US20130112619A1 - Solvent resistant polyamide nanofiltration membranes - Google Patents
Solvent resistant polyamide nanofiltration membranes Download PDFInfo
- Publication number
- US20130112619A1 US20130112619A1 US13/810,935 US201113810935A US2013112619A1 US 20130112619 A1 US20130112619 A1 US 20130112619A1 US 201113810935 A US201113810935 A US 201113810935A US 2013112619 A1 US2013112619 A1 US 2013112619A1
- Authority
- US
- United States
- Prior art keywords
- membrane
- solvent
- membranes
- solution
- nanofiltration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 353
- 239000002904 solvent Substances 0.000 title claims abstract description 95
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 61
- 239000004952 Polyamide Substances 0.000 title description 18
- 229920002647 polyamide Polymers 0.000 title description 18
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 230000003213 activating effect Effects 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 230000003750 conditioning effect Effects 0.000 claims abstract description 26
- 238000010791 quenching Methods 0.000 claims abstract description 18
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 109
- 239000000243 solution Substances 0.000 claims description 76
- 239000000178 monomer Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 40
- -1 polypropylene Polymers 0.000 claims description 37
- 229920001223 polyethylene glycol Polymers 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 22
- 239000004642 Polyimide Substances 0.000 claims description 19
- 229920001721 polyimide Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920002530 polyetherether ketone Polymers 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004693 Polybenzimidazole Substances 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000008282 halocarbons Chemical class 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229920002480 polybenzimidazole Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- HXUUVGVJMIBARI-UHFFFAOYSA-N hex-1-ene-1,6-diamine Chemical compound NCCCCC=CN HXUUVGVJMIBARI-UHFFFAOYSA-N 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 235000019871 vegetable fat Nutrition 0.000 claims description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 230000004907 flux Effects 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- 239000004793 Polystyrene Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 238000012695 Interfacial polymerization Methods 0.000 description 23
- 239000010409 thin film Substances 0.000 description 22
- 238000011282 treatment Methods 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000001412 amines Chemical group 0.000 description 16
- 239000012527 feed solution Substances 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- 239000002609 medium Substances 0.000 description 13
- 238000001223 reverse osmosis Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229940018564 m-phenylenediamine Drugs 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 241000894007 species Species 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 150000001266 acyl halides Chemical class 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical group 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical class C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920001108 Polyimide P84 Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 150000007513 acids Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AMBFNDRKYCJLNH-UHFFFAOYSA-N 1-(3-piperidin-1-ylpropyl)piperidine Chemical compound C1CCCCN1CCCN1CCCCC1 AMBFNDRKYCJLNH-UHFFFAOYSA-N 0.000 description 1
- DPQNQLKPUVWGHE-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-amine Chemical compound NCC(F)(F)C(F)(F)F DPQNQLKPUVWGHE-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
-
- 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
- B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
-
- 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
- B01D61/027—Nanofiltration
-
- 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
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Definitions
- the present invention relates to thin film composite membranes formed by interfacial polymerisation.
- Membranes and membrane systems described herein may be used in a variety of applications, including, but not limited to, nanofiltration, desalination and water treatment, and particularly the nanofiltration of solutes dissolved in organic solvents.
- Membrane processes have been widely applied in separation science, and can be applied to a range of separations of species of varying molecular weights in liquid and gas phases (see for example “Membrane Technology and Applications” 2 nd Edition, R. W. Baker, John Wiley and Sons Ltd, ISBN 0-470-85445-6).
- Nanofiltration is a membrane process utilising membranes of molecular weight cut-off in the range of 200-2,000 Daltons.
- Molecular weight cut-off of a membrane is generally defined as the molecular weight of a molecule that would exhibit a rejection of 90% when subjected to nanofiltration by the membrane.
- Nanofiltration has been widely applied to filtration of aqueous fluids, but due to a lack of suitable solvent stable membranes, it has not been widely applied to the separation of solutes in organic solvents.
- Nanofiltration membranes for aqueous applications are generally fabricated by making composite membranes.
- Thin film composite membranes may be fabricated via interfacial polymerization (herein also referred to as IP) or by dip-coating [Lu, X.; Bian, X.; Shi, L., “ Preparation and characterization of NF composite membrane.” J. Membr. Sci., 210, 3-11, 2002].
