CN117883987B - Preparation method of polyamide reverse osmosis membrane modified by swelling - Google Patents
Preparation method of polyamide reverse osmosis membrane modified by swelling Download PDFInfo
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- CN117883987B CN117883987B CN202410293992.5A CN202410293992A CN117883987B CN 117883987 B CN117883987 B CN 117883987B CN 202410293992 A CN202410293992 A CN 202410293992A CN 117883987 B CN117883987 B CN 117883987B
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- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 239000004952 Polyamide Substances 0.000 title claims abstract description 35
- 229920002647 polyamide Polymers 0.000 title claims abstract description 35
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 27
- 230000008961 swelling Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 239000002033 PVDF binder Substances 0.000 claims abstract description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 150000001263 acyl chlorides Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- -1 acyl chloride modified molecular sieve Chemical class 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- UCVODTZQZHMTPN-UHFFFAOYSA-N heptanoyl chloride Chemical compound CCCCCCC(Cl)=O UCVODTZQZHMTPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 claims description 2
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 2
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 2
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 claims description 2
- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 claims description 2
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 claims description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000002522 swelling effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 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 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a membrane, in particular to a preparation method of a polyamide reverse osmosis membrane modified by swelling, which enables a molecular sieve to be embedded into a polymer network on the surface of a carrier through the swelling action of an organic solvent of a polyvinylidene fluoride carrier so as to improve the pore diameter and the hydrophilicity of the surface of the carrier, thereby improving the amine absorption capacity of the surface of the carrier and further improving the separation performance of the polyamide membrane.
Description
Technical Field
The invention relates to a preparation method of a membrane, in particular to a preparation method of a polyamide reverse osmosis membrane modified by swelling.
Background
Reverse osmosis membranes are the core component of reverse osmosis technology, which separates other substances from water by virtue of their inability to permeate the semipermeable membrane at pressures above that of the solution. The pore size of the reverse osmosis membrane is very small, so that dissolved salts, colloids, microorganisms, organic matters and the like in water can be effectively removed. The system has the advantages of good water quality, low energy consumption, no pollution, simple process, simple and convenient operation and the like.
Polyamide reverse osmosis membranes are the most common membrane materials in the field of reverse osmosis membranes, and most of the reverse osmosis membranes on the market are made of polyamide materials. The polyamide reverse osmosis membrane is generally formed by interfacial polymerization, namely, a carrier is firstly contacted with a water phase monomer and an oil phase monomer in sequence to carry out interfacial polymerization reaction. In order to ensure that the carrier adsorbs the aqueous monomer solution with more energy, the carrier is often modified. The existing modification comprises post-carrier modification and carrier modification, wherein the former is to coat the existing carrier with an intermediate layer, but the method blocks the combination of the polyamide layer and the carrier layer, so that the combination of the intermediate layer, the carrier layer and the polyamide layer is difficult to ensure, and the stability is poor; the latter is a modification of the support preparation, and it is common to blend a modifier with the support polymer material to functionalize the support surface with certain specific groups, but this method requires a specially prepared support, which is not practical for reverse osmosis membrane manufacturers, and the hydrophilically modified support can hinder the transfer of water molecules from the support to the polyamide layer. Accordingly, there is a need for an improvement in the existing methods for preparing polyamide reverse osmosis membranes to overcome the above-described problems.
Disclosure of Invention
The invention provides a preparation method of a novel polyamide reverse osmosis membrane, which enables a molecular sieve to be embedded into a polymer network on the surface of a carrier through swelling action of an organic solvent of a polyvinylidene fluoride carrier so as to improve the pore diameter and the hydrophilicity of the surface of the carrier, thereby improving the amine absorption capacity of the surface of the carrier and further improving the separation performance of the polyamide membrane.
The invention provides a preparation method of a polyamide reverse osmosis membrane modified by swelling, which is characterized by comprising the following steps of;
firstly, performing acyl chlorination modification on a molecular sieve to obtain an acyl chlorination modified molecular sieve;
Secondly, placing one side of the polyvinylidene fluoride ultrafiltration membrane in an acetone solution containing an acyl chloride modified molecular sieve for swelling modification;
and thirdly, taking the swelled and modified ultrafiltration membrane as a carrier to impregnate the water phase monomer and the oil phase monomer so as to form a polyamide separation layer, thereby obtaining the polyamide reverse osmosis membrane.
Preferably, the acid chloride modified molecular sieve is prepared by the following method: the molar ratio of the acyl chloride modifier to the sodium carbonate is 1: 1-1.5% of the organic solvent to form 0.5-20wt% of acyl chloride modified liquid, quickly adding molecular sieve accounting for 1-10wt% of the acyl chloride modified liquid, reacting for 2-8h under stirring, filtering, washing and drying after the reaction is finished.
Preferably, the molecular sieve is one or more of LTA, MFI, CHA, FAU, and the particle size range is 20-500nm.
Preferably, the acyl chloride modifier is selected from one or more of pentanoyl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, dodecanoyl chloride and palmitoyl chloride.
