CN114247297A - Nanofiltration membrane and preparation method thereof - Google Patents
Nanofiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN114247297A CN114247297A CN202111586385.0A CN202111586385A CN114247297A CN 114247297 A CN114247297 A CN 114247297A CN 202111586385 A CN202111586385 A CN 202111586385A CN 114247297 A CN114247297 A CN 114247297A
- Authority
- CN
- China
- Prior art keywords
- membrane
- cucurbituril
- nanofiltration membrane
- monomer
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 126
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 12
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 41
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010668 complexation reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 8
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 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 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 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
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 30
- 150000002500 ions Chemical class 0.000 description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 24
- 108091006146 Channels Proteins 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 19
- 238000000926 separation method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 14
- 239000004202 carbamide Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 230000004907 flux Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- 239000007832 Na2SO4 Substances 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 238000010612 desalination reaction Methods 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 235000009852 Cucurbita pepo Nutrition 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 150000001408 amides Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 241000219122 Cucurbita Species 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000284466 Antarctothoa delta Species 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present disclosure provides a nanofiltration membrane and a preparation method thereof, wherein the method comprises: contacting the support film with an aqueous solution of a complex monomer to obtain the support film adsorbing the complex monomer, wherein the complex monomer is formed by cucurbituril molecules and amino-containing polymers; contacting a support membrane for adsorbing a complex monomer with an organic phase solution containing a polybasic acyl chloride monomer, and carrying out interfacial polymerization reaction to obtain a nascent state nanofiltration membrane, wherein the nascent state nanofiltration membrane has an amino complexation cucurbituril molecular channel structure; and (3) carrying out heat treatment on the nascent nanofiltration membrane to obtain the nanofiltration membrane with the amino complexation cucurbituril molecular channel structure.
Description
Technical Field
The disclosure relates to the technical field of nanofiltration membrane separation, in particular to a nanofiltration membrane and a preparation method thereof.
Background
The industrial wastewater usually contains NaCl and Na2SO4Mixed salts, etc., which cause not only serious damage to the ground water and soil, but also waste of a large amount of raw materials. On the one hand, the need for further improvement of the product quality is increasing for the purification process. On the other hand, wastewater treatment in these industries is still an urgent challenge to realize zero discharge recycling of wastewater and sustainable development.
The membrane separation technology has the advantages of high separation efficiency, convenient operation, energy conservation, emission reduction and the like, and is widely applied to industrial production and water treatment.
The aperture of the nanofiltration membrane is generally about 0.5-2 nm, small molecules with the molecular weight of 100-2000 Da can be intercepted, effective interception of the small molecules and high-valence ions is realized through the synergistic effect of aperture screening and the southward effect, and the nanofiltration membrane has a good application prospect. However, most inorganic salts are electrically neutral, anions and cations interact in the form of hydrated ion pairs, and on the premise of keeping high flux, the existing nanofiltration membrane cannot realize separation of salts with different valence states and desalination of organic matter molecular solution.
Disclosure of Invention
In view of the above technical problems, the present disclosure provides a nanofiltration membrane and a preparation method thereof, so as to at least partially solve the above technical problems.
In order to solve the technical problem, the technical scheme of the disclosure is as follows:
a method for preparing a nanofiltration membrane comprises the following steps:
contacting the support film with an aqueous solution of a complex monomer to obtain the support film adsorbing the complex monomer, wherein the complex monomer is formed by cucurbituril molecules and amino-containing polymers;
contacting the support membrane for adsorbing the complex monomer with an organic phase solution containing a polybasic acyl chloride monomer, and carrying out interfacial polymerization reaction to obtain a nascent-state nanofiltration membrane, wherein the nascent-state nanofiltration membrane has an amino complexation cucurbituril molecular channel structure;
and (3) carrying out heat treatment on the nascent nanofiltration membrane to obtain the nanofiltration membrane with the amino complexation cucurbituril molecular channel structure.
