CN114797490B - Preparation method of high-selectivity separation membrane for separating anionic salt - Google Patents
Preparation method of high-selectivity separation membrane for separating anionic salt Download PDFInfo
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- CN114797490B CN114797490B CN202210776053.7A CN202210776053A CN114797490B CN 114797490 B CN114797490 B CN 114797490B CN 202210776053 A CN202210776053 A CN 202210776053A CN 114797490 B CN114797490 B CN 114797490B
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 238000000926 separation method Methods 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 125000000129 anionic group Chemical group 0.000 title abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002091 nanocage Substances 0.000 claims abstract description 25
- -1 anion salt Chemical class 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 6
- 230000002745 absorbent Effects 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 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 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- 101000668432 Homo sapiens Protein RCC2 Proteins 0.000 claims description 4
- 101000951234 Homo sapiens Solute carrier family 49 member 4 Proteins 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 102100039972 Protein RCC2 Human genes 0.000 claims description 4
- 102100037945 Solute carrier family 49 member 4 Human genes 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 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
- 239000004642 Polyimide Substances 0.000 claims description 3
- 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 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- OTFAWEIFBPUXOH-UHFFFAOYSA-N 4-(4-chlorosulfonylphenyl)benzenesulfonyl chloride Chemical compound C1=CC(S(=O)(=O)Cl)=CC=C1C1=CC=C(S(Cl)(=O)=O)C=C1 OTFAWEIFBPUXOH-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 101000668416 Homo sapiens Regulator of chromosome condensation Proteins 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- 102100039977 Regulator of chromosome condensation Human genes 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-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
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims 1
- PUIBKAHUQOOLSW-UHFFFAOYSA-N octanedioyl dichloride Chemical compound ClC(=O)CCCCCCC(Cl)=O PUIBKAHUQOOLSW-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 19
- 238000001728 nano-filtration Methods 0.000 abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 63
- 239000011734 sodium Substances 0.000 description 33
- 239000011780 sodium chloride Substances 0.000 description 30
- 230000004907 flux Effects 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000012267 brine Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 108091006146 Channels Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 108090000862 Ion Channels Proteins 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
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- 239000002351 wastewater Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OSUWBBMPVXVSOA-UHFFFAOYSA-N 4-(4-carbonochloridoylphenoxy)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1OC1=CC=C(C(Cl)=O)C=C1 OSUWBBMPVXVSOA-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
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- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005303 weighing 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
-
- 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
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a high-selectivity separation membrane for separating anionic salts, which comprises the following steps of (1) dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10h under the condition that the stirring temperature is 30-50 ℃, centrifuging and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; (2) Mixing the supermolecule complex, the acid absorbent and the balance of water to prepare an aqueous solution; (3) Contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex; (4) The support film absorbed with supermolecular complex contacts with organic phase solution containing binary or above acyl chloride molecules to generate interfacial polymerization reaction. The invention adopts the preparation method of the high-selectivity separation membrane for separating the anion salt with the structure, so as to solve the problem that the monovalent/divalent anion salt of the traditional nanofiltration membrane material has low selectivity and is difficult to meet the requirement of industrial salt purity.
Description
Technical Field
The invention relates to the technical field of nanofiltration membrane separation, in particular to a preparation method of a high-selectivity separation membrane for separating anionic salts.
Background
NaCl/Na 2 SO 4 The separation of the inorganic salt mixture solution has great application requirements in the fields of strong brine recycling, chlor-alkali brine denitration, water softening, harmful ion removal and the like. The concentrated water of the seawater desalination plant, the outlet water of the sewage treatment plant, the salt-containing wastewater of the mineral exploitation and processing industry and the like have NaCl, naCl/Na as main components 2 SO 4 And the salt is low in industrial application value, and monovalent/divalent salt separation is needed to improve the salt purity of the product. The wastewater of the chlor-alkali production industry contains high-concentration Na + 、Cl - And SO 4 2- Ions, adopting reasonable treatment technology to recover Na 2 SO 4 And water, so that resource recycling is realized.
