CN115646212B - Nanofiltration membrane and preparation method thereof - Google Patents
Nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN115646212B CN115646212B CN202211681545.4A CN202211681545A CN115646212B CN 115646212 B CN115646212 B CN 115646212B CN 202211681545 A CN202211681545 A CN 202211681545A CN 115646212 B CN115646212 B CN 115646212B
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- 239000012528 membrane Substances 0.000 title claims abstract description 93
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012071 phase Substances 0.000 claims abstract description 50
- 239000008346 aqueous phase Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 19
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 18
- 238000011033 desalting Methods 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002492 poly(sulfone) Polymers 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 17
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 208000037516 chromosome inversion disease Diseases 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical compound C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 12
- 230000004907 flux Effects 0.000 abstract description 9
- 239000004952 Polyamide Substances 0.000 abstract description 8
- 229920002647 polyamide Polymers 0.000 abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 78
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- -1 benzene compound Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of separation membranes, and particularly relates to a nanofiltration membrane and a preparation method thereof. The nanofiltration membrane provided by the invention comprises a non-woven fabric layer, a porous supporting layer and a desalting layer which are contacted in sequence; the desalting layer is formed by performing interfacial polymerization reaction on the water phase solution and the oil phase solution on the surface of the porous supporting layer; the aqueous phase solution contains polyamine monomers; the oil phase solution contains a sulfinyl chloride monomer with a structure shown in a formula (I); in the formula (I), R 1 、R 2 And R 3 Is a hydrocarbyl group. According to the invention, through optimized selection of the reaction monomer in the oil phase solution, the polyamide desalting layer formed after interfacial polymerization has certain acid resistance and a relatively loose structure, so that the membrane can keep higher membrane flux on the premise of good acid resistance, the service life of the membrane element is prolonged, and the operation cost is reduced.
Description
Technical Field
The invention belongs to the field of separation membranes, and particularly relates to a nanofiltration membrane and a preparation method thereof.
Background
The nanofiltration membrane can effectively intercept macromolecular substances (substances with molecular weight of 200-1000) and ions with more than two valences due to the characteristic of selective separation, so that most of small molecules and monovalent ions can permeate through the nanofiltration membrane, and the nanofiltration membrane can be operated under lower working pressure compared with a reverse osmosis membrane, and has wide application in the aspects of metal ion and acid recovery, medicine and biological product processing industry, water body organic waste removal and the like.
The conventional nanofiltration membrane mainly comprises polyamide and polypiperazine amide structures, the pH tolerance range of the conventional nanofiltration membrane is generally 2 to 10, and when a strong acidic substance is encountered, oxygen atoms of amide groups are attacked by hydrated acid and are easily hydrolyzed into carboxylic acid and amine, so that the membrane structure is damaged and loses functions. In addition, the monomer substance adopted in the preparation process of the existing nanofiltration membrane has a violent reaction process, the generated polyamide network structure is relatively compact, the membrane flux is low, the operation pressure is high, and the energy consumption is high.
Disclosure of Invention
In view of the above, the present invention provides a nanofiltration membrane and a preparation method thereof, and the nanofiltration membrane provided by the present invention has good acid resistance and membrane flux.
The invention provides a nanofiltration membrane, which comprises a non-woven fabric layer, a porous supporting layer and a desalting layer which are contacted in sequence;
the desalting layer is formed by performing interfacial polymerization reaction on the water phase solution and the oil phase solution on the surface of the porous supporting layer;
the aqueous phase solution contains polyamine monomers; the oil phase solution contains a sulfinyl chloride monomer with a structure shown in a formula (I):
in the formula (I), R 1 、R 2 And R 3 Is a hydrocarbyl group.
Preferably, said R 1 、R 2 And R 3 Is an alkyl group.
Preferably, said R 1 、R 2 And R 3 Independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
Preferably, the polyamine monomer is one or more of piperazine, hexahydropyrimidine, m-phenylenediamine, p-phenylenediamine, ethylenediamine and propylenediamine.
The invention provides a preparation method of a nanofiltration membrane, which comprises the following steps:
a) Providing a base film, wherein the base film is of a double-layer structure, the front surface of the base film is a porous supporting layer, and the back surface of the base film is a non-woven fabric layer;
b) Soaking the base membrane into the aqueous phase solution, and removing the redundant aqueous phase solution on the base membrane after taking out;
c) Coating the oil phase solution on the front surface of the base film treated in the step b) to perform interfacial polymerization reaction, and then removing the redundant oil phase solution on the front surface of the base film;
d) Drying the base membrane treated in the step c) to obtain the nanofiltration membrane.