In one embodiment, the above cucurbituril molecule has a cavity diameter size range including: 0.4-1.0 nm;
the above-mentioned amino group-containing polymer includes: one or more of polyvinylamine, polyethyleneimine and polyetheramine.
In one embodiment, the above-mentioned polybasic acid chloride monomer comprises: one or more of 1,3, 5-trimesoyl chloride, terephthaloyl chloride, glutaryl chloride and 1, 3-benzene disulfonyl chloride.
In one embodiment, the film material of the support film includes any one of the following:
polyethylene, polypropylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone, polyethersulfone, polyimide, polytetrafluoroethylene, and alumina.
In one embodiment, the mass ratio of the cucurbituril molecule to the amino-containing polymer ranges include: 1: 2-10: 2;
the concentration range of the polybasic acyl chloride monomer comprises the following steps: 1 to 10 g.L-1。
In one embodiment, the reaction time range for the cucurbituril molecule and the amino group-containing polymer to form a complex includes: 1-24 h.
In one embodiment, the time range for contacting the support membrane with the aqueous solution of the complex monomer comprises: 10-120 min;
the temperature range of the aqueous monomer solution includes: 15 to 40 ℃.
In one embodiment, the time range for contacting the support membrane adsorbing the complex monomer with the organic phase solution containing the polyacid chloride monomer includes: 10-600 s;
the temperature range of the contact reaction includes: 15 to 40 ℃.
In one embodiment, the temperature range of the heat treatment includes: 50-90 ℃;
the time range of the above heat treatment includes: 1-10 min.
Another aspect of the disclosure provides a nanofiltration membrane prepared by the method in the above embodiment.
According to the technical scheme, the nanofiltration membrane and the preparation method thereof provided by the embodiment of the disclosure have at least one of the following beneficial effects:
(1) in the embodiment of the disclosure, because the cucurbituril molecules have a special cavity structure, the cucurbituril molecules are strung together by utilizing chain-shaped amino molecules to form a continuous channel to obtain a pseudo-rotaxane complex of amino composite cucurbituril molecules, and then the complex and polyacyl chloride are subjected to interfacial polymerization reaction to form a hydrophilic and continuous through amino composite cucurbituril molecule channel with an amide structure end capping, namely a nascent state nanofiltration membrane, wherein the nanofiltration membrane has high crosslinking degree and compactness.
(2) The nanofiltration membrane utilizes a cavity structure with a specific size of cucurbituril, so that monovalent ions, divalent ions and multivalent ions which are difficult to separate in a salt solution can be separated, and the nanofiltration membrane has good selectivity; or realizing the desalination of organic molecule solution, the purification of mixed salt solution and the desalination of dye/drug molecule solution.
(3) The nanofiltration membrane has a continuous through molecular channel structure, so that the permeation flux of the nanofiltration membrane is high, and the nanofiltration membrane also has good long-term operation stability.
Drawings
Figure 1 is a flow diagram of a method of preparing nanofiltration membranes according to an embodiment of the disclosure;
FIG. 2 is a surface scanning electron micrograph of a support film in example 1 of the present disclosure;
figure 3 is a scanning electron microscope image of the surface of the nanofiltration membrane in example 1 of the present disclosure;
fig. 4 is a scanning electron microscope image of a cross section of the nanofiltration membrane in example 1 of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to the accompanying drawings in combination with the embodiments.
Cucurbituril molecules are organic matters with specific cavity structures, are widely introduced and used as transmission channels, and particularly, the cucurbituril molecules and amino-containing molecules or amino polymers interact through hydrogen bonds or ion dipoles, long-chain amino molecules or amino polymers and the cucurbituril molecules form a string-shaped complex, and then the long-chain amino molecules or amino polymers and the cucurbituril molecules are polymerized with polybasic acyl chloride monomers to form a continuous through nanofiltration membrane channel.