- IP interfacial polymerization
- an aqueous solution of a reactive monomer (often a polyamine) is first deposited in the pores of a microporous support membrane, often a polysulfone ultrafiltration membrane. Then, the polysulfone support membrane loaded with the monomer is immersed in a water-immiscible solvent solution containing a reactive monomer, such as diacid chloride in hexane. The two monomers react at the interface of the two immiscible solutions, until a thin film presents a diffusion barrier and the reaction is completed to form a highly cross-linked thin film layer that remains attached to the support membrane.
- the thin film layer can be from several tens of nanometres to several micrometres thick.
- the IP technique is well known to those skilled in the art [Petersen, R. J. “ Composite reverse osmosis and nanofiltration membranes”. J. Membr. Sci, 83, 81-150, 1993].
- the thin film is selective between molecules, and this selective layer can be optimized for solute rejection and solvent flux by controlling the coating conditions and characteristics of the reactive monomers.
- the microporous support membrane can be selectively chosen for porosity, strength and solvent resistance.
- a particularly preferred class of thin film materials for nanofiltration are polyamides formed by interfacial polymerization. Examples of such polyamide thin films are found in U.S. Pat. Nos. 5,582,725, 4,876,009, 4,853,122, 4,259,183, 4,529,646, 4,277,344 and 4,039,440, the pertinent disclosures of which are incorporated herein by reference.
- U.S. Pat. No. 4,277,344 describes an aromatic polyamide membrane produced by the interfacial polymerization of an aromatic polyamine with at least two primary amine substituents and an acyl halide having at least three acyl halide substituents.
- the aqueous solution contains a monomeric aromatic polyamine reactant and the organic solution contains an amine-reactive polyfunctional acyl halide.
- the polyamide layer of TFC membranes is typically obtained via an interfacial polymerization between a piperazine or an amine substituted piperidine or cyclohexane, and a polyfunctional acyl halide as described in U.S. Pat. Nos. 4,769,148 and 4,859,384.
- U.S. Pat. No. 5,246,587 describes an aromatic polyamide RO membrane that is made by first coating a porous support material with an aqueous solution containing a polyamine reactant and an amine salt.
- suitable polyamine reactants include aromatic primary diamines (such as, m-phenylenediamine or p-phenylenediamine or substituted derivatives thereof, wherein the substituent is an alkyl group, an alkoxy group, a hydroxy alkyl group, a hydroxy group or a halogen atom; aromatic secondary diamines (such as, N,N-diphenylethylene diamine), cycloaliphatic primary diamines (such as cyclohexane diamine), cycloaliphatic secondary diamines (such as, piperazine or trimethylene dipiperidine); and xylene diamines (such as m-xylene diamine).
- aromatic primary diamines such as, m-phenylenediamine or p-phenylenedi
- a TFC polyamide membrane is made by first coating a porous polysulfone support with an aqueous solution containing: 1) a polyfunctional primary or secondary amine; 2) a polyfunctional tertiary amine; and; 3) a polar solvent. The excess aqueous solution is removed and the coated support is then dipped in an organic solvent solution of trimesoyl chloride (TMC) and a mixture of alkanes having from eight to twelve carbon atoms.
- TMC trimesoyl chloride
- Polymers typically used in interfacial polymerization applications include, but are not limited to, polyamides, polyurea, polypyrrolidines, polyesters, polyurethanes, polysiloxanes, poly(amide imide), poly(ether amide), poly(urea amide) (PUA) [Petersen, R. J.
- the support membranes generally used for commercial TFC membranes are often polysulfone or polyethersulfone ultrafiltration membranes. These supports have limited stability for organic solvents and, therefore, thin film composites membranes of the prior art which are fabricated with such supports cannot be effectively utilized for all organic solvent nanofiltration applications.
- TFC membranes of the prior art have been specifically designed to separate aqueous feed streams down to a molecular level, they can be applied in certain organic solvents as well [Koseoglu, S. S., Lawhon, J. T. & Lusas, E. W. “ Membrane processing of crude vegetable oils pilot plant scale removal of solvent from oil miscellas”, J. Am. Oil Chem. Soc. 67, 315-322, 1990., U.S. Pat. No. 5,274,047]. Their effectiveness depends on the specific molecular structure of the thin film layer and the stability of the support membrane. U.S. Pat. No.
- TFC membranes comprising a thin film synthesized from piperazine/m-phenylenediamine and trimesoyl chloride on a PAN support membrane performed well in methanol, ethanol and acetone, less well in i-propanol and MEK, and gave no flux in hexane [Kim, I.-C., Jegal, J. & Lee, K.-H. “ Effect of aqueous and organic solutions on the performance of polyamide thin - film - composite nanofiltration membranes.” Journal of Polymer Science Part B: Polymer Physics 40, 2151-2163, 2002].