Preferably, in step a), the base film is prepared according to the following steps:
coating the casting solution on the surface of one side of the non-woven fabric, and then carrying out phase inversion curing in water to obtain a base film;
the components of the membrane casting solution comprise sulfonated polysulfone and an organic solvent.
Preferably, the casting solution further comprises a pore-forming agent.
Preferably, in the step b), the soaking temperature is 10 to 40 ℃; the soaking time is 10 to 30s.
Preferably, in the step c), the temperature of the interfacial polymerization reaction is 10 to 40 ℃; the time of the interfacial polymerization reaction is 5 to 20s.
Preferably, in the step d), the drying temperature is 50-60 ℃.
Compared with the prior art, the invention provides a nanofiltration membrane and a preparation method thereof. The nanofiltration membrane provided by the invention comprises a non-woven fabric layer, a porous supporting layer and a desalting layer which are contacted in sequence; the desalting layer is formed by performing interfacial polymerization reaction on the water phase solution and the oil phase solution on the surface of the porous supporting layer; the aqueous phase solution contains polyamine monomers; the oil phase solution contains a sulfinyl chloride monomer with a structure shown in formula (I); in the formula (I), R 1 、R 2 And R 3 Is a hydrocarbyl group. By optimally selecting the reaction monomer in the oil phase solution, the polyamide desalting layer formed after the interfacial polymerization reaction has certain acid resistance and a relatively loose structure, so that the membrane can keep relatively loose structure on the premise of good acid resistanceHigh membrane flux, prolonged service life of the membrane element and reduced operation cost.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a nanofiltration membrane, which comprises a non-woven fabric layer, a porous supporting layer and a desalting layer which are contacted in sequence;
the desalting layer is formed by performing interfacial polymerization reaction on the water phase solution and the oil phase solution on the surface of the porous supporting layer;
the aqueous phase solution contains polyamine monomers; the oil phase solution contains a sulfinyl chloride monomer with a structure shown in a formula (I):
in the formula (I), R 1 、R 2 And R 3 Is a hydrocarbyl group.
In the nanofiltration membrane provided by the invention, the thickness of the non-woven fabric layer is preferably 50 to 200 μm, and specifically can be 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm; the air permeability of the non-woven fabric layer is preferably 0.5 to 5cc/cm 2 The specific value of the concentration is 0.5cc/cm 2 /s、0.7cc/cm 2 /s、1cc/cm 2 /s、1.2cc/cm 2 /s、1.5cc/cm 2 /s、1.7cc/cm 2 /s、2cc/cm 2 /s、2.3cc/cm 2 /s、2.5cc/cm 2 /s、2.7cc/cm 2 /s、3cc/cm 2 /s、3.2cc/cm 2 /s、3.5cc/cm 2 /s、3.7cc/cm 2 /s、4cc/cm 2 /s、4.2cc/cm 2 /s、4.5cc/cm 2 /s、4.7cc/cm 2 (s) or 5cc/cm 2 /s。
In the nanofiltration membrane provided by the invention, the porous support layer is formed by curing the membrane casting solution on one side surface of the non-woven fabric layer. Wherein, the components of the membrane casting solution preferably comprise sulfonated polysulfone and an organic solvent; the sulfonated polysulfone is preferably purchased from basf under the cat # S2010G6; the organic solvent includes, but is not limited to, dimethylformamide (DMF); the content of the sulfonated polysulfone in the membrane casting solution is preferably 10 to 30wt%, and specifically may be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%. In the present invention, the components of the casting solution preferably further include a pore-forming agent; the porogens include, but are not limited to, polyvinylpyrrolidone; the content of the polyvinylpyrrolidone in the casting solution is preferably 0 to 15wt%, and specifically may be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, or 15wt%. In the present invention, the curing mode is preferably phase inversion curing; the temperature of the phase inversion curing is preferably 5 to 30 ℃, and specifically can be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃ or 30 ℃.