The existing nanofiltration membranes have low permeability and selectivity for specific targets, such as monovalent and divalent salt separation, desalination of organic molecules, and the like. This is because in aqueous solutions of inorganic salts, the anions and cations interact as hydrated ion pairs, the number and density of charges of the ions being different, and the presence of these factors results in nanofiltration membranes that are generally less selective for monovalent and divalent salts. Therefore, the disclosure provides a nanofiltration membrane and a preparation method thereof, and by using the specific cavity size of the cucurbituril molecule, ions with a valence state with a smaller ionic radius can easily pass through the nanofiltration membrane with a cucurbituril molecule channel structure, and ions with a larger ionic radius cannot pass through the nanofiltration membrane. And by utilizing the characteristic that the surface of the cucurbituril molecule has a certain positive charge, for ions with the same valence state, the anion passing rate through the nanofiltration membrane is higher than the cation passing rate in the same valence state. Based on the characteristics of the cucurbituril molecular channel, monovalent ions, divalent ions and multivalent ions can be selectively separated, and the desalination of organic molecular solution, the purification of mixed salt solution and the desalination of dye/drug molecular solution can be realized, so that the cucurbituril molecular channel has good selectivity. Meanwhile, the nano-filtration membrane has a channel structure, so that the higher water molecule transmission rate of the nano-filtration membrane is provided.
Fig. 1 is a flow chart of a method for preparing a nanofiltration membrane in an embodiment of the disclosure.
As shown in fig. 1, the preparation method of the nanofiltration membrane comprises the following steps: step S101 to step S103.
In step S101, the support film is contacted with an aqueous solution of a complex monomer formed from a cucurbituril molecule and an amino group-containing polymer to obtain a support film on which the complex monomer is adsorbed.
According to the embodiment of the disclosure, cucurbituril molecules and amino-containing polymers are reacted, and the amino-containing polymers are strung together to form a complex through the interaction of hydrogen bonds or ion dipoles, so that the pseudo rotaxane of the amino-compound cucurbituril molecules is obtained. Then the aqueous phase solution of the complex monomer is contacted with the supporting membrane, and the supporting membrane absorbing the complex monomer can be obtained.
In step S102, the support membrane adsorbing the complex monomer is contacted with an organic phase solution containing a polyacyl chloride monomer to perform an interfacial polymerization reaction, thereby obtaining a nascent nanofiltration membrane, wherein the nascent nanofiltration membrane has an amino-complexed cucurbituril molecular channel structure.
According to the embodiment of the disclosure, a support membrane for adsorbing a complex monomer is contacted with a monomer organic solution containing polybasic acyl chloride, and at an interface, amino molecules on the surface of cucurbituril molecules react with the acyl chloride to generate amino compound cucurbituril molecule channels with end-capped amide structures, namely nascent nanofiltration membranes.
In step S103, the nascent nanofiltration membrane is subjected to heat treatment to obtain the nanofiltration membrane with the amino complexation cucurbituril molecular channel structure.
According to the embodiment of the disclosure, the nascent nanofiltration membrane is subjected to heat treatment, so that the molecular structures are more stable and the membrane is solidified.
According to the embodiment of the disclosure, because the cucurbituril molecules have a cavity structure with a specific size, the cucurbituril molecules are connected in series by utilizing an amino-containing polymer to form a continuous channel, so as to obtain a pseudo-rotaxane complex of amino composite cucurbituril molecules, and then an aqueous solution containing a complex monomer and an organic phase solution containing a polybasic acyl chloride monomer are subjected to an amide reaction to form a hydrophilic and continuous through amino composite cucurbituril molecule channel with an amide structure end capping, namely a nascent state nanofiltration membrane, wherein the nanofiltration membrane has high crosslinking degree and compactness. By utilizing the cavity structure of the cucurbituril molecule with a specific size, monovalent ions which are difficult to separate in a salt solution can be separated from divalent ions and multivalent ions, and the cucurbituril molecule has good selectivity; or realizing the desalination of organic molecule solution, the purification of mixed salt solution and the desalination of dye/drug molecule solution.
According to an embodiment of the present disclosure, the range of cavity diameter sizes of cucurbituril molecules includes: 0.4 to 1.0 nm.