Preferably, the thickness of the polyvinylidene fluoride ultrafiltration membrane is 100-400 mu m, and the aperture is 3-20nm.
Preferably, the content of the acyl chloride modified molecular sieve in the acetone solution is 1-5wt%.
Preferably, the time for swelling modification in the second step is 0.5 to 5 hours.
Preferably, the aqueous phase monomer in the third step is one or more of piperazine, m-phenylenediamine, ethylenediamine, p-phenylenediamine and o-phenylenediamine, the concentration is 0.5-5wt%, and the contact time of the carrier in the aqueous phase monomer is 50-100s.
Preferably, in the third step, the oil phase monomer is one of isophthaloyl dichloride, isophthaloyl trichloride and terephthaloyl dichloride, the concentration is 0.2-3wt%, the oil phase monomer adopts one of normal hexane, cyclohexane, normal heptane and octane, and the contact time of the carrier in the oil phase monomer is 10-120s.
Compared with the prior art, the invention has the following advantages:
Firstly, the present invention can adopt the existing commercial polyvinylidene fluoride ultrafiltration membrane as a carrier, the pore diameter and the hydrophilicity of the carrier surface are improved by swelling the polyvinylidene fluoride carrier in an acetone solvent so that the molecular sieve is embedded in a polymer network on the carrier surface, the amine absorption capacity of the carrier surface is improved, and the molecular sieve is embedded in a polymer material on the carrier surface and does not block the combination of the polymer material and a subsequent polyamide separation layer; secondly, the molecular sieve is modified by acyl chloride, so that the molecular sieve can be combined with the polyamide layer through chemical bonds, and the stability of the molecular sieve in the subsequent application process is improved.
Detailed Description
Examples
The polyamide reverse osmosis membrane of example 1 was prepared by the following steps:
Firstly, heptanoyl chloride and sodium carbonate are mixed according to the mole ratio of 1:1.2, adding the mixture into dichloromethane to form 5wt% of acyl chloride modified liquid, rapidly adding NaA molecular sieve (silicon-aluminum ratio is 1, particle size is 85 nm) accounting for 5wt% of the acyl chloride modified liquid, reacting for 6h under stirring, filtering, washing and drying after the reaction is finished to obtain the acyl chloride modified molecular sieve;
Secondly, placing one side of a polyvinylidene fluoride ultrafiltration membrane (with the thickness of 400 mu m and the aperture of 18nm in an acetone solution containing an acyl chloride modified molecular sieve for swelling modification for 2 hours, and drying, wherein the molecular sieve content in the acetone solution is 2wt%;
and thirdly, taking the ultrafiltration membrane after swelling modification as a carrier, firstly immersing the ultrafiltration membrane in an aqueous solution containing 0.5wt% of m-phenylenediamine for 100s, and then immersing the ultrafiltration membrane in an n-hexane solution containing 2wt% of trimesoyl chloride for 120s to form a polyamide separation layer, thereby obtaining the polyamide reverse osmosis membrane.
Comparative example 1
The polyamide reverse osmosis membrane of comparative example 1 was prepared by the following steps:
firstly, heptanoyl chloride and sodium carbonate are mixed according to the mole ratio of 1:1.2, adding the mixture into dichloromethane to form 5wt% of acyl chloride modified liquid, rapidly adding the mixture accounting for 5wt% of the acyl chloride modified liquid, reacting for 6 hours under the condition of stirring, and filtering, washing and drying after the reaction is finished to obtain the acyl chloride modified molecular sieve;
Secondly, placing one side of the polyvinylidene fluoride ultrafiltration membrane (with the thickness of 400 mu m and the aperture of 18nm in an aqueous solution containing an acyl chloride modified molecular sieve for dip modification for 2 hours, and drying, wherein the molecular sieve content in the aqueous solution is 2wt%;
and thirdly, taking the ultrafiltration membrane after swelling modification as a carrier, firstly immersing the ultrafiltration membrane in an aqueous solution containing 0.5wt% of m-phenylenediamine for 100s, and then immersing the ultrafiltration membrane in an n-hexane solution containing 2wt% of trimesoyl chloride for 120s to form a polyamide separation layer, thereby obtaining the polyamide reverse osmosis membrane.
Comparative example 2
The polyamide reverse osmosis membrane of comparative example 2 was prepared by the following steps:
Firstly, placing one side of a polyvinylidene fluoride ultrafiltration membrane (with the thickness of 400 mu m and the aperture of 18 nm) into an acetone solution containing an unmodified NaA molecular sieve (with the silicon-aluminum ratio of 1 and the particle diameter of 85 nm) for swelling modification for 2 hours, and drying, wherein the molecular sieve content in the acetone solution is 2wt%;
And secondly, taking the ultrafiltration membrane after swelling modification as a carrier, firstly immersing the ultrafiltration membrane in an aqueous solution containing 0.5wt% of m-phenylenediamine for 100s, and then immersing the ultrafiltration membrane in an n-hexane solution containing 2wt% of trimesoyl chloride for 120s to form a polyamide separation layer, thereby obtaining the polyamide reverse osmosis membrane.
