CN117323822A - Preparation method of high-temperature-resistant reverse osmosis membrane - Google Patents
Preparation method of high-temperature-resistant reverse osmosis membrane Download PDFInfo
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- CN117323822A CN117323822A CN202311565979.2A CN202311565979A CN117323822A CN 117323822 A CN117323822 A CN 117323822A CN 202311565979 A CN202311565979 A CN 202311565979A CN 117323822 A CN117323822 A CN 117323822A
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- reverse osmosis
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- 239000012528 membrane Substances 0.000 title claims abstract description 173
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 135
- 239000011248 coating agent Substances 0.000 claims abstract description 121
- 238000000576 coating method Methods 0.000 claims abstract description 121
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000005266 casting Methods 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 57
- 239000012071 phase Substances 0.000 claims abstract description 54
- 239000008346 aqueous phase Substances 0.000 claims abstract description 51
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 29
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 30
- -1 amine compounds Chemical class 0.000 claims description 27
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 22
- YBGQXNZTVFEKEN-UHFFFAOYSA-N benzene-1,2-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1S(Cl)(=O)=O YBGQXNZTVFEKEN-UHFFFAOYSA-N 0.000 claims description 22
- 230000001112 coagulating effect Effects 0.000 claims description 22
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002346 layers by function Substances 0.000 claims description 20
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical group CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- MHQULXYNBKWNDF-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1C MHQULXYNBKWNDF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000010612 desalination reaction Methods 0.000 abstract description 19
- 230000004907 flux Effects 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 230000002238 attenuated effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 119
- 239000002585 base Substances 0.000 description 71
- 238000002156 mixing Methods 0.000 description 46
- 239000004745 nonwoven fabric Substances 0.000 description 25
- 238000001914 filtration Methods 0.000 description 24
- 229920000728 polyester Polymers 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 19
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 19
- 230000001965 increasing effect Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 230000001976 improved effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008093 supporting effect Effects 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to the technical field of membrane separation material preparation, in particular to a preparation method of a high-temperature-resistant reverse osmosis membrane, which comprises the following steps: preparing a casting solution: the casting film liquid comprises 8-14 parts by weight of solid polysulfone, 5-10 parts by weight of bismaleimide resin, 1-3 parts by weight of fumed silica, 75-82 parts by weight of N, N-dimethylformamide and 0.5-3 parts by weight of pore-forming agent, and the raw materials are uniformly mixed, placed still, defoamed and filtered to obtain the casting film liquid; uniformly coating the casting film liquid on a base film, standing, and then placing the film in water solidification liquid to obtain a porous support composite base film; coating aqueous phase solution on the porous support composite base film, and drying; then coating the acyl chloride oil phase solution, and post-treating to obtain the reverse osmosis composite membrane. The reverse osmosis composite membrane in the application improves the heat resistance and the stability of the membrane under the condition that the membrane flux and the desalination rate are not obviously attenuated, reduces the running cost of high-temperature water treatment and prolongs the service life of the membrane to a certain extent.
Description
Technical Field
The application relates to the technical field of membrane separation material preparation, in particular to a preparation method of a high-temperature-resistant reverse osmosis membrane.
Background
The membrane separation technology is one of the preferred technologies in the field of water pollution control engineering, and can be classified into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane according to its filtration accuracy. The reverse osmosis membrane technology has a plurality of advantages in the desalination of salt water, including the characteristics of low energy consumption, low investment cost, high recovery rate, small occupied area, high salt removal rate, stable water quality and the like. In addition, the reverse osmosis membrane system has long service life, so that the reverse osmosis membrane system is widely applied to the fields of drinking water purification, sewage and wastewater treatment and reuse.
However, the application of reverse osmosis membranes in different fields is increasing, and higher requirements are put on the performance of the reverse osmosis membranes, especially in the fields of food, medicine, textile and the like, raw water is often high-temperature wastewater, and the temperature is usually higher than 45 ℃. Reverse osmosis membranes currently on the market are generally composed of a non-woven fabric, a porous support layer and a separation layer, and have the defects of low strength, easy deformation, easy breakage and easy stripping. In addition, the existing reverse osmosis membranes generally have a service temperature of less than 40 ℃ and thus cannot operate effectively under high temperature conditions. At high temperature, the desalination performance of the existing membrane can be rapidly reduced, so that the membrane flux and the desalination rate are reduced, the quality of produced water is affected, the running cost is increased, and the service life of the membrane is reduced.