According to embodiments of the present disclosure, cucurbituril molecules within a range of cavity diameter sizes comprise: gourds [5]Urea (C)30H30N20O10CAS:259886-49-2), cucurbit [6]Urea (C)36H36N24O12CAS:80262-44-8), cucurbit [7]Urea (C)42H42N28O14CAS:259886-50-5), cucurbit [8]Urea (C)48H48N32O16CAS:259886-51-6), cucurbit [10]Urea (C)60H60N40O20CAS: 307001-50-9).
Through the embodiment of the disclosure, by utilizing the cavity structure with special size of cucurbituril molecule, valence state ions with different particle sizes can be selectively separated.
According to embodiments of the present disclosure, an amino-containing polymer includes: one or more of polyvinylamine, polyethyleneimine and polyetheramine, wherein the polyethyleneimine is more preferable and has the molecular weight of 600-70000 Da.
According to an embodiment of the present disclosure, the film material of the support film includes any one of:
polyethylene, polypropylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone, polyethersulfone, polyimide, polytetrafluoroethylene, and alumina.
According to an embodiment of the present disclosure, the polybasic acid chlorides include: one or more of 1,3, 5-trimesoyl chloride, terephthaloyl chloride, glutaryl chloride and 1, 3-benzene disulfonyl chloride;
organic solutions include, but are not limited to: one or more of C5-C10 alkanes, wherein the C5-C10 alkanes can be selected from n-hexane, cyclopentane, n-heptane, cyclohexane, etc.
According to embodiments of the present disclosure, the mass ratio range of the cucurbituril molecule to the amino-containing polymer includes: 1: 2-10: 2, and can be selected from 1:2, 2:2, 3:2, 4:2, 5:2, 6:2, 7:2, 8:2, 9:2, 10:2 and the like.
According to an embodiment of the present disclosure, the mass concentration range of cucurbituril molecules includes: 0.1 to 2 g.L-1Wherein, 0.1, 0.5, 0.8, 1.0, 1.5, 1.8, 2.0 g.L can be selected-1Etc.;
the mass concentration range of the amino group-containing polymer includes: 1 to 10 g.L-1Wherein, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g.L can be selected-1And the like.
According to the embodiments of the present disclosure, when a plurality of N-containing groups on the cucurbituril molecule form a complex with the amino-containing polymer, a plurality of amino molecules are required to be bonded with the cucurbituril molecule, so that the mass concentration of the amino-containing polymer is higher than that of the cucurbituril molecule.
According to embodiments of the present disclosure, the concentration range of the polybasic acid chloride monomer includes: 1 to 10 g.L-1Wherein, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g.L can be selected-1And the like.
According to embodiments of the present disclosure, the reaction time range for the cucurbituril molecule and the amino-containing polymer to form a complex includes: 1-24 h, wherein the time can be 1, 4, 8, 12, 16, 20, 24h and the like.
According to embodiments of the present disclosure, the time range for contacting the support membrane with the aqueous solution of the complex monomer includes: 10-120 min, wherein 10, 20, 40, 60, 80, 100, 120min and the like can be selected;
the temperature range of the aqueous monomer solution includes: 15-40 ℃, wherein the preferable temperature is 25 ℃.
According to an embodiment of the present disclosure, the time range for contacting the support membrane adsorbing the complex monomer with the organic phase solution containing the polyacyl chloride monomer includes: 10-600 s, wherein the time can be 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600s and the like;
the temperature range of the contact reaction includes: 15-40 ℃, wherein the preferable temperature is 25 ℃.
According to an embodiment of the present disclosure, the temperature range of the heat treatment includes: 50-90 ℃, wherein the temperature can be selected from 50, 60, 70, 80, 90 ℃ and the like, and preferably 80 ℃;
the time ranges of the heat treatment include: 1-10 min, wherein, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10min, etc. can be selected, and 5min is preferred.
The technical solution of the present disclosure is described in detail below by referring to a plurality of specific examples. It should be noted that the following specific examples are only for illustration and are not intended to limit the disclosure.
