CN110756065B - Hydrotalcite-like nanosheet modified separation membrane, and preparation method and application thereof - Google Patents
Hydrotalcite-like nanosheet modified separation membrane, and preparation method and application thereof Download PDFInfo
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- CN110756065B CN110756065B CN201911044977.2A CN201911044977A CN110756065B CN 110756065 B CN110756065 B CN 110756065B CN 201911044977 A CN201911044977 A CN 201911044977A CN 110756065 B CN110756065 B CN 110756065B
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- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 238000000926 separation method Methods 0.000 title claims abstract description 65
- 239000002135 nanosheet Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 57
- 239000002131 composite material Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 238000012695 Interfacial polymerization Methods 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 45
- 230000004907 flux Effects 0.000 abstract description 28
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- 239000010410 layer Substances 0.000 description 13
- 229920002647 polyamide Polymers 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- -1 acetate radical Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D69/06—Flat membranes
-
- 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
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The preparation method comprises the step of coating and converting a casting solution, wherein the casting solution contains the hydrotalcite-like nanosheets. The mutual synergistic action between the hydrotalcite-like compound and the hydrophilic polymer ensures that the hydrophilic polymer is stabilized in the membrane and cannot be separated out in the phase inversion process, thereby reducing the using amount of the hydrophilic polymer and reducing the pollution to the water environment. In addition, the preparation process of the porous separation membrane is simple in process and low in cost, and has very important significance for realizing application. Under the same test conditions, the separation membrane prepared by the method has the characteristics of high flux, good hydrophilicity and high mechanical strength.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a membrane material and a preparation method thereof.
Background
Membrane separation is a physical process in which no phase change occurs. Techniques for achieving separation by using a polymeric membrane as the selective separation layer to allow certain components to permeate while retaining other components in the mixture. At present, the method is applied to the fields of seawater desalination, wastewater treatment, food and medicine, energy and the like. The separation membrane is the core of the membrane separation process, and the quality of the membrane performance determines the operation cost of the membrane separation process and whether the membrane separation process can be popularized on a large scale. Therefore, separation membranes with high flux, high rejection, and contamination resistance are desired.
Currently, most commercial separation membranes are prepared by phase inversion of polymers, which is usually performed by dissolving polymers in organic solvents to obtain a casting solution with a certain concentration, coating the casting solution into a liquid film, and converting the liquid film in a non-solvent (usually water) to obtain a porous separation membrane. In order to improve the flux of separation and contamination resistance, a hydrophilic polymer is generally used as a membrane material for preparing a porous separation membrane. However, since the hydrophilic polymer is less stable in water, it is easily precipitated from the porous membrane into water during phase inversion, which causes loss of the amount of the hydrophilic polymer; meanwhile, the precipitated hydrophilic polymer can cause serious pollution to the water environment.
The nano material as a modified material promotes the physical and chemical properties of the porous separation membrane. In the prior art, the conventional method is to directly blend and modify a porous separation membrane with a nano material to improve the flux and the hydrophilicity of the membrane, and the core of the function is the nano material. For example: CN 105056768A reports a technical scheme of modifying a support layer of a forward osmosis composite membrane by using spherical hydrotalcite-like nano-particles and co-particles, and the support layer is a hydrotalcite-like composite porous support layer membrane which has more excellent porosity, hydrophilicity and flux. Hydrotalcite-like compounds are Layered metal hydroxides (LDHs) which have high specific surface area, good hydrophilicity and good catalytic performance; meanwhile, the material also has heat resistance and radiation resistance, and is a good two-dimensional inorganic nano material. The stripped hydrotalcite-like nanosheets are commonly used in the fields of catalysis, supercapacitors, light-emitting devices, flame retardants and the like.
Disclosure of Invention
The invention aims to provide a porous separation membrane which reduces the use amount of hydrophilic polymers, is environment-friendly and has better performance.
Therefore, the invention firstly provides a preparation method of the hydrotalcite-like nano-sheet modified separation membrane, which comprises the step of coating and converting a casting solution, wherein the casting solution contains the hydrotalcite-like nano-sheets.