At present, the common method for industrially treating the high-temperature wastewater is to introduce the wastewater into a wastewater transfer tank for cooling treatment, and then use a reverse osmosis membrane system for water purification treatment. This method increases the treatment process, causes accumulation of wastewater, and is unfavorable for industrial production.
Therefore, developing a high temperature resistant reverse osmosis membrane would greatly improve the application potential of reverse osmosis membranes in the field of drinking water purification and sewage/wastewater treatment. Improving the high temperature resistance and stability of membranes without significantly reducing membrane flux and desalination rates has become a major challenge in overcoming the challenges of membrane separation technologies in the areas of potable water purification and sewage/wastewater treatment.
Disclosure of Invention
In order to solve the stability and performance problems of the existing reverse osmosis membrane for treating high-temperature raw water, the application provides a preparation method of a high-temperature-resistant reverse osmosis membrane, which comprises the following steps:
s1: preparing a casting solution: the casting film liquid comprises 8-14 parts by weight of solid polysulfone, 5-10 parts by weight of bismaleimide resin, 1-3 parts by weight of fumed silica, 75-82 parts by weight of N, N-dimethylformamide and 0.5-3 parts by weight of pore-forming agent, and the casting film liquid is obtained by uniformly mixing the above raw materials, standing, defoaming and filtering;
s2: uniformly coating the casting film liquid on a polyester non-woven fabric, and placing the film obtained after standing in water coagulating liquid to obtain a porous support composite base film;
S3: contacting the porous support composite base film with an aqueous phase solution containing amine compounds in a coating mode, and drying;
s4: contacting the film obtained in the step S3 with an oil phase solution containing acyl chloride compounds in a coating mode to form a functional layer; drying to obtain the reverse osmosis composite membrane.
According to the technical scheme, the defects of lack of active groups and insufficient branching or crosslinking on polysulfone high-molecular chains are overcome by introducing bismaleimide resin containing benzene rings, imide heterocycle and having high crosslinking density into the porous support composite base membrane layer. In addition, the bismaleimide resin effectively disperses the nanomaterial between polysulfone molecular chains through a twisted non-coplanar structure, thereby enhancing the stability and mechanical properties of the membrane. Meanwhile, the strong electron-withdrawing effect of the carbonyl in the bismaleimide enables the bismaleimide to easily perform addition reaction with substances containing active hydrogen such as amide, so that the supporting layer and the functional layer are better crosslinked, and the thermal stability of the reverse osmosis composite membrane is greatly improved.
Meanwhile, the toughness and ageing resistance of the prepared reverse osmosis composite membrane can be greatly improved by compounding the reverse osmosis composite membrane with fumed silica in proper proportion. The inventor finds that by means of the nanoparticle characteristic and three-dimensional chain microstructure characteristic of the fumed silica, and the hydroxyl groups rich in surface, or the hydroxyl groups can be firmly crosslinked with the inherent electron withdrawing groups of the bismaleimide resin, a stable space network structure is formed, so that the physical and chemical properties of the whole reverse osmosis membrane material, such as toughness, high temperature resistance and the like, are greatly improved, in the practical application process, the water flux of the membrane is also obviously increased, analysis shows that the fumed silica possibly has higher porosity, the water flux of the membrane is greatly increased, the fumed silica is light in weight and high in strength, and the reverse osmosis membrane can play a role in protecting the stability of the reverse osmosis membrane structure when the reverse osmosis membrane runs at high temperature. Under the condition that the membrane flux and the desalination rate are not obviously attenuated, the heat resistance and the stability of the reverse osmosis composite membrane are greatly improved, the running cost of high-temperature water treatment is reduced, and the service life of the membrane is prolonged to a certain extent.
In a specific embodiment, the fumed silica has an average particle size of from 6 to 8nm.
By adopting the technical scheme, the uniform microporous fumed silica can be better crosslinked with organic matters to form a stable space reticular structure, the contact area with the porous support composite membrane is increased, the stress of the membrane layer is concentrated, and the heat-resistant stability is better.