The sources of all the raw materials in the present disclosure and the following examples are not particularly limited and may be those commercially available.
The detection method of the membrane flux in the embodiment of the disclosure is as follows:
testing the permeation flux of the membrane to water and the interception of dye molecules and salt by adopting a laboratory self-made membrane permeation selection performance testing systemThe testing system consists of a pump, a membrane pool, a pipeline, a regulating valve, a pressure and flow detector and the like, wherein the area of an effective membrane to be tested is 9.61cm2The test pressure was 3bar and the test temperature was 25. + -. 0.5 ℃.
The water flux is calculated as follows: j ═ V/(a. delta. t. P), (one)
Wherein J is the water flux (L.m) of the membrane-2·h-1·bar-1) V is the volume of water (L) permeating the membrane, A is the effective area of the membrane (m)2) Δ t is the permeation time(s) and P is the operating pressure (bar).
The calculation formula of the retention rate is as follows: r ═ 1-Cp/Cf) 100%, (two)
Wherein C ispIs the concentration (g.L) of the permeated liquid-1)，CfIs the concentration (g.L) of the raw material liquid-1)。
Rejection of single salt test salt concentration: NaCl, MgCl2、Na2SO4And MgSO4The concentration is 1000 mg.L-1. Testing the separation performance of the monovalent/divalent ion mixed salt: MgSO (MgSO)4/NaCl、Na2SO4/NaCl、MgCl2NaCl, wherein the mixed salt concentration is 2000 mg.L-1Wherein the monovalent/divalent ion concentration ratio is 1. The monovalent/divalent ion concentration was detected using inductively coupled plasma emission spectroscopy (ICP-OES, VISTA-MPX, Varian).
The formula for the monovalent/divalent ion selectivity is calculated as follows:
wherein R ismIs the rejection (%) of monovalent salts; rdIs the retention (%) of divalent salt.
Example 1
The preparation content of the product is 4 g.L-1Of (D) polyethyleneimine (molecular weight 600Da) and 0.5 g.L-1Gourd [6 ]]Aqueous urea, reacted for 6h as aqueous solution. Next, an n-heptane solution containing 0.1% of 1,3, 5-trimesoyl chloride was prepared as an organic solventPhase solution. Firstly, the aqueous solution is placed on the surface of a modified polysulfone support membrane, the support membrane is contacted with the aqueous solution for 20min at 25 ℃ and the excess aqueous solution is removed. Then, placing the organic phase solution on the surface of the membrane, reacting for 30s at 25 ℃, removing the redundant organic phase solution, and washing the residual organic phase monomer on the surface of the membrane by using n-heptane. And then, drying the membrane in a forced air drying oven at 80 ℃ for 5min to further crosslink the membrane, thereby obtaining a nanofiltration membrane with an amino complexation cucurbituril molecular channel structure, and storing the nanofiltration membrane in deionized water to be further tested for separation performance.
It can be seen from the tests and combinations of Table 1 that the gourd [6 ] is utilized]Size of the Urea molecule Cavity and cucurbit [6 ]]The urea has the characteristic of positive charge, and the cucurbituril molecule has higher selective separation effect on ions in an electrically neutral solution. Nanofiltration membrane pair MgSO prepared by adopting the method4、Na2SO4、MgCl2The retention rates of NaCl are 97%, 90%, 42% and 12% respectively, which are caused by the difference of the radius of solution ions and the electron logarithm of the ions; MgSO (MgSO)4NaCl selectivity 30, Na2SO4NaCl selectivity 8.9, MgCl2The selectivity/NaCl was 1.5. Water permeation flux of 26L-1·m-2·h-1·bar-1The membrane can maintain stable separation performance in 10 days of continuous operation, wherein Mg2+The ionic radius is 0.072nm, Na+Ionic radius of 0.102nm, Cl-Ionic radius of 0.181nm, SO4 2-The ionic radius was 0.580 nm.
The nanofiltration membrane and the support membrane obtained in this example 1 were characterized by a scanning electron microscope.