In the nanofiltration membrane provided by the invention, the polyamine monomer contained in the aqueous phase solution comprises but is not limited to one or more of piperazine, hexahydropyrimidine, m-phenylenediamine, p-phenylenediamine, ethylenediamine and propylenediamine; the content of the polyamine monomer in the aqueous phase solution is preferably 0.5 to 3wt%, and specifically can be 0.5wt%, 0.7wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%. In the present invention, the aqueous phase solution preferably further contains a surfactant and/or a pH adjuster; the surfactant is preferably sodium dodecyl sulfate, and the content of the sodium dodecyl sulfate in the aqueous phase solution is preferably 0.1 to 1wt%, and specifically can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt%; the pH regulator is preferably sodium hydroxide, and the content of the sodium hydroxide in the aqueous phase solution is preferably 0.5 to 3wt%, and specifically can be 0.5wt%, 0.7wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%.
In the nanofiltration membrane provided by the invention,r in sulfinyl chloride monomer with structure shown in formula (I) contained in oil phase solution 1 、R 2 And R 3 Preferably an alkyl group, more preferably independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, said propyl group preferably being n-propyl or isopropyl; the content of the sulfinyl chloride monomer in the oil phase solution is preferably 0.05 to 0.5wt%, and specifically may be 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, or 0.5wt%; the solvent in the oil phase solution includes but is not limited to n-hexane.
The invention also provides a preparation method of the nanofiltration membrane, which comprises the following steps:
a) Providing a base film, wherein the base film is of a double-layer structure, the front surface of the base film is a porous supporting layer, and the back surface of the base film is a non-woven fabric layer;
b) Soaking the base membrane into the aqueous phase solution, and removing the redundant aqueous phase solution on the base membrane after taking out;
c) Coating the oil phase solution on the front surface of the base film treated in the step b) to perform interfacial polymerization reaction, and then removing the redundant oil phase solution on the front surface of the base film;
d) Drying the base membrane treated in the step c) to obtain the nanofiltration membrane.
In the preparation method provided by the invention, in the step a), the base film is preferably prepared according to the following steps:
and coating the casting solution on the surface of one side of the non-woven fabric, and then carrying out phase inversion curing in water to obtain the base film.
In the base film preparation step provided by the invention, the thickness of the non-woven fabric is preferably 50 to 200 μm, and specifically can be 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm; the air permeability of the non-woven fabric layer is preferably 0.5 to 5cc/cm 2 The specific value of the concentration of the carbon dioxide is 0.5cc/cm 2 /s、0.7cc/cm 2 /s、1cc/cm 2 /s、1.2cc/cm 2 /s、1.5cc/cm 2 /s、1.7cc/cm 2 /s、2cc/cm 2 /s、2.3cc/cm 2 /s、2.5cc/cm 2 /s、2.7cc/cm 2 /s、3cc/cm 2 /s、3.2cc/cm 2 /s、3.5cc/cm 2 /s、3.7cc/cm 2 /s、4cc/cm 2 /s、4.2cc/cm 2 /s、4.5cc/cm 2 /s、4.7cc/cm 2 (s) or 5cc/cm 2 /s。
In the above-mentioned base film preparation step provided by the present invention, the components of the membrane casting solution preferably include sulfonated polysulfone and an organic solvent; the sulfonated polysulfone is preferably purchased from basf under the catalog number S2010G6; the organic solvent includes, but is not limited to, dimethylformamide (DMF); the content of the sulfonated polysulfone in the membrane casting solution is preferably 10 to 30wt%, and specifically may be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%. In the present invention, the components of the casting solution preferably further include a pore-forming agent; the porogens include, but are not limited to, polyvinylpyrrolidone; the content of the polyvinylpyrrolidone in the casting solution is preferably 0 to 15wt%, and specifically may be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, or 15wt%.
In the preparation step of the base film provided by the invention, the temperature of the phase transformation curing is preferably 5 to 30 ℃, and specifically can be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃ or 30 ℃; the time for the phase inversion curing is not particularly limited, and the casting solution may be completely cured.
In the preparation method provided by the invention, in the step b), the aqueous phase solution contains polyamine monomer and water; the polyamine monomer includes but is not limited to one or more of piperazine, hexahydropyrimidine, m-phenylenediamine, p-phenylenediamine, ethylenediamine and propylenediamine; the content of the polyamine monomer in the aqueous phase solution is preferably 0.5 to 3wt%, and specifically can be 0.5wt%, 0.7wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%. In the present invention, the aqueous phase solution preferably further contains a surfactant and/or a pH adjuster; the surfactant is preferably sodium dodecyl sulfate, and the content of the sodium dodecyl sulfate in the aqueous phase solution is preferably 0.1-1wt%, and specifically can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt%; the pH regulator is preferably sodium hydroxide, and the content of the sodium hydroxide in the aqueous phase solution is preferably 0.5 to 3wt%, and specifically can be 0.5wt%, 0.7wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%.