Unlike the prior art method of blending hydrotalcite-like compounds to modify porous separation membranes, the present invention does not rely on the proven effects of hydrotalcite-like compounds. Tests prove that the hydrotalcite-like compound is more suitable to be defined as a fixing material to play a role. The mutual synergistic effect between the hydrophilic polymer and the hydrophilic polymer ensures that the hydrophilic polymer is stabilized in the membrane and cannot be separated out in the phase inversion process, thereby reducing the using amount of the hydrophilic polymer and reducing the pollution to the water body environment. In addition, the preparation process of the porous separation membrane is simple in process and low in cost, and has very important significance for realizing application. Under the same test conditions, the porous separation membrane prepared by the invention has the characteristics of high flux, good hydrophilicity and high mechanical strength. Accordingly, it is another aspect of the present invention to provide a hydrotalcite-like nanosheet-modified separation membrane prepared by the above-described method. Based on the application of the porous separation membrane of the present invention as described above, the present invention further provides a composite membrane comprising: the porous separation membrane of the present invention and the composite membrane obtained by performing interfacial polymerization on the surface of the porous separation membrane are provided.
Drawings
The invention is illustrated in figure 5:
FIG. 1 shows the turbidity of the NMP solvent and hydrotalcite-like stripping solution;
FIG. 2 is turbidity of the gel bath;
FIG. 3 is a UV-Vis spectroscopy spectrum of a gel bath;
FIG. 4 is a pure water flux of a porous separation membrane;
FIG. 5 is water flux and reverse salt flux of composite membranes
Detailed Description
The core technical scheme of the invention is to provide a method for preparing a porous separation membrane with reduced amount and environmental protection, and the main technical purposes comprise preparation of the porous separation membrane, reduction of the using amount of a hydrophilic polymer and improvement of membrane performance. In an improved technical scheme about the preparation method, a step of coating and converting a casting solution is included, and the core technology is characterized in that the casting solution containing hydrotalcite-like nano-sheets is used. More specifically, the content of the hydrotalcite-like nanosheets in the casting solution is 0.1-1 wt%. Preferably, the content of the hydrotalcite-like nano-sheets is 0.3-0.5 wt%.
In a specific embodiment, a hydrotalcite-like compound stripping solution is added into the casting solution to obtain a casting solution containing hydrotalcite-like compound nanosheets; the hydrotalcite-like compound is selected from hydrotalcite-like compounds with nitrate radical, acetate radical, lactate radical and stearate radical intercalation; the organic solvent is selected from one or a mixture of more of formamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone. Nitrate intercalated magnesium aluminium hydrotalcite is preferred.
The above hydrotalcite-like exfoliating solution can be prepared by referring to the prior art in the field, and as a specific embodiment, the hydrotalcite-like exfoliating solution is prepared by mechanically exfoliating hydrotalcite-like in an organic solvent. In order to obtain the technical effect required by the invention, the concentration of the hydrotalcite-like nanosheet in the obtained hydrotalcite-like stripping liquid is ensured to be 1-10 g L-1. The hydrotalcite-like stripping liquid plays a role in fixing a hydrophilic polymer material, and the selection of the concentration of the hydrotalcite-like stripping liquid influences important parameters such as the pore size, the pore distribution, the porosity and the like of the prepared porous separation membrane; the examples of the invention fully demonstrate the 1,2,4 and 6g L tested-1The hydrotalcite-like compound stripping liquid under the condition of equal concentration can meet the technical requirements of the invention and realize corresponding technical effects.
On the other hand, in the solution of the present invention, the casting solution further contains a hydrophilic polymer, but the polymer in the casting solution is much less limited. It is easily understood based on the core technical solution of the present invention that, supported by the prior art conditions, polymers capable of constructing porous separation membranes can be used in the present invention, and the polymers are selected from but not limited to one or a mixture of more of polysulfone, polyethersulfone, polyphenylenesulfone, polyvinylidene fluoride, polybenzimidazole, sulfonated polysulfone, sulfonated polyethersulfone, and sulfonated polyetheretherketone; sulfonated polysulfone, sulfonated polyethersulfone, and sulfonated polyetheretherketone are preferred.