By adopting the technical scheme, the mass ratio of the bismaleimide resin to the fumed silica is (2-5): 1.
through adopting the technical scheme, through the organic compounding of the bismaleimide resin and the fumed silica, the fumed silica is properly dispersed in gaps among polymer molecular chains, and the polymer molecular chains are connected together, so that the stress of the porous support composite membrane is more concentrated, and when the reverse osmosis composite membrane runs at a high temperature, the reinforcing and toughening effects are exerted to keep stable crosslinking of the membrane, thereby enhancing the heat-resistant stability of the membrane.
In a specific embodiment, the aqueous phase solution comprises the following components in parts by weight: 4-12 parts of diamine, 0.5-3 parts of silver nano particles, 2-2.5 parts of pH regulator, 0.15-0.45 part of surfactant, 0.15-1.2 parts of acid acceptor, 2-4 parts of modifier, 1-2.5 parts of N, N-dimethylacetamide and 72-78 parts of pure water, wherein the casting solution also comprises 1-3 parts of mercaptosilane coupling agent. Preferably, the average particle size of the silver nanoparticles is not greater than 10nm.
By adopting the technical scheme, diamine is used as an amine monomer to carry out cross-linking polymerization with acyl chloride. The pH regulator is used for regulating the pH value of the liquid and promoting the smooth progress of the interface reaction of the functional layer. The silver nano particles can be embedded into the functional layer with interface polymerization reaction through interaction with the mercapto silane coupling agent, so that the water flux of the reverse osmosis membrane is increased, the nano silver is prevented from losing in water, the uniform stability of the reverse osmosis composite membrane can be effectively improved by the silver nano particles with uniform particle size, and the nano silver can also promote the sterilization or bacteriostasis performance of the composite membrane. The sulfhydryl silane coupling agent better adheres to the porous supporting layer, effectively crosslinks silver nano particles of the functional layer, and promotes efficient interface fusion. The surfactant has better tensile property, can optimize the performance of the composite film, and the acid acceptor can prevent the interface polymerization reaction from being influenced by the combination of the acid acceptor and chloride ions in water by neutralizing the generated acid substance. The modifier hydrolyzes and modifies the surface of the supporting layer, and increases active groups on the surface of the supporting layer. N, N-dimethylacetamide has good solubility as a polar solvent and has the function of catalyzing the generation of a composite film.
In a specific embodiment, the diamine is one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-chloro-1, 3-phenylenediamine and dimethylbenzenediamine; the pH regulator is one or more of camphorsulfonic acid, tannic acid and citric acid; the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate and sodium glycocholate; the acid acceptor is sodium hydroxide; the modifier is N-methyl pyrrolidone.
By adopting the technical scheme, the desalination rate of the composite membrane can be improved by selecting specific phenyl diamine, the desalination rate is ensured to be kept in a higher range continuously when the reverse osmosis composite membrane runs at a high temperature, and analysis shows that a great amount of phenyl groups in the functional layer form a conjugated system in the functional layer, so that the system is more stable, the internal energy is smaller, and the heat-resistant stability of the functional layer membrane can be enhanced. The pH regulator, the surfactant and the acid acceptor can further optimize the overall structural performance of the reverse osmosis composite membrane. The pH regulator and the acid acceptor are favorable for regulating the smooth progress of the interfacial polymerization reaction of the functional layer. The surfactant has better tensile property, and can optimize the integral crosslinking heat-resistant stability of the composite film.
In a specific embodiment, the acyl chloride oil phase solution comprises 1-4 parts by weight of acyl chloride monomer and 80-88 parts by weight of oil phase solvent, wherein the acyl chloride monomer is one or more of trimesoyl chloride, 4' -biphenyl dicarboxylic acid chloride, benzene disulfonyl chloride and terephthaloyl chloride, and the oil phase solvent is one or more of normal hexane, cyclohexane or heptane.
By adopting the technical scheme, the acyl chloride monomer is dissolved in the organic solvent, and the oil phase polar solvent acyl chloride monomer has better solubility, thereby being beneficial to the interfacial polymerization with the aqueous phase solution to form the polyamide functional layer.