The nanofiltration membrane separation technology is a new monovalent/divalent inorganic salt solution separation method, and has wide application potential in economy and operability. The preparation of the high-performance nanofiltration membrane is the key for improving the separation efficiency of the monovalent/divalent inorganic salts. The preparation process of the nanofiltration membrane mainly comprises an interface polymerization method, a layer-by-layer self-assembly method and a phase inversion method. The commercial nanofiltration membrane is a polyamide membrane prepared by interfacial polymerization of piperazine and trimesoyl chloride, has high rejection rate on divalent salt, but the selectivity of monovalent/divalent inorganic salt of the nanofiltration membrane cannot meet the requirement of industrial salt separation. Therefore, to be able to realize NaCl/Na 2 SO 4 The efficient and precise separation of the monovalent salt requires the development of a high-selectivity nanofiltration membrane with monovalent salt channels.
Disclosure of Invention
The invention aims to provide a preparation method of a high-selectivity separation membrane for separating anion salts, so as to solve the problems that the monovalent/divalent anion salts of the traditional nanofiltration membrane material have low selectivity and are difficult to meet the requirement of industrial salt purity.
In order to achieve the above objects, the present invention provides a method for preparing a high selectivity separation membrane for separating an anion salt, comprising the steps of:
(1) Dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10 h under the condition of stirring temperature of 30-50 ℃, centrifuging, and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; the mass fraction of the porous organic molecular cage in the host-guest solution is 0.1 to 2%, and the molar ratio of the porous organic molecular cage to the surfactant is 1 to 1;
(2) Mixing 0.1-2% of the supramolecular complex, 0.1-2% of an acid absorbent and the balance of water according to mass fraction to prepare an aqueous solution;
(3) Contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex;
(4) Contacting the support membrane adsorbed with the supermolecule complex with an organic phase solution containing binary and above acyl chloride molecules to generate interfacial polymerization reaction; the organic phase solution comprises 0.1 to 2 mass percent of organic phase monomer and the balance of organic solvent;
(5) And (3) placing the membrane obtained in the step into a drying oven for heat treatment to obtain the monovalent/divalent inorganic salt separation membrane.
Preferably, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 20, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
More preferably, the surfactant is one or more of sodium dodecyl sulfate and dodecyl trimethyl ammonium bromide.
Preferably, the porous organic molecular cage is prepared from 1,3,5-benzenetricarboxylic acid and 1,2-cyclohexanediamine through dehydration condensation and unsaturated bond addition reaction, and is one or more of RCC1, RCC2, RCC3 and RCC4, and the window pore diameter is 2 to 10A.
Preferably, the support membrane is selected from polymer porous membranes with the molecular weight cut-off of 10 kDa to 50 kDa.
Preferably, the material of the polymer porous membrane is one or more of polyethylene, polypropylene, polyvinylidene fluoride, polyamide, polyacrylonitrile, polysulfone, polyethersulfone, polyimide and polytetrafluoroethylene.
Preferably, the acid absorbent is selected from one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
More preferably, the acid absorbent is one or more of sodium carbonate and sodium bicarbonate.
Preferably, the di-and higher acid chloride molecules are selected from one or more of 1,3,5-benzenetricarbonyl chloride, suberoyl malonyl chloride, glutaryl chloride, terephthaloyl chloride, 1,7-pimeloyl chloride, sebacoyl dichloride, adipoyl chloride, sebacoyl chloride, azelaioyl chloride, 1,3-benzenedisulfonyl chloride, 4,4 '-biphenyl disulfonyl chloride, 4,4' -oxybis (benzoyl chloride) isophthaloyl chloride.
More preferably, the di-and poly-acyl chloride molecules are selected from one or more of 1,3-benzene disulfonyl chloride and terephthaloyl chloride.
Preferably, the organic solvent is selected from one or more of n-hexane, n-heptane, isohexane, cyclohexane, cycloheptane and isoheptane.
More preferably, the organic solvent is selected from one or more of n-hexane and n-heptane.
Preferably, in the step (3), the support film is contacted with the aqueous solution for soaking or dipping, the contact time is 1 to 10 min, and the temperature of the aqueous solution is 15 to 40 ℃.