On the other hand, the hydrotalcite-like nano-scale stripping solution used in the present invention is also well reported in the prior art, and can be described according to the existing records in the field of nano-materials (appl.clay sci.55(2012) 18-26), and its general formula is: [ M ] A(II) 1-xM(III) x(OH)2]x+[(An-)x/n·mH2O]x-Wherein M is(II)May be Mg2+、Cu2+、Co2+、Zn2+、Ni2+Any divalent metal ion; m(III)May be Al3+、Ti3+、Fe3+、Cr3+And the like, any trivalent metal ion; a. then-Can be NO3 –、SO4 2–、PO4 3–One or more of inorganic, organic or complex anions such as stearate, lactate, lauryl sulfate and fatty acid radical. The hydrotalcite-like stripping solution capable of stripping is formed by preferably selecting metal cations and interlayer anions suitable for stripping, wherein the interlayer anions are preferably nitrate radical, acetate radical, lactate radical and stearate radical intercalated hydrotalcite-like.
Finally, in the preparation of the casting solution, the solvent used is an organic solvent selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or tetrahydrofuran. It is to be understood that this is by way of illustration and not of limitation.
In a more specific embodiment, the preparation method of the hydrotalcite-like nanosheet modified separation membrane comprises the following steps:
the first step is as follows: and (3) synthesizing hydrotalcite-like particles. The hydrotalcite-like particles can be synthesized by the traditional coprecipitation method, hydrothermal method, solvothermal method, urea method and the like. The synthesized hydrotalcite-like particles are washed with deionized water to pH 7, and then thoroughly washed and dried with an organic solvent such as acetone, methanol, or ethanol for use.
The second step is that: preparing hydrotalcite-like compound stripping liquid and casting liquid. And dispersing hydrotalcite-like compound with certain mass in an organic solvent, stirring, and carrying out ultrasonic treatment for a period of time to obtain hydrotalcite-like compound stripping liquid with certain concentration. And adding a polymer into the stripping solution, and stirring and defoaming to obtain the hydrotalcite-like nanosheet/polymer membrane casting solution.
The third step: and (3) coating the casting solution on a smooth glass plate or spinning in a spinning machine, then soaking in water for 12 hours, and performing phase inversion to obtain the flat plate type or hollow fiber porous separation membrane.
Further, the invention provides a porous separation membrane prepared according to any of the above technical schemes; and carrying out reaction on the surface of the porous separation membrane layer to obtain the composite membrane.
Generally, a composite membrane includes a porous separation membrane layer and a polyamide active layer, and the polyamide active layer is obtained by interfacial polymerization at the surface of the porous separation membrane. The selection of the polyamide active layer in the specific embodiments, based on the description above, can be carried out by a person skilled in the art on the basis of the description of such composite films in the prior art. The following will further explain the preparation process of the composite film.
In the present invention, the preparation of the composite membrane includes the steps of sequentially immersing the dense side of the porous separation membrane in an amine solution and an acid chloride solution, and then performing a thermal polymerization process. In a specific embodiment, the mass concentration of the amine solution is 1-5 wt%, the solvent is water, and the amine is selected from, but not limited to, m-phenylenediamine, p-phenylenediamine and piperazine; the mass concentration of the acyl chloride solution is 0.05-0.5%, and the solvent is selected from but not limited to n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, Isopar E or Isopar G.
A further specific method of preparing the composite membrane can be described as: immersing the compact side of the porous separation membrane into 1-5 wt% of amine water solution for 1-3 min, and removing redundant solution on the surface after taking out; then putting the porous support layer soaked by the amine into 0.05-0.5 wt% of acyl chloride solution for 1-3 min; taking out, carrying out heat treatment for 1-3 min, then respectively washing with 200ppm of sodium hypochlorite aqueous solution and 1000ppm of sodium bisulfite aqueous solution, and finally carrying out heat treatment for 2min to obtain the composite film. Wherein the temperature of the heat treatment is determined according to the specific selected amine substance and acid chloride substance, and the prior art can be referred to.
In a more specific embodiment, the method for preparing the composite membrane comprises the following steps:
immersing the dense side of the porous separation membrane into 1-5 wt% of amine water solution for 2min, taking out, and blowing off redundant solution droplets on the surface by using an air knife; then placing the compact side into 0.05-0.5 wt% of acyl chloride solution for 1-3 min; taking out, performing heat treatment for 2min by using 95-degree deionized water, respectively washing for 2min and 0.5min by using 200ppm of sodium hypochlorite aqueous solution and 1000ppm of sodium bisulfite aqueous solution, taking out, and performing heat treatment for 2min by using 95-degree deionized water to obtain the composite film.