Comparative example 3
The polyamide reverse osmosis membrane of comparative example 3 was prepared by the following steps:
Firstly, heptanoyl chloride and sodium carbonate are mixed according to the mole ratio of 1:1.2, adding the mixture into dichloromethane to form 5wt% of acyl chloride modified liquid, rapidly adding NaA molecular sieve (silicon-aluminum ratio is 1, particle size is 85 nm) accounting for 5wt% of the acyl chloride modified liquid, reacting for 6h under stirring, filtering, washing and drying after the reaction is finished to obtain the acyl chloride modified molecular sieve;
Secondly, stirring and mixing 20wt% of polyvinylidene fluoride, 2wt% of acyl chloride modified molecular sieve, 77wt% of N, N-dimethylformamide and 1 wt% of pore-forming agent polyvinylpyrrolidone for 12 hours, defoaming for 12 hours, scraping a film on a glass plate, soaking in distilled water for 10 minutes, and drying to obtain a blending ultrafiltration film;
and thirdly, taking the blended ultrafiltration membrane as a carrier, firstly immersing the carrier in an aqueous solution containing 0.5wt% of m-phenylenediamine for 100s, and then immersing the carrier in an n-hexane solution containing 2wt% of trimesoyl chloride for 120s to form a polyamide separation layer, thereby obtaining the polyamide reverse osmosis membrane.
The polyamide reverse osmosis membrane samples of the above examples and comparative examples were tested for initial properties of the membranes with 2000ppm aqueous sodium chloride solution at a pressure of 1MPa and for post-properties after 30 days of continuous operation, and the results are shown in the following table:
Table 1 film properties of the different examples and comparative example 1
| Sample of | Initial rejection rate | Initial water flux | Retention after 30d | Water flux after 30d |
| Example 1 | 98.9% | 43.6L/(m2h) | 98.3% | 44.0L/(m2h) |
| Comparative example 1 | 98.2% | 45.1L/(m2h) | 95.8 | 55.2L/(m2h) |
| Comparative example 2 | 98.3% | 45.6L/(m2h) | 89.3 | 60.2L/(m2h) |
| Comparative example 3 | 99.0% | 35.5L/(m2h) | 98.7% | 34.1L/(m2h) |
While the invention has been illustrated and described in connection with embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (9)
1. The preparation method of the polyamide reverse osmosis membrane modified by swelling is characterized by comprising the following steps of;
firstly, performing acyl chlorination modification on a molecular sieve to obtain an acyl chlorination modified molecular sieve;
Secondly, placing one side of the polyvinylidene fluoride ultrafiltration membrane in an acetone solution containing an acyl chloride modified molecular sieve for swelling modification;
And thirdly, sequentially soaking the water phase monomer solution and the oil phase monomer solution by taking the swelled and modified ultrafiltration membrane as a carrier to form a polyamide separation layer so as to obtain the polyamide reverse osmosis membrane.
2. The method according to claim 1, characterized in that the acid chloride modified molecular sieve is prepared by the following method: the molar ratio of the acyl chloride modifier to the sodium carbonate is 1: 1-1.5% of the organic solvent to form 0.5-20wt% of acyl chloride modified liquid, quickly adding molecular sieve accounting for 1-10wt% of the acyl chloride modified liquid, reacting for 2-8h under stirring, filtering, washing and drying after the reaction is finished.
3. The method according to claim 2, wherein the molecular sieve is one or more of types LTA, MFI, CHA, FAU, and has a particle size ranging from 20 to 500nm and a silica-alumina ratio ranging from 0.5 to 5.
4. The method according to claim 2, characterized in that the acyl chloride modifier is selected from one or more of pentanoyl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, dodecanoyl chloride, palmitoyl chloride.
5. The method according to claim 1, characterized in that the polyvinylidene fluoride ultrafiltration membrane has a thickness of 100-400 μm and a pore size of 3-20nm.
6. The method according to claim 1, characterized in that the content of acid chloride modified molecular sieve in the acetone solution is 1-5wt%.
7. The method according to claim 1, wherein the time for swelling modification in the second step is 0.5 to 5 hours.
8. The method according to claim 1, wherein the aqueous monomer in the third step is one or more of piperazine, m-phenylenediamine, ethylenediamine, p-phenylenediamine, and o-phenylenediamine, the concentration is 0.5-5wt%, and the contact time of the carrier in the aqueous monomer solution is 50-100s.
9. The method according to claim 1, wherein in the third step, the oil phase monomer is one of isophthaloyl dichloride, isophthaloyl trichloride and terephthaloyl dichloride, the concentration is 0.2-3wt%, the solvent used in the oil phase monomer solution is one of n-hexane, cyclohexane, n-heptane and octane, and the contact time of the carrier in the oil phase monomer solution is 10-120s.
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Citations (7)
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