Preferably, in the step (4), the contact operation is soaking or dipping, the contact time is 1 to 10 min, and the temperature of the organic phase mixed solution is 15 to 40 ℃.
The mechanism of the invention is as follows: the surfactant in the host-guest solution can replace high-energy water molecules in the inner cavity of the porous organic molecular cage through hydrophobic effect to form a supramolecular complex with host-guest interaction, so that the water solubility and the dispersibility of RCC3 are improved, and the diffusion of an aqueous phase monomer RCC3@ DTAB to a phase interface is promoted. Furthermore, amino groups of a porous organic molecular cage in the supramolecular complex and acyl chloride groups of binary and above acyl chloride molecules form a supramolecular separation membrane with an ordered, porous and topological structure through interfacial polymerization reaction. Wherein the diameter of the window of the porous organic molecular cage can exert the transmission channel of univalent ions and water molecules and exert NaCl/Na 2 SO 4 The function of selective separation. The surface of the supramolecular separation membrane can reject hydrated ions with larger radius and higher hydration energy and Na through the pore diameter of the separation membrane + And Cl - Equivalent ratio of monovalent hydrated ions to SO 4 2- And Mg 2+ The isodivalent hydrated ions have larger hydrated ion radius and more stable hydrated layer structure, the hydrated layer is not easy to fall off during transmembrane transmission, the steric hindrance is relatively large, and the membrane channel only allows water molecules and monovalent ions (Na) + And Cl - ) And (4) permeating. Therefore, the supramolecular separation membrane of the present invention has supramolecular channels for efficient separation of monovalent/divalent salts, thereby having high permeation flux and monovalent/divalent salt selectivity.
The kind and concentration of the porous organic molecular cage,The type and concentration of the surfactant, and the type and concentration of the binary and higher acyl chloride molecules are related to the structure of the supramolecular membrane formed. The pH value of the aqueous phase solution can be adjusted by adding the acid acceptor, and the polymerization reaction of the porous organic molecular cage and binary and above acyl chloride molecules is promoted. The prepared separation membrane has negative charge on the surface and is used for anion (Cl) - 、SO 4 2- ) Has strong repulsive effect, and can promote the separation of monovalent/divalent anion salt (NaCl/Na) 2 SO 4 Etc.). The electrostatic repulsion strength depends mainly on the total amount of charge carried by the ions. With Cl - Equivalent ratio of monovalent hydrated ions to SO 4 2- The plasma carries more charge and therefore has greater electrostatic repulsion. Thus, na separating the membrane 2 SO 4 The retention rate is higher than NaCl.
Therefore, the invention adopts the NaCl/Na with the structure 2 SO 4 The preparation method of the high-selectivity separation membrane has at least one or part of the following beneficial effects:
（1）NaCl/Na 2 SO 4 the separation layer of the high-selectivity separation membrane is stable and firm, has large permeation flux and good long-term operation stability;
（2）NaCl/Na 2 SO 4 the selectivity is high, and the method can be applied to strong brine recycling, chlor-alkali brine denitration, water softening and harmful ion removal;
（3）NaCl/Na 2 SO 4 the preparation method with high selectivity has the advantages of simple process, mild preparation conditions, wide application range, easy amplification and popularization and easy realization of industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a surface scanning electron micrograph of a support film in example 1 of the present invention;
FIG. 2 shows NaCl/Na in example 1 of the present invention 2 SO 4 Scanning electron microscope images of the surface of the high-selectivity separation membrane;
FIG. 3 shows NaCl/Na in example 1 of the present invention 2 SO 4 Sectional scanning electron microscope images of the high selectivity separation membrane.
Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment is based on the technical solution, and a detailed implementation manner and a specific operation process are provided, but the present invention is not limited to the present embodiment.
The materials used in the present invention: in the present invention and the following examples, all the raw materials may be commercially available without any particular limitation.