FIG. 2 is a surface scanning electron micrograph of a support film in example 1 of the present disclosure; fig. 3 is a scanning electron microscope image of the surface of the nanofiltration membrane in example 1 of the present disclosure.
As shown in fig. 2 to 3, the nanofiltration membrane has a smooth surface, is dense and has no defects.
Fig. 4 is a scanning electron microscope image of a cross section of the nanofiltration membrane in example 1 of the present disclosure.
As shown in FIG. 4, the SEM image of the nanofiltration membrane shows that the thickness of the selective separation layer of the membrane is about 50 nm.
Example 2
The preparation content is 5 g.L-1Of (D) a polyethyleneimine (molecular weight 70000Da) and 0.7 g.L-1Gourd [7 ]]Aqueous urea, reacted for 9h as aqueous solution. Subsequently, an n-heptane solution containing 0.15% of terephthaloyl chloride was prepared as an organic phase solution. Firstly, placing the aqueous solution on the surface of a polyether sulfone support membrane, and contacting the support membrane with the aqueous solution at 25 ℃ for 50min to remove the redundant aqueous solution. Then, the organic phase solution is placed on the surface of the membrane and reacts for 10s at 25 ℃, the redundant organic phase solution is removed, and the residual organic phase monomer on the surface of the membrane is washed by n-heptane. And then, drying the membrane in a forced air drying oven at 80 ℃ for 5min to further crosslink the membrane, thereby obtaining a nanofiltration membrane with an amino complexation cucurbituril molecular channel structure, and storing the nanofiltration membrane in deionized water to be further tested for separation performance.
It can be seen from the tests and combinations of Table 1 that the gourd [7 ] is utilized]Size of the Urea molecule Cavity and cucurbit [7 ]]The positive charge of urea, the nanofiltration membrane over MgSO4、Na2SO4、MgCl2The retention rates of NaCl are respectively 99%, 95%, 64% and 34%; MgSO (MgSO)4NaCl selectivity 38, Na2SO4NaCl selectivity 8.9, MgCl2The selectivity/NaCl was 1.5. The water permeation flux is 17L-1·m-2·h-1·bar-1The membrane can maintain stable separation performance in 10 days of continuous operation.
Example 3
The preparation content is 2 g.L-1Of (D) polyethyleneimine (molecular weight 4000Da) and 0.3 g.L-1Gourd [6 ]]Aqueous urea, reacted for 3h as aqueous solution. Next, an n-heptane solution containing 0.1% of 1,3, 5-trimesoyl chloride was prepared as an organic phase solution. Firstly, placing the aqueous solution on the surface of a polyimide support membrane, and contacting the support membrane with the aqueous solution at 25 ℃ for 40min to remove the excess aqueous solution. Then, placing the organic phase solution on the surface of the membrane, reacting for 50s at 25 ℃, removing the redundant organic phase solution, and flushing the residual organic phase on the surface of the membrane by using n-heptaneA monomer. And then, drying the membrane in a forced air drying oven at 80 ℃ for 5min to further crosslink the membrane, thereby obtaining a nanofiltration membrane with an amino complexation cucurbituril molecular channel structure, and storing the nanofiltration membrane in deionized water to be further tested for separation performance.
It can be seen from the tests and combinations of Table 1 that the gourd [6 ] is utilized]Size of the Urea molecule Cavity and cucurbit [6 ]]The positive charge of urea, the nanofiltration membrane over MgSO4、Na2SO4、MgCl2The retention rates of NaCl are 84%, 80%, 22% and 15% respectively; MgSO (MgSO)4NaCl selectivity 19, Na2SO4NaCl selectivity 8.9, MgCl2The selectivity/NaCl was 1.5. Water permeation flux of 38L-1·m-2·h-1·bar-1The membrane can maintain stable separation performance in 10 days of continuous operation.