In the preparation method provided by the invention, in the step b), the soaking temperature is preferably 10 to 40 ℃, and specifically can be 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃; the soaking time is preferably 10 to 30s, and specifically may be 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s, 25s, 26s, 27s, 28s, 29s or 30s.
In the preparation method provided by the invention, in the step b), the mode of removing the excessive aqueous phase solution is preferably as follows: removing the redundant aqueous phase solution on the surface of the base film by using a surface roller, and removing the residual aqueous solution on the front surface and the back surface of the base film by using a hot air knife and vacuum water absorption to ensure that no aqueous phase solution can be seen by naked eyes on the base film.
In the preparation method provided by the invention, in the step c), the oil-phase solution contains solvent oil and sulfinyl chloride monomer with the structure shown in the formula (I);
in the formula (I), R 1 、R 2 And R 3 Is a hydrocarbon group, preferably an alkyl group, more preferably independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, said propyl group preferably being n-propyl or isopropyl.
In the preparation method provided by the invention, in the step c), the content of the sulfinyl chloride monomer in the oil phase solution is preferably 0.05 to 0.5wt%, and specifically may be 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, or 0.5wt%; the solvent oil includes, but is not limited to, n-hexane.
In the preparation method provided by the invention, in the step c), the temperature of the interfacial polymerization reaction is preferably 10 to 40 ℃, and specifically can be 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃; the time for the interfacial polymerization reaction is preferably 5 to 20s, and specifically may be 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s, or 20s.
In the preparation method provided by the invention, in the step c), the mode of removing the excessive oil phase solution is preferably as follows: excess oil phase solution was removed with a face-side roller and air knife.
In the preparation method provided by the invention, in the step d), the drying temperature is preferably 50 to 60 ℃, and specifically can be 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃; the drying time is not particularly limited, and the surface of the membrane sheet may be completely dried.
According to the technical scheme provided by the invention, through optimizing and selecting the reaction monomer in the oil phase solution, the polyamide desalting layer formed after the interfacial polymerization reaction has certain acid resistance and a relatively loose structure, so that the membrane can keep higher membrane flux on the premise of good acid resistance, the service life of the membrane element is prolonged, and the operation cost is reduced. More specifically, the technical scheme provided by the invention at least has the following beneficial effects:
1) The oil phase reaction monomer adopted by the invention has S = O bond, and sulfur atom has certain electron-withdrawing effect, so that the polarity of the S = O bond is less than that of the C = O bond, and oxygen is not easily attacked by hydrogen proton under acidic condition, so that the polyamide desalting layer formed after reaction has certain acid resistance;
2) The oil phase reaction monomer adopted by the invention introduces alkyl (R) between sulfinyl chloride group and benzene ring 1 、R 2 、R 3 ) The structure of the membrane has stronger hydrophobicity, so that a polyamide desalting layer formed after reaction can be more tightly combined with a porous supporting layer, and the tolerance of the membrane material is enhanced;
3) R in oil phase reaction monomer adopted by the invention 1 、R 2 、R 3 The hydrocarbyl group belongs to an electron-donating group, and enables adjacent S atoms to have certain electronegativity; the hydrocarbon radical being added to separate the benzene ring from the sulfinesThe direct connection of acyl weakens the electron-withdrawing induction effect of the conjugated large pi-bond structure of the benzene ring; in addition, lone pair electrons exist on the S atom, so that the activity of aniline group attacking the S atom is lower than that of the aniline group attacking the S atom in the amidation nucleophilic substitution reaction process, and the interfacial polymerization reaction of the polyamine monomer and the sulfinyl chloride monomer can be limited to a certain extent, so that the density and the crosslinking degree of a desalting layer network structure are reduced, the desalting layer structure is loose, and the membrane flux is high.
For the sake of clarity, the following examples and comparative examples are given in detail below. In the following examples and comparative examples of the present invention, the relevant operations were carried out at room temperature and normal pressure unless otherwise specified.
In the following examples of the present invention, the polybasic sulfinyl chlorides having the formula (I) used were prepared according to the following steps:
adding 0.1mol of benzene compound with the structure of the formula (i) into a flask, stirring with Tetrahydrofuran (THF) until the benzene compound is dissolved, and adding 3g of an acid-binding agent (triethylamine); then 0.3mol of thionyl chloride (SOCl) was slowly added through a dropping funnel at 0 deg.C 2 ) Reacting for 5 hours; after the reaction is finished, distilling the reactant to remove low boiling point substances; finally, obtaining the polybasic sulfinyl chloride through reduced pressure distillation;
in the formula (i), R 1 、R 2 And R 3 Is ethyl, n-propyl or isopropyl.
Example 1
1. Preparing a base film: 84 parts by mass of N, N-dimethylformamide, 15 parts by mass of sulfonated polysulfone (Pasv, germany, S2010G 6) and 1 part by mass of polyvinylpyrrolidone (with the number average molecular weight of 24000 to 130000), and stirring at a high speed for 4 hours at 70 ℃ to obtain a uniform and transparent solution; uniformly coated on a non-woven fabric (thickness 100 microns, air permeability 2.5 cc/cm) 2 /s) one side surface of the base material, immersing in pure water at 15 ℃ for phase conversion curing to obtain a polysulfone-based film(the front surface is a polysulfone porous supporting layer, and the back surface is a non-woven fabric layer).
2. Preparing an aqueous phase solution: 1 part by mass of piperazine, 0.5 part by mass of sodium dodecyl sulfate, 1.5 parts by mass of sodium hydroxide and 97 parts by mass of pure water are stirred for 0.5 hour to obtain a homogeneous transparent solution.
3. Preparing an oil phase solution: a polybasic sulfinyl chloride (R) with the structure of formula (I) 1 、R 2 And R 3 Are all ethyl-CH 2 -CH 2 -) 0.1 part by mass and 99.9 parts by mass of n-hexane were stirred for 0.5 hour to obtain a homogeneous solution.
4. Preparing a nanofiltration membrane: soaking the base film in the aqueous phase solution for 20s, removing the redundant aqueous phase solution on the surface by using a surface roller, and removing the residual aqueous solution on the front side and the back side of the diaphragm by using a hot air knife and vacuum water absorption to ensure that the aqueous phase solution is not visible on the base film; coating the oil phase solution on the front surface of a polysulfone membrane for interfacial polymerization reaction, and removing the redundant oil phase solution by using a front roller and an air knife after the reaction is carried out for 10 s; and then, conveying the membrane into a 60 ℃ oven, and taking the membrane out of the oven after the membrane is completely dried to obtain the nanofiltration membrane.
Example 2
1. Preparing a polysulfone-based membrane: the same as in example 1.
2. Preparing an aqueous phase solution: the same as in example 1.
3. Preparing an oil phase solution: a polybasic sulfinyl chloride (R) with the structure of formula (I) 1 、R 2 And R 3 Are all n-propyl-CH 2 -CH 2 -CH 2 -) 0.1 part by mass and 99.9 parts by mass of n-hexane were stirred for 0.5 hour to obtain a homogeneous solution.
4. Preparing a nanofiltration membrane: the same as in example 1.
Example 3
1. Preparing a polysulfone-based membrane: the same as in example 1.
2. Preparing an aqueous phase solution: the same as in example 1.
3. Preparing an oil phase solution: a polybasic sulfinyl chloride (R) with the structure of formula (I) 1 、R 2 And R 3 Are all isopropyl-C (CH) 3 ) 2 -) 0.1 part by mass of n-hexane and 99.9 parts by mass of n-hexane, and stirring for 0.5h to obtain a homogeneous solutionAnd (4) liquid.
4. Preparing a nanofiltration membrane: the same as in example 1.
Example 4
1. Preparing a polysulfone-based membrane: the same as in example 1.
2. Preparing an aqueous phase solution: the same as in example 1.
3. Preparing an oil phase solution: a polybasic sulfinyl chloride (R) with the structure of formula (I) 1 、R 2 And R 3 Are all isopropyl-C (CH) 3 ) 2 -) 0.2 parts by mass and n-hexane 99.8 parts by mass, and stirred for 0.5h to obtain a homogeneous solution.
4. Preparing a nanofiltration membrane: the same as in example 1.
Comparative example 1
1. Preparing a polysulfone-based membrane: polysulfone (Suwei, USA, PSU-3500) was used, and the other examples were the same as example 1.
2. Preparing an aqueous phase solution: the same as in example 1.
3. Preparing an oil phase solution: 0.1 part by mass of trimesoyl chloride and 99.9 parts by mass of n-hexane are stirred for 0.5h to obtain a homogeneous solution.