The separation and selectivity parameters of the membrane are mainly determined by the permeation flux: (P) Retention rate ofR) And optionally (α) And (4) forming. Permeate flux: (P) The volume of solution permeated in unit time, unit pressure and unit membrane area is calculated according to the following formula:
wherein,P(unit: L.m) -2 ·h -1 ·bar -1 ) In order to realize the solution permeation flux,V'(unit: L) is the volume of permeate collected over a period of time,A(unit: m) 2 ) Is the effective filtration area of the membrane,Δt(unit: h) is a permeation time,ΔP(unit: bar) is the transmembrane pressure.
Retention rate: (R) The degree of interception of inorganic salt in solution by a separation membrane is obtained by the salt concentration of feed liquid and penetrating fluid, and the calculation formula is as follows:
wherein,C p (unit: g. L) -1 ) Is the concentration of the permeate liquid,C f (unit: g. L) -1 ) Is the concentration of the raw material liquid.
Selectivity (α) Refers to the selection of monovalent and divalent mixed salts by a separation membraneSelectivity, derived from the rejection of monovalent and divalent ions, is calculated as follows:
wherein,R m (unit:%) is the rejection of monovalent salts;R d (unit:%) is the retention of the divalent salt.
The salt concentration in the rejection test was 1000 mg. L -1 NaCl or 1000 mg. L -1 Na 2 SO 4 . NaCl/Na in the selectivity test 2 SO 4 The concentration of the mixed salt is 2000 mg. L -1 And the monovalent/divalent ion concentration ratio is 1:1. The monovalent or divalent ion concentration was measured by inductively coupled plasma emission spectroscopy (ICP-OES, VISTA-MPX, varian).
Preparation of porous organic molecular cage RCC 3:
(1) 0.5 g of 1,3, 5-benzenetricarboxylic acid was weighed out and dissolved in 10 mL dichloromethane, and labeled as solution A. 0.5 g of 1, 2-cyclohexanediamine was weighed out and dissolved in 10 mL dichloromethane and labeled as solution B. The solution B was added to the solution A, and 10. Mu.L of trifluoroacetic acid was added to promote the formation of imine bonds. After stirring for 7 days, the white precipitate was collected, washed and dried to obtain a white powder.
(2) The white powder was dissolved in 25 mL dichloromethane and methanol solution (V: V = 1:1), 0.5 g sodium borohydride was added, 15 h was stirred at room temperature, 1 mL deionized water was added, and 9 h was stirred. Collecting a sample, and performing rotary evaporation, washing and drying to obtain the porous organic molecular cage powder.
(3) Weighing 100 g molecular cage powder, dissolving in 10 mL acetone, standing 24 h, centrifuging to collect the sample, placing into 10 mL dichloromethane and ethanol mixed solution (vol: vol = 1:1), adding 0.1 mL deionized water, stirring 48 h, removing the solvent to obtain purified RCC3 particles, and keeping the RCC3 particles for use.
Example 1
Preparing a sodium dodecyl trimethyl benzene sulfonate aqueous solution containing 0.1 percent of porous organic molecular cage RCC3 and 0.1 percent of RCC3 with the molar ratio of 1:1 (mol: mol), and stirring the aqueous solution at 30 ℃ for 2 h; 0.4% sodium carbonate was added as an aqueous phase mixture. An n-heptane solution containing 0.5% of terephthaloyl chloride was prepared as an organic phase mixture. Firstly, placing the water phase mixed solution on the surface of a polysulfone support membrane, adsorbing for 10 min at 30 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 1 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for the separation performance.
Through tests, the rejection rate of the separation membrane to NaCl is 20%, and the rejection rate to Na is 2 SO 4 The rejection rate of the sodium chloride is 98 percent, and the sodium chloride/Na 2 SO 4 The selectivity is 42, and the water permeation flux is 14L m -2 ·h -1 ·bar -1 。
Example 2
Preparing an aqueous solution containing 1% of porous organic molecular cage RCC4, 1:4 (mol: mol) of sodium dodecyl sulfate and 0.4% of sodium bicarbonate according to the mol ratio of 1% of RCC4, and stirring 8 h at 50 ℃; then adding the mixture to obtain a water phase mixed solution. An n-hexane solution containing 1.2% of 1,3-benzenedisulfonyl chloride was prepared as an organic phase mixture. Firstly, placing the water phase mixed solution on the surface of a polyamide support membrane, adsorbing for 5 min at 50 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 9 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for the separation performance.