In a specific embodiment, the mercaptosilane coupling agent is gamma-mercaptopropyl trimethoxysilane or gamma-mercaptopropyl triethoxysilane.
By adopting the technical scheme, the mercapto silane coupling agent is gamma-mercaptopropyl trimethoxy silane or gamma-mercaptopropyl triethoxy silane, can interact with silver nano particles of aqueous phase solution, and is embedded in a separation layer where interfacial polymerization reaction occurs, so that a stable functional surface layer is formed.
In a specific embodiment, the porogen is selected from one or more of polyethylene glycol, polyvinylpyrrolidone and 1, 4-dioxane.
By adopting the technical scheme, the resistance in the water mass transfer process can be reduced, and the improvement of the water flux of the reverse osmosis membrane is facilitated.
In a specific embodiment, the temperature of the aqueous solidification liquid is in the range of 8-16 ℃.
By adopting the technical scheme, the casting solution is beneficial to being phase-converted into the porous support base film meeting the requirements in water.
In a specific embodiment, after the step S4, the obtained reverse osmosis membrane is cleaned by pure water, wetted by glycerol, and then coated on the surface of the composite membrane by PVA, and is dried at 60-80 ℃.
Through adopting above-mentioned technical scheme, through polyvinyl alcohol at the surface cross-linking adhesion of functional layer, form the antifouling layer on polyamide layer surface, can improve reverse osmosis membrane complex film's hydrophilicity and chlorine resistance simultaneously, consequently, prolonged reverse osmosis membrane complex film's life.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the defects of lack of active groups and branches or insufficient crosslinking on polysulfone high polymer chains are overcome by introducing bismaleimide resin containing benzene rings, imide heterocycle and having higher crosslinking density into the porous support composite base membrane layer. In addition, the bismaleimide resin effectively disperses the nanomaterial between polysulfone molecular chains through a twisted non-coplanar structure, thereby enhancing the stability and mechanical properties of the membrane. Meanwhile, the strong electron-withdrawing effect of the carbonyl in the bismaleimide enables the bismaleimide to easily perform addition reaction with substances containing active hydrogen such as amide, so that the supporting layer and the functional layer are better crosslinked, and the thermal stability of the reverse osmosis composite membrane is greatly improved.
2. Through the organic compounding of the bismaleimide resin and the fumed silica, the fumed silica is properly dispersed in gaps among polymer molecular chains, the fumed silica is of a three-dimensional chain structure, a large number of free hydroxyl groups distributed on the surface can be fully embedded into the bismaleimide resin to be connected with strong electron-withdrawing groups rich in molecular chains, and the polymer molecular chains are connected together, so that the stress of the porous support composite membrane is more concentrated, and when the reverse osmosis composite membrane is impacted by external force, the effects of reinforcing and toughening are exerted, and the stability of the membrane is enhanced.
3. The silver nano particles can be embedded into the functional layer with interface polymerization reaction through interaction with the mercapto silane coupling agent, so that the water flux of the reverse osmosis membrane is increased, the nano silver is prevented from losing in water, a stable functional layer is formed, the nano silver is crosslinked with the porous supporting layer, the stability of the composite membrane is enhanced, and meanwhile, the water flux and the retention rate of the membrane are not obviously attenuated.
Detailed Description
Some of the starting materials used in the preparation examples and examples:
bismaleimide resin CAS number: 13676-54-5 model: pe331; gamma-mercaptopropyl trimethoxysilane CAS No.: 4420-74-0, model: KH-591; gamma-mercaptopropyl triethoxysilane CAS number: 14814-09-6, model: KH-592; fumed silica model: a380; the bottom film is polyester non-woven fabric.
The relevant raw materials used in the examples and comparative examples, which were not noted, were conventional products commercially available.
Examples
Example 1
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: dissolving 8g of solid polysulfone, 5g of bismaleimide resin and 1g of fumed silica with the average particle size of 6-8nm in 75g of N, N-dimethylformamide, adding 0.5g of 1, 4-dioxane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution; s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 4-chloro-1, 3-phenylenediamine into 72g of water for dissolution, then sequentially adding 1g of N, N-dimethylacetamide, 0.15g of sodium hydroxide, 0.15g of sodium dodecyl sulfate, 2g of camphorsulfonic acid and 2g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 1g of benzene disulfonyl chloride and 80g of normal hexane to obtain an oil phase solution, uniformly coating the oil phase solution containing acyl chloride compounds on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 2
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 10g of solid polysulfone, 6g of bismaleimide resin, 2g of fumed silica with the average particle size of 6-8nm, dissolving in 82g of N, N-dimethylformamide, adding 3g of polyvinylpyrrolidone, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in a water solidification liquid at 10 ℃ to obtain a porous support composite base film;
s3: adding 6g of o-phenylenediamine into 78g of water for dissolution, then sequentially adding 2g of N, N-dimethylacetamide, 1.2 sodium hydroxide, 0.15 sodium dodecyl benzene sulfonate, 2g of tannic acid and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: mixing 2g of 4,4' -biphenyl dicarboxylic acid chloride and 84g of cyclohexane uniformly to obtain an oil phase solution, uniformly coating the oil phase solution containing acyl chloride compounds on the membrane obtained in the step S3 in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 3
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin, 2g of fumed silica with the average particle size of 6-8nm, dissolving in 80g of N, N-dimethylformamide, adding polyethylene glycol, uniformly mixing with the mixture, standing for 10s, and defoaming and filtering to obtain a casting solution; s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 0.35g of citric acid and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 4
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 14g of solid polysulfone, 6g of bismaleimide resin and 3g of fumed silica with the average particle size of 6-8nm, placing the mixture into 80g of N, N-dimethylformamide, adding 2g of polyvinylpyrrolidone, uniformly mixing, standing for 10s, and filtering to obtain a casting solution after defoaming;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in a water solidification liquid at 16 ℃ to obtain a porous support composite base film;
s3: adding 12g of m-phenylenediamine into 78g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.45g of sodium glycocholate, 0.45g of citric acid and 4g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 4g of terephthaloyl chloride and 88g of heptane to obtain an oil phase solution, uniformly coating the oil phase solution containing acyl chloride compounds on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 5
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 6g of bismaleimide resin, 2g of fumed silica with the average particle size of 6-8nm, placing in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting film solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 2.5g of sodium hydroxide, 2.5g of sodium lauryl sulfonate, 2.5g of citric acid and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 6
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the mixture in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 2.5g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 7
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 1g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 2.5g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 8
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 5g of bismaleimide resin and 3g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 2.5g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 9
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 6g of bismaleimide resin and 3g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 10
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of triethylene diamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 11
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 25nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 12
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing acyl chloride compounds on the membrane obtained in the step (S3) in a contact coating mode, drying at 60 ℃ for 5min after completion, washing with pure water and wetting with glycerol, coating PVA on the surface of the composite membrane, and finally drying at 60 ℃ for 6min to obtain the reverse osmosis composite membrane.
Example 13
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 1.2g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 2.5g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing acyl chloride compounds on the membrane obtained in the step (S3) in a contact coating mode, drying at 60 ℃ for 5min after completion, washing with pure water and wetting with glycerol, coating PVA on the surface of the composite membrane, and finally drying at 80 ℃ for 6min to obtain the reverse osmosis composite membrane.
Example 14
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 1g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid and 0.35g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 15
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 3g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid and 0.35g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 16
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 17
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 18
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Example 19
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone, 10g of bismaleimide resin and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol and 1g of gamma-mercaptopropyl trimethoxy silane, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Comparative example
Comparative example 1
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: dissolving 12g of solid polysulfone in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing, defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Comparative example 2
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: taking 12g of solid polysulfone and 2g of fumed silica with the average particle size of 6-8nm, placing the fumed silica in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting film liquid;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Comparative example 3
The preparation method of the high-temperature-resistant reverse osmosis membrane comprises the following steps:
s1: placing 12g of solid polysulfone and 10g of bismaleimide resin in 80g of N, N-dimethylformamide, adding 2g of polyethylene glycol, uniformly mixing, standing for 10s, and defoaming and filtering to obtain a casting solution;
s2: uniformly extruding and coating the casting film liquid on a polyester non-woven fabric, standing for 10s to obtain a film, and then placing the film in 8 ℃ water coagulating liquid to obtain a porous support composite base film;
s3: adding 10g of m-phenylenediamine into 76g of water for dissolution, then sequentially adding 2.5g of N, N-dimethylacetamide, 0.35g of sodium hydroxide, 0.35g of sodium lauryl sulfonate, 2.5g of citric acid, 3g of silver nano particles and 3g of N-methylpyrrolidone to obtain an aqueous phase solution, uniformly coating the aqueous phase solution containing amine compounds on the porous support composite base film obtained in the step S2 in a contact coating mode, and placing the porous support composite base film in a vacuum oven at 60 ℃ for 3min to remove surface moisture;
s4: and (3) uniformly mixing 3g of benzene disulfonyl chloride and 86g of cyclohexane to obtain an oil phase solution, uniformly coating the oil phase solution containing the acyl chloride compound on the membrane obtained in the step (S3) in a contact coating mode, and drying at 60 ℃ for 5min after completion to obtain the reverse osmosis composite membrane.
Performance detection
The composite reverse osmosis membranes of examples 1 to 19 and comparative examples 1 to 3 were continuously operated for 72 hours at three operating temperatures of 25, 50, 85℃and an operating pressure of 1.55MPa in a 2000ppm sodium chloride solution to test desalination and water permeation properties, and the results are shown in Table I.
TABLE 1 Performance test results
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Referring to table 1, after the high temperature reverse osmosis membranes were continuously operated at 25, 50, and 85 ℃ for 72 hours, respectively, the high temperature reverse osmosis composite membranes of examples 1 to 5 were tested for desalination and water permeation properties, and compared with comparative examples 1 to 3, the high temperature reverse osmosis composite membranes of examples 1 to 5 were increased in water permeation rate with increasing test temperature, were less in desalination rate change, and maintained high desalination rate all the time, whereas the reverse osmosis composite membrane of comparative example 1 was significantly reduced in desalination rate with increasing treatment temperature, and as seen from the comparative examples, the high temperature reverse osmosis composite membrane was maintained relatively high in desalination rate and water permeation rate all the time, and was not deformed, broken or peeled off at the time of high temperature operation, and was effective in improving heat resistance and mechanical properties.
The proper compounding of bismaleimide resin and fumed silica in comparative examples 6-9 can effectively improve the desalination rate and heat-resistant stability of the high-temperature-resistant reverse osmosis composite membrane, and the desalination rate is less when the water flux is obviously increased during operation at a higher temperature, so that the reverse osmosis composite membranes prepared in examples 6 and 9 have higher heat-resistant stability and more stable water production quality during operation, are more suitable for industrial large-scale stable production, and ensure the water production efficiency.
Analysis shows that when the mass ratio of the bismaleimide resin to the fumed silica is greater than 5, the fumed silica cannot fully generate cross-linking interpenetrating characteristic in the obtained mixed bismaleimide resin, and is partially dispersed in the porous separation layer with weaker intermolecular force, so that heat resistance is affected, and further desalination rate is affected, and when the proportion is less than 2, the content proportion of the obtained bismaleimide resin in the porous support layer is reduced, the fumed silica is relatively increased, heat resistance is reduced, stability is stable, and in addition, the permeability of water is increased along with the increase of temperature, the diffusion rate of solute in the aqueous solution is increased, so that solute is easier to permeate through the membrane, and the rejection effect of salt is reduced. While fumed silica further increases the water flux of the membrane, it is difficult to ensure the desired salt removal rate, and therefore these mixing ratios are undesirable and not recommended.
As can be seen from comparative examples 3 and examples 14 to 19, the interaction of the silver nanoparticles and the mercaptosilane coupling agent significantly affects the water flux of the functional layer, and promotes the functional layer to be connected with the porous support layer, thereby increasing the desalination rate and water flux of the high temperature-resistant reverse osmosis composite membrane. The higher desalination rate of the high temperature resistant reverse osmosis composite membrane in example 19 than examples 14-18 can be explained by the silver nanoparticles being embedded in the functional layer undergoing interfacial polymerization reaction through interaction with the mercaptosilane coupling agent, thereby increasing the water flux of the reverse osmosis membrane and simultaneously effectively preventing the nano silver from losing in water, thereby increasing the crosslinking of the functional layer and the porous support layer and effectively improving the heat resistance stability of the membrane.
By combining the embodiment 6 and the embodiments 12-13, the polyvinyl alcohol is coated on the surface of the high-temperature-resistant reverse osmosis composite membrane, so that an antifouling layer can be formed on the surface of the functional layer, meanwhile, the hydrophilicity and chlorine resistance of the reverse osmosis composite membrane can be improved, and the high-temperature-resistant reverse osmosis composite membrane has good durability while maintaining higher flux and retention rate.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The preparation method of the high-temperature-resistant reverse osmosis membrane is characterized by comprising the following steps of:
s1: preparing a casting solution: the casting film liquid comprises 8-14 parts by weight of solid polysulfone, 5-10 parts by weight of bismaleimide resin, 1-3 parts by weight of fumed silica, 75-82 parts by weight of N, N-dimethylformamide and 0.5-3 parts by weight of pore-forming agent, and the raw materials are uniformly mixed, placed still, defoamed and filtered to obtain the casting film liquid;
S2: uniformly coating the casting film liquid on a porous base film, and placing the film obtained after standing in water coagulating liquid to obtain a porous support composite base film;
s3: contacting the porous support composite base film with an aqueous phase solution containing amine compounds in a coating mode, and drying;
s4: and (3) contacting the film obtained in the step (S3) with an oil phase solution containing acyl chloride compounds in a coating mode to form a functional layer, and drying to obtain the reverse osmosis composite film.
2. The method for preparing a high temperature reverse osmosis membrane according to claim 1, wherein the fumed silica has an average particle diameter of 6-8nm.
3. The method for preparing a high temperature reverse osmosis membrane according to claim 1, wherein the mass ratio of the bismaleimide resin to the fumed silica is (2-5): 1.
4. the method for preparing a high temperature-resistant reverse osmosis membrane according to claim 1, wherein the aqueous phase solution comprises the following components in parts by weight: 4-12 parts of diamine, 0.5-3 parts of silver nano particles, 2-2.5 parts of pH regulator, 0.15-0.45 part of surfactant, 0.15-1.2 parts of acid acceptor, 2-4 parts of modifier, 1-2.5 parts of N, N-dimethylacetamide and 72-78 parts of pure water, wherein the casting solution also comprises 1-3 parts of mercaptosilane coupling agent by weight.
5. The method for preparing a high temperature-resistant reverse osmosis membrane according to claim 4, wherein the diamine is one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4-chloro-1, 3-phenylenediamine and dimethylbenzenediamine; the pH regulator is one or more of camphorsulfonic acid, tannic acid and citric acid; the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate and sodium glycocholate; the acid acceptor is sodium hydroxide; the modifier is N-methyl pyrrolidone.
6. The method for preparing the high-temperature-resistant reverse osmosis membrane according to claim 1, wherein the acyl chloride oil phase solution comprises 1-4 parts by weight of acyl chloride monomers and 80-88 parts by weight of oil phase solvents, wherein the acyl chloride monomers are one or more of trimesoyl chloride, 4' -biphenyl dicarboxylic acid chloride, benzene disulfonyl chloride and terephthaloyl chloride, and the oil phase solvents are one or more of n-hexane, cyclohexane and heptane.
7. The method for preparing a high temperature resistant reverse osmosis membrane according to claim 4, wherein the mercaptosilane coupling agent is gamma-mercaptopropyl trimethoxysilane or gamma-mercaptopropyl triethoxysilane.
8. The method for preparing a high temperature resistant reverse osmosis membrane according to claim 1, wherein the pore-forming agent is one or more selected from polyethylene glycol, polyvinylpyrrolidone and 1, 4-dioxane.
9. The method for preparing a high temperature reverse osmosis membrane according to claim 1, wherein the temperature of the aqueous condensate is in the range of 8-16 ℃.
10. The method for preparing a high temperature resistant reverse osmosis membrane according to claim 1, wherein after step S4, the obtained reverse osmosis membrane is cleaned with pure water, wetted with glycerol, coated with PVA on the surface of the composite membrane, and dried at 60-80 ℃.
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