Example 4
The preparation content is 2 g.L-1The polyethyleneimine (molecular weight: 10000Da) was used as an aqueous solution. An n-heptane solution containing 0.1% of 1,3, 5-benzenetricarboxylic acid chloride was prepared as an organic phase solution. Firstly, placing the aqueous solution on the surface of a polysulfone support membrane, and contacting the support membrane with the aqueous solution at 25 ℃ for 30min to remove the excess aqueous solution. And then placing the organic phase solution on the surface of the membrane, reacting for 50s at 25 ℃, removing the redundant organic phase solution, and washing the residual organic phase monomer on the surface of the membrane by using n-heptane. And then, drying the membrane in a forced air drying oven at 80 ℃ for 5min to further crosslink the membrane, thereby obtaining a nanofiltration membrane with an amino complexation cucurbituril molecular channel structure, and storing the nanofiltration membrane in deionized water to be further tested for separation performance.
Tests show that for the nanofiltration membrane without the cucurbituril molecular channel structure, the rejection rate of NaCl is 46 percent, and the rejection rate of MgSO is MgSO4The retention of (2) was 87%, MgSO4NaCl selectivity 7, water permeation flux 9L m-2·h-1·bar-1。
TABLE 1 comparison of cucurbit [ n ] uril structural parameters
Based on the above examples, the nanofiltration membrane of the present disclosure has higher water flux and better monovalent/divalent ion selectivity and better operation stability than the polyamide nanofiltration membrane formed without cucurbituril molecules.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. A method for preparing a nanofiltration membrane comprises the following steps:
contacting the support film with an aqueous phase solution of a complex monomer to obtain the support film adsorbing the complex monomer, wherein the complex monomer is formed by cucurbituril molecules and amino-containing polymers;
contacting the support membrane for adsorbing the complex monomer with an organic phase solution containing a polybasic acyl chloride monomer, and carrying out interfacial polymerization reaction to obtain a nascent-state nanofiltration membrane, wherein the nascent-state nanofiltration membrane has an amino complexation cucurbituril molecular channel structure;
and carrying out heat treatment on the nascent nanofiltration membrane to obtain the nanofiltration membrane with an amino complexation cucurbituril molecular channel structure.
2. The method of claim 1, wherein the cucurbituril molecule has a cavity diameter size range comprising: 0.4-1.0 nm;
the amino-containing polymer comprises: one or more of polyvinylamine, polyethyleneimine and polyetheramine.
3. The method of claim 1, wherein the polyacyl chloride monomer comprises: one or more of 1,3, 5-trimesoyl chloride, terephthaloyl chloride, glutaryl chloride and 1, 3-benzene disulfonyl chloride.
4. The method of claim 1, wherein the membrane material of the support membrane comprises any one of:
polyethylene, polypropylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone, polyethersulfone, polyimide, polytetrafluoroethylene, and alumina.
5. The method of claim 1, wherein the range of mass ratios of the cucurbituril molecules to amino-containing polymer comprises: 1: 2-10: 2;
the concentration range of the polyacyl chloride monomer comprises: 1 to 10 g.L-1。
6. The method of claim 1, wherein the reaction time range for the cucurbituril molecule and the amino-containing polymer to form a complex comprises: 1-24 h.
7. The method of claim 1, wherein the support membrane is contacted with the aqueous solution of the complex monomer for a time period comprising: 10-120 min;
the temperature range of the aqueous monomer solution includes: 15 to 40 ℃.
8. The method of claim 1, wherein the support membrane adsorbing the complex monomer is in liquid phase contact with the organic phase containing the poly-acid chloride monomer for a time period comprising: 10-600 s;
the temperature range of the contact reaction comprises: 15 to 40 ℃.
9. The method of claim 1, wherein the temperature range of the heat treatment comprises: 50-90 ℃;
the time range of the heat treatment includes: 1-10 min.