Tests show that the rejection rate of the separation membrane to NaCl is 15%, and the rejection rate to Na 2 SO 4 The rejection rate of (A) is 95%, naCl/Na 2 SO 4 The selectivity is 20, and the water permeation flux is 25L. M -2 ·h -1 ·bar -1 。
Example 3
Preparing sodium dodecyl sulfate containing 1.4 percent of porous organic molecular cage RCC2 and having a molar ratio of 1.4 percent of RCC2 to 1:6 (mol: mol), and stirring 4 h at 40 ℃; then, 0.4% aqueous sodium hydroxide solution was added as an aqueous mixture. An n-heptane solution containing 0.5% of 1,3-benzenedisulfonyl chloride was prepared as an organic phase mixture. Firstly, placing the water phase mixed solution on the surface of a polyimide support membrane, adsorbing for 3 min at 40 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 7 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for separation performance.
Tests show that the separation membrane has NaCl rejection rate of 30% and Na rejection rate 2 SO 4 The rejection rate of (A) is-99%, naCl/Na 2 SO 4 The selectivity is 47, and the water permeation flux is 15L m -2 ·h -1 ·bar -1 。
Comparative example
The aqueous phase mixture of this comparative example contained no porous molecular cages, as in example 1.
Tests show that the separation membrane has a NaCl rejection rate of 10% and a Na rejection rate 2 SO 4 The rejection rate of the sodium chloride is 65 percent, and the sodium chloride/Na 2 SO 4 The selectivity is 17, the water permeation flux is 4L. M -2 ·h -1 ·bar -1 。
As can be seen by comparing the test results of example 1 and comparative example, example 1 was conducted for NaCl and Na 2 SO 4 The retention rate of NaCl/Na is greatly different 2 SO 4 The selectivity is higher, the water permeation flux of example 1 is much larger than that of the comparative example, which shows that the comparative example does not add an organic porous molecular cage in the reaction process of an organic monomer and an aqueous phase monomer, the organic monomer and the aqueous phase monomer directly undergo a polymerization reaction, and water molecules and monovalent ion channels with ordered, porous and topological structures cannot be formed, so that the higher water permeation flux and NaCl/Na are difficult to obtain 2 SO 4 High selectivity separation membranes.
The separation membrane obtained in example 1 was subjected to a long-term stability test, and the water permeation flux and NaCl/Na of the membrane were measured by a continuous separation test for 72 hours 2 SO 4 The selectivity was essentially unchanged, indicating that NaCl/Na was produced 2 SO 4 The separation membrane has good long-term stability. Scanning Electron microscope was used to obtain highly selective NaCl/Na solution in example 1 2 SO 4 The separation membrane is characterized, fig. 1 shows the surface morphology of the support membrane, and as shown in fig. 2 and fig. 3 shows the surface morphology and the cross-sectional morphology of the obtained membrane, analysis shows that the surface of the separation membrane is smooth, and the attached particles are also small, which indicates that the surfactant-complexed RCC3 supramolecule shows better dispersibility in aqueous solution, and the cross-sectional diagram shows that the separation membrane shows a selective layer thickness of about 100 nm. The appearance change of the surface and the section is mainly due to the fact that the DTAB is introduced, the dispersity of RCC3 molecules in an aqueous solution is improved, and interfacial polymerization reaction between water and organic phase monomers is promoted.
Therefore, the invention adopts the NaCl/Na with high selectivity of the structure 2 SO 4 The preparation method of the separation membrane has the advantages of simple preparation method, mild conditions, wide application range, easy amplification and realization of industrial production, and the prepared high-selectivity NaCl/Na 2 SO 4 The separation layer of the separation membrane has strong firmness, large permeation flux and good long-term operation stability.