4. Preparing a nanofiltration membrane: as in comparative example 1.
Comparative example 2
1. Preparing a polysulfone-based membrane: the same as in example 1.
2. Preparing an aqueous phase solution: the same as in example 1.
3. Preparing an oil phase solution: 0.1 part by mass of benzene trisulfonyl chloride and 99.9 parts by mass of n-hexane are stirred for 0.5h to obtain a homogeneous solution.
4. Preparing a nanofiltration membrane: as in comparative example 1.
Performance test
The nanofiltration membranes prepared in the above examples and comparative examples were taken to perform performance tests in a standard membrane test bench, and the results are shown in the following table:
the above membrane performance test was performed with 2000mg/L MgSO 4 Aqueous solution under 70psi pressure at 25 + -1 deg.CThe test was performed.
Wherein:
the flux F is calculated as follows:
in the formula, V is the volume of the penetrating fluid, S is the area of the effective membrane, and t is the time.
The salt rejection R is calculated as follows:
in the formula, C f Is MgSO in stock solution 4 Concentration, C p Is MgSO in the penetrating fluid 4 And (4) concentration.
From the initial performance of the membrane, in the embodiment, the reaction activity of the sulfinyl chloride and the polyamine is reduced, so that the polyamide structure is loose, the membrane flux is greatly improved compared with that of a comparative example, and the salt rejection rate is slightly reduced. Wherein, the poly-acyl chloride alkyl in the embodiment 4 and the embodiment 3 is 3-carbon propyl, but the isopropyl electron-donating effect is stronger, so that the electronegativity of the S atom of the adjacent sulfinyl chloride group is larger, the nucleophilic reaction activity during the amidation reaction is reduced, the flux of the obtained membrane is increased, and the salt rejection rate is reduced.
In order to further verify the acid resistance of the membrane prepared by the invention, a hydrochloric acid solution with pH =2 is prepared, the solution is heated and maintained at the temperature of 40 +/-0.5 ℃, and after the membrane is soaked for 24 hours, mgSO is carried out 4 Standard tests, the results obtained are shown in the following table:
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A nanofiltration membrane is characterized by comprising a non-woven fabric layer, a porous supporting layer and a desalting layer which are contacted in sequence;
the desalting layer is formed by performing interfacial polymerization reaction on the water phase solution and the oil phase solution on the surface of the porous supporting layer;
the aqueous phase solution contains polyamine monomers; the oil phase solution contains a sulfinyl chloride monomer with a structure shown in a formula (I):
in the formula (I), R1, R2 and R3 are alkyl.
2. Nanofiltration membrane according to claim 1, wherein R1, R2 and R3 are alkyl groups.
3. Nanofiltration membrane according to claim 2, wherein R1, R2 and R3 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
4. Nanofiltration membrane according to claim 1, wherein the polyamine monomer is one or more of piperazine, hexahydropyrimidine, meta-phenylenediamine, para-phenylenediamine, ethylene diamine and propane diamine.
5. A method of producing nanofiltration membrane according to any one of claims 1~4, comprising the steps of:
a) Providing a base film, wherein the base film is of a double-layer structure, the front surface of the base film is a porous supporting layer, and the back surface of the base film is a non-woven fabric layer;
b) Soaking the base membrane into the aqueous phase solution, taking out the base membrane, and removing the redundant aqueous phase solution on the base membrane;
c) Coating the oil phase solution on the front surface of the base film treated in the step b) to perform interfacial polymerization reaction, and then removing the redundant oil phase solution on the front surface of the base film;
d) Drying the base membrane treated in the step c) to obtain the nanofiltration membrane.
6. The method according to claim 5, wherein the base film is prepared in step a) according to the following steps:
coating the casting solution on the surface of one side of the non-woven fabric, and then carrying out phase inversion curing in water to obtain a base film;
the components of the membrane casting solution comprise sulfonated polysulfone and an organic solvent.
7. The preparation method according to claim 6, wherein the components of the membrane casting solution further comprise a pore-foaming agent.
8. The preparation method according to claim 5, wherein in the step b), the soaking temperature is 10 to 40 ℃; the soaking time is 10 to 30s.
9. The preparation method according to claim 5, wherein in the step c), the temperature of the interfacial polymerization reaction is 10 to 40 ℃; the time of the interfacial polymerization reaction is 5 to 20s.
10. The method according to claim 5, wherein the drying temperature in step d) is 50 to 60 ℃.
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