10. A nanofiltration membrane prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111586385.0A CN114247297B (en) | 2021-12-23 | 2021-12-23 | Nanofiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111586385.0A CN114247297B (en) | 2021-12-23 | 2021-12-23 | Nanofiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114247297A true CN114247297A (en) | 2022-03-29 |
| CN114247297B CN114247297B (en) | 2023-10-20 |
Family
ID=80796927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111586385.0A Active CN114247297B (en) | 2021-12-23 | 2021-12-23 | Nanofiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114247297B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106731841A (en) * | 2016-12-29 | 2017-05-31 | 南京工业大学 | A kind of supermolecule composite nanometer filtering film and its preparation method and application |
| CN111013391A (en) * | 2019-11-28 | 2020-04-17 | 南京工业大学 | Modified nanofiltration membrane and preparation method thereof |
| CN111545083A (en) * | 2020-03-24 | 2020-08-18 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration |
-
2021
- 2021-12-23 CN CN202111586385.0A patent/CN114247297B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106731841A (en) * | 2016-12-29 | 2017-05-31 | 南京工业大学 | A kind of supermolecule composite nanometer filtering film and its preparation method and application |
| CN111013391A (en) * | 2019-11-28 | 2020-04-17 | 南京工业大学 | Modified nanofiltration membrane and preparation method thereof |
| CN111545083A (en) * | 2020-03-24 | 2020-08-18 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114247297B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | High nanoparticles loadings mixed matrix membranes via chemical bridging-crosslinking for CO2 separation | |
| Wu et al. | A novel nanofiltration membrane with [MimAP][Tf2N] ionic liquid for utilization of lithium from brines with high Mg2+/Li+ ratio | |
| CN107158980B (en) | Thin-layer composite membrane based on gas/liquid interface reaction and preparation method and application thereof | |
| Bhavsar et al. | Ultrahigh-permeance PIM-1 based thin film nanocomposite membranes on PAN supports for CO2 separation | |
| Zhang et al. | Layer-by-layer construction of graphene oxide (GO) framework composite membranes for highly efficient heavy metal removal | |
| Wang et al. | Covalent organic framework modified polyamide nanofiltration membrane with enhanced performance for desalination | |
| Ji et al. | Preparation of novel positively charged copolymer membranes for nanofiltration | |
| Wang et al. | A novel highly permeable positively charged nanofiltration membrane based on a nanoporous hyper-crosslinked polyamide barrier layer | |
| Shi et al. | Layer-by-layer (LbL) polyelectrolyte membrane with Nexar™ polymer as a polyanion for pervaporation dehydration of ethanol | |
| Ren et al. | Oligo-ethylene-glycol based thin-film composite nanofiltration membranes for effective separation of mono-/di-valent anions | |
| Jin et al. | Preparation of thin-film composite nanofiltration membranes with improved antifouling property and flux using 2, 2′-oxybis-ethylamine | |
| Zhang et al. | Preparation of high performance polyamide membrane by surface modification method for desalination | |
| Ma et al. | Polyamide nanofilms synthesized via controlled interfacial polymerization on a “jelly” surface | |
| CN108325389B (en) | Azlactone-based polyamide membrane and preparation method thereof | |
| Zhao et al. | Amino acid-based loose polyamide nanofiltration membrane with ultrahigh water permeance for efficient dye/salt separation | |
| US20140311347A1 (en) | Polaniline based membranes for separation of carbon dioxide and methane | |
| He et al. | Cyclic tertiary amino group containing fixed carrier membranes for CO2 separation | |
| CN110787644B (en) | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof | |
| Liu et al. | Regulating the morphology of nanofiltration membrane by thermally induced inorganic salt crystals for efficient water purification | |
| CN111686594A (en) | High-flux high-retention composite membrane and preparation method thereof | |
| Iranizadeh et al. | Preparation and characterization of thin-film composite reverse osmosis membrane on a novel aminosilane-modified polyvinyl chloride support | |
| CN111644080B (en) | High-hydrophilicity nanofiber coating-based nanofiltration membrane and preparation method thereof | |
| Shen et al. | MeSiCl3 functionalized polyamide thin film nanocomposite for low pressure RO membrane desalination | |
| CN115554849A (en) | Preparation method of polyethyleneimine-based positively-charged nanofiltration membrane | |
| CN113144915B (en) | Modified polyamide composite nanofiltration membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |