long-term filtration experiments.
The composite membrane prepared by the research meets the industrial requirement, and provides guidance and technical methods for efficiently extracting high-purity Li. The invention is not limited to the specific embodiments described above, which are intended to be illustrative only and not limiting, as many variations can be made by a person skilled in the art without departing from the spirit of the invention, which fall within the protection of the invention.
Claims (5)
1. The synthesis of the triamino quaternary ammonium salt monomer comprises the following steps:
(1) Mixing 3, 5-diamino-1, 2, 4-triazole (DAT) and 2-bromoethylamine in a molar ratio of 1:1-3 thoroughly in dimethylformamide;
(2) Stirring and reacting in a water bath at constant temperature to obtain light green liquid, transferring, adding acetonitrile, and precipitating to obtain green oily matter;
(3) By separating the suspension of the upper layer,adding DMF, dissolving completely, adding acetonitrile, separating white floccule precipitate, centrifuging at high speed after ultrasound, pouring out upper suspension, transferring the rest white solid, and vacuum drying to obtain triamino quaternary ammonium salt monomer (DAT-NH) 2 ) Powder, prepared by the following reaction:
2. the preparation method of the polyamide composite membrane is characterized by comprising the following steps:
(1) Mixing Polyethyleneimine (PEI) and DAT-NH with the mass concentration ratio of 5-10:1 2 Sodium Dodecyl Sulfate (SDS), na 2 CO 3 Sequentially adding a container with deionized water, and performing ultrasonic treatment until the deionized water is completely dissolved to obtain a water phase solution for later use;
(2) Adding 0.1-0.5wt% of trimesoyl chloride (TMC) into a container with normal hexane, and carrying out ultrasonic treatment until the trimesoyl chloride is completely dissolved to obtain an organic phase solution;
(3) Pouring the aqueous phase solution into a container, drying the water by using a polyether sulfone (PES) ultrafiltration membrane soaked in deionized water for 12 hours, and then placing the water into the container for soaking for 5 minutes;
(4) After the PES film is extracted, the redundant liquid is sucked up;
(5) And fixing the polymer on a customized interfacial polymerization mold, adding an organic phase solution for full reaction, and drying to obtain the DAT/PEI-TMC polyamide composite film.
3. The method according to claim 2, wherein the step (1) comprises mixing Polyethyleneimine (PEI) with DAT-NH 2 Mass concentration ratio is 6-8:1.
4. the preparation method according to claim 2, wherein the mass concentration of trimesic chloride (TMC) in the step (2) is 0.3%.
5. The DAT/PEI-TMC polyamide composite membrane prepared by the method of claims 2-4 is used for efficiently separating magnesium ions and lithium ions in water.
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