The technical effect of the present invention will be further explained with reference to the following non-limiting examples. It is to be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any manner. Unless otherwise indicated, the data described in this section of this specification is measured/calculated using the following parameters:
in the evaluation of the porous separation membrane, pure water flux (L m) was used-2h-1bar-1) Evaluating the performance of the porous separation membrane; in the evaluation of the composite membrane performance, the water flux (L m)-2h-1) The water permeability, reverse salt flux of the composite membrane was evaluated (g m)-2h-1) The salt rejection performance of the composite membrane was evaluated.
Example 1
The preparation method of the porous separation membrane comprises the following specific steps:
(1) 9.6g Mg (NO)3)2·6H2O and 4.7g Al (NO)3)3·9H2O is added with 50ml of pure water to prepareAs a salt solution, it was added dropwise to 2.12g of NaNO3Adding 50ml of water solution prepared by pure water, controlling the pH value to be 10 by using 3.4M NaOH, stirring for 1h, transferring into a reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12h to obtain MgAl-NO3Hydrotalcite-like compounds. Then, the solution was washed with pure water to pH 7, washed 3 times with acetone, and dried at 100 degrees for use.
The prepared MgAl-NO is mixed3Adding hydrotalcite-like compound into N-methylpyrrolidone solvent, and stirring to obtain the final product with concentration of 1,2,4, 6g L-1The turbidity of the hydrotalcite-like release agent (2) is shown in FIG. 1.
(2) Adding hydrophilic sulfonated polysulfone (sPSf) into an N-methylpyrrolidone solvent, stirring and dissolving, and then adding polysulfone (PSf) to obtain the polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Wherein the sulfonated polysulfone accounts for 0 wt%, 5 wt%, 10 wt% and 15 wt% of the total polymer, i.e. PSf, PSf/sPSf5、PSf/sPSf10And PSf/sPSf15. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtainedx(x-5, 10,15) a porous separation membrane.
(3) A porous separation membrane of a hydrophilic polymer fixed by hydrotalcite-like nano-sheets. Adding 5 wt% of sulfonated polysulfone (sPSf) into hydrotalcite-like compound stripping liquid with different concentrations, stirring and dissolving, and then adding polysulfone (PSf) to obtain the hydrotalcite-like compound nanosheet/polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtained5-LDHx(x is 1,2,4,6) porous separation membrane, x corresponding to the concentration of hydrotalcite-like release fluid. In addition, in order to explain the effect of the hydrotalcite-like compound having the hydrophilic polymer immobilized thereon, the turbidity of the gel bath was compared, as shown in FIG. 2. In addition, uv-vis spectroscopy characterization (fig. 3) also demonstrated that as the amount of stripping solution increased, the precipitated sulfonated polysulfone decreased.
The performance of the prepared porous separation membrane was evaluated at 25 ℃. The measuring method comprises the following steps: the pressure is tested to be 1bar by adopting a cross-flow filtration mode and taking deionized water as a raw material liquid. The performance of the prepared porous separation membrane is shown in fig. 4.
The results of the comparative test groups, with the same preparation process parameters and test conditions, include:
(1) the pure water flux of PSf of the porous separation membrane without adding the hydrophilic sPSf was 96.7L m-2h-1bar-1。
(2) Porous separation membrane PSf/sPSf added with 5 wt% of hydrophilic sPSf5Has a pure water flux of 146.3L m-2h- 1bar-1(ii) a Porous separation membrane PSf/sPSf added with 10 wt% of hydrophilic sPSf10Has a pure water flux of 181.6L m-2h-1bar-1(ii) a Porous separation membrane PSf/sPSf added with 15 wt% of hydrophilic sPSf15Has a pure water flux of 226.5L m-2h-1bar-1。
(3) Porous separation membrane PSf/sPSf at 5 wt% sPSf5Based on (2), adding 4g L-1After the hydrotalcite-like compound stripping solution (accounting for 0.34 wt% of the total amount of the membrane casting solution) is fixed, the porous separation membrane PSf/sPSf5-LDH4Has a pure water flux of 212.8L m-2h-1bar-1Higher than PSf/sPSf5And PSf/sPSf10A porous separation membrane.