Finally, it should be noted that: the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts, comprising the steps of:
(1) Dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10 h under the condition of stirring temperature of 30-50 ℃, centrifuging, and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; the mass fraction of the porous organic molecular cage in the host-guest solution is 0.1 to 2%, and the molar ratio of the porous organic molecular cage to the surfactant is 1 to 1; the porous organic molecular cage is one or more of RCC1, RCC2, RCC3 and RCC4, and the window aperture is 2 to 10A;
(2) Mixing 0.1-2% of the supramolecular complex, 0.1-2% of an acid absorbent and the balance of water according to mass fraction to prepare an aqueous solution;
(3) Contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex;
(4) Contacting the support membrane adsorbed with the supermolecule complex with an organic phase solution containing binary and above acyl chloride molecules to generate interfacial polymerization reaction; the organic phase solution comprises 0.1 to 2 mass percent of organic phase monomers and the balance of organic solvent;
(5) And (3) putting the membrane obtained in the step into a drying box for heat treatment to obtain the high-selectivity separation membrane of the monovalent/divalent anion salt.
2. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 20, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
3. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the porous organic molecular cage RCC3 is prepared from 1,3,5-benzenetricarboxylic acid and 1,2-cyclohexanediamine by a dehydration condensation and unsaturated bond addition reaction method.
4. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the support membrane is selected from a polymer porous membrane with the molecular weight cutoff of 10 kDa to 50 kDa.
5. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 4, wherein: the material of the polymer porous membrane is one of polyethylene, polypropylene, polyvinylidene fluoride, polyamide, polyacrylonitrile, polysulfone, polyethersulfone, polyimide and polytetrafluoroethylene.
6. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the acid absorbent is one or more selected from sodium hydroxide, sodium carbonate and sodium bicarbonate.
7. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the di-and above-acyl chloride molecules are selected from one or more of 1,3,5-benzenetricarbonyl chloride, suberoyl chloride, malonyl chloride, glutaryl chloride, terephthaloyl chloride, 1,7-pimeloyl chloride, sebacoyl chloride, adipoyl chloride, sebacoyl chloride, azelaioyl chloride, 1,3-benzenedisulfonyl chloride, 4,4 '-biphenyl disulfonyl chloride, 4,4' -oxydi (benzoyl chloride) isophthaloyl chloride.
8. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: the organic solvent is selected from one or more of n-hexane, n-heptane, isohexane, cyclohexane, cycloheptane and isoheptane.
9. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: in the step (3), the support film is in contact with the aqueous phase solution for soaking or dipping for 1 to 10 min, and the temperature of the aqueous phase solution is 15 to 40 ℃.
10. The method for preparing a high selectivity separation membrane for separating monovalent/divalent anion salts according to claim 1, wherein: in the step (4), the contact operation is soaking or dipping, the contact time is 1 to 10 min, and the temperature of the organic phase mixed solution is 15 to 40 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058247A1 (en) * | 2005-11-17 | 2007-05-24 | Daikin Industries, Ltd. | Clathrate compound of fluoropolyether molecule |
| CN103635242A (en) * | 2011-07-01 | 2014-03-12 | 国际商业机器公司 | Thin film composite membranes embedded with molecular cage compounds |
| CN106390769A (en) * | 2016-12-07 | 2017-02-15 | 江南大学 | Water-soluble metallic organic molecular cage-based polydimethylsiloxane composite membrane and preparation method thereof |
| CN112390803A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Imine bond-connected porous organic molecular cage material, and preparation and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058247A1 (en) * | 2005-11-17 | 2007-05-24 | Daikin Industries, Ltd. | Clathrate compound of fluoropolyether molecule |
| CN103635242A (en) * | 2011-07-01 | 2014-03-12 | 国际商业机器公司 | Thin film composite membranes embedded with molecular cage compounds |
| CN106390769A (en) * | 2016-12-07 | 2017-02-15 | 江南大学 | Water-soluble metallic organic molecular cage-based polydimethylsiloxane composite membrane and preparation method thereof |
| CN112390803A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Imine bond-connected porous organic molecular cage material, and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Advanced nanofiltration membrane fabricated on the porous organic cage;Zhe Zhai等;《Separation and Purification Technology》;20190721;全文 * |
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