Example 2
The preparation method of the composite membrane comprises the following specific steps:
(1) 9.6g Mg (NO)3)2·6H2O and 4.7g Al (NO)3)3·9H2O was added to 50ml of pure water to prepare a salt solution, which was added dropwise to 2.12g of NaNO3Adding 50ml of water solution prepared by pure water, controlling the pH value to be 10 by using 3.4M NaOH, stirring for 1h, transferring into a reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12h to obtain MgAl-NO3Hydrotalcite-like compounds. Then, the solution was washed with pure water to pH 7, washed 3 times with acetone, and dried at 100 degrees for use. A certain amount of MgAl-NO is added3Adding hydrotalcite-like compound into N-methylpyrrolidone solvent, and stirring to obtain a mixture with certain concentration (1, 2,4 and 6g L)-1) The hydrotalcite-like compound stripping solution of (1).
(2) Hydrophilic sulfonated polysulfone (sPSf)) Adding the solution into an N-methyl pyrrolidone solvent, stirring and dissolving, and then adding polysulfone (PSf) to obtain a polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Wherein the sulfonated polysulfone accounts for 0 wt%, 5 wt%, 10 wt% and 15 wt% of the total polymer, i.e. PSf, PSf/sPSf5、PSf/sPSf10And PSf/sPSf15. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtainedx(x-5, 10,15) a porous separation membrane.
(3) A porous separation membrane of a hydrophilic polymer fixed by hydrotalcite-like nano-sheets. Adding 5 wt% of sulfonated polysulfone (sPSf) into hydrotalcite-like compound stripping liquid with different concentrations, stirring and dissolving, and then adding polysulfone (PSf) to obtain the hydrotalcite-like compound nanosheet/polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtained5-LDHx(x is 1,2,4,6) porous separation membrane, x corresponding to the concentration of hydrotalcite-like release fluid.
(4) And (2) putting the compact side of the prepared porous separation membrane into a 3.4 wt% m-phenylenediamine aqueous solution for 2min, taking out, blowing off redundant solution droplets on the surface by using an air knife, putting the compact side into a 0.15 wt% 1,3, 5-benzene tricarboxychloride Isopar-G organic solution for 1min, taking out, performing heat treatment on the compact side for 2min by using 95-degree deionized water, soaking the compact side in 200ppm sodium hypochlorite aqueous solution and 1000ppm sodium bisulfite aqueous solution for 2min and 0.5min respectively, taking out, and performing heat treatment on the compact side for 2min by using 95-degree deionized water to obtain a Polyamide (PA) active layer, namely the composite membrane.
The performance of the prepared composite membrane was evaluated at 25 ℃. The measuring method comprises the following steps: by adopting a cross-flow filtration mode, deionized water is taken as raw material liquid, 1mol/L sodium chloride is taken as driving liquid, the interception layer of the membrane faces to one side of the driving liquid, and the porous supporting layer faces to the side of the raw material liquid, and the performance of the prepared composite membrane is shown in figure 5.
The results of the comparative test groups, with the same preparation process parameters and test conditions, include:
(1) the water flux of the composite membrane PA @ PSf without adding the hydrophilic sPSf is 18.2L m-2h-1Reverse salt flux of 5.1g m-2h-1。
(2) Composite membrane PA @ PSf/sPSf added with 5 wt% of hydrophilic sPSf5Has a water flux of 35.7L m-2h-1Reverse salt flux of 7.3g m-2h-1(ii) a Composite membrane PA @ PSf/sPSf added with 10 wt% of hydrophilic sPSf10Has a water flux of 40.1L m-2h-1Reverse salt flux of 8.7g m-2h-1(ii) a 15 wt% of hydrophilic sPSf composite membrane PA @ PSf/sPSf is added15Has a water flux of 48.4L m-2h-1Reverse salt flux of 9.3g m-2h-1。
(3) Porous separation membrane PSf/sPSf at 5 wt% sPSf5Based on (2), adding 4g L-1After being fixed, the hydrotalcite-like compound stripping liquid (0.34 wt% of the total amount of the casting solution) is subjected to interfacial polymerization reaction to obtain a composite membrane PA @ PSf/sPSf5-LDH4Has a water flux of 51.7L m-2h-1Higher than PA @ PSf/sPSf5、PA@PSf/sPSf10And PA @ PSf/sPSf15The water flux of (a); reverse salt flux of 9.5g m-2h-1。
The foregoing is illustrative and explanatory only, and it is intended that the present invention be covered by the appended claims, as well as the appended claims, which are appended or substituted in their equivalents.
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