- US 2008/0197070 describes the formation of thin film composite membranes on polyolefin (e.g. polypropylene) supports prepared by interfacial polymerization. These membranes performed well in water, ethanol and methanol.
- polyolefin e.g. polypropylene
- Non-reactive polydimethylsiloxane has been added during the interfacial polymerization reaction using polyacrylonitrile (PAN) as the support membrane [Kim, I. C. & Lee, K. H. “Preparation of interfacially synthesized and silicone - coated composite polyamide nanofiltration membranes with high performance.” Ind. Eng. Chem. Res. 41, 5523-5528, 2002, U.S. Pat. No. 6,887,380, U.S. Pat. Applic No. 0098274 2003]. The resulting silicone-blended PA membrane showed high hexane permeabilities.
- TFC membranes have also been applied for filtration in apolar solvents.
- a method for the separation of lube oil from organic solvents (e.g. furfural, MEK/toluene, etc.) with a TFC membrane using poly(ethylene imine) and a diisocyanate on a solvent resistant nylon 6,6 support has been described in U.S. Pat. No. 5,173,91.
- 5,989,426; 6,024,873; 5,843,351; 5,614,099; 5,733,602 and 5,576,057 describe the addition of selected alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds to the aqueous amine solution and/or organic acid halide solution prior to the interfacial polymerization reaction.
- TFC membrane physical properties can also be improved by applying an aqueous solution composed of poly(vinyl alcohol) (PVA) and a buffer solution as a post formation step during membrane preparation.
- PVA poly(vinyl alcohol)
- Adding alcohols, ethers, sulfur-containing compounds, monohydric aromatic compounds and more specifically dimethyl sulfoxide (DMSO) in the aqueous phase can produce TFC membranes with an excellent performance [S.-Y. Kwak, S. G. Jung, S. H. Kim, “ Structure - motion - performance relationship of flux - enhanced reverse osmosis ( RO ) membranes composed of aromatic polyamide thin films”, Environ. Sci. Technol. 35, 4334, 2001; U.S. Pat. No. 5,576,057; U.S. Pat. No. 5,614,099].
- DMSO dimethyl sulfoxide
- TFC membranes with water flux five times greater than the normal TFC water flux with a small loss in rejection were obtained [S. H. Kim, S.-Y. Kwak, T. Suzuki, “Positron annihilation spectroscopic evidence to demonstrate the flux-enhancement mechanism in morphology-controlled thin-film-composite (TFC) membrane”, Environ. Sci. Technol. 39, 1764, 2005].
- U.S. Pat. No. 5,876,602 describes treating the TFC membrane with an aqueous chlorinating agent to improve flux, lower salt passage, and/or increase membrane stability to bases.
- U.S. Pat. No. 5,755,965 discloses a process wherein the surface of the TFC membrane is treated with ammonia or selected amines, e.g., 1,6, hexane diamine, cyclohexylamine and butylamine.
- U.S. Pat. No. 4,765,879 describes the post treatment of a membrane with a strong mineral acid followed by treatment with a rejection enhancing agent.
- a method of chemical treatment is claimed to be able to cause a simultaneous improvement of water flux and salt rejection of thin-film composite (TFC) membranes for reverse osmosis [Debabrata Mukherjee, Ashish Kulkarni, William N. Gill, “ Chemical treatment for improved performance of reverse osmosis membranes”, Desalination 104, 239-249, 1996].
- Hydrophilization by treating the membrane surface with water soluble solvent is a known surface modification technique. This method increases the flux without changing the chemical structure [Kulkarni, D. Mukherjee, W. N. Gill, “ Flux enhancement by hydrophilization of thin film composite reverse osmosis membranes”, J. Membr. Sci.
- a hydrophilic, charged TFC can be achieved by using radical grafting of two monomers, methacrylic acid and poly(ethylene glycol) methacrylate onto a commercial PA-TFC—RO membrane [S. Belfer, Y. Purinson, R. Fainshtein, Y. Radchenko, O. Kedem, “ Surface modification of commercial composite polyamide reverse osmosis membranes”, J. Membr. Sci. 139, 175, 1998]. It was found that the use of amine containing ethylene glycol blocks enhanced the performance of the membrane, and highly improved membrane water permeability by increasing hydrophilicity [M. Sforca, S. P. Nunes, K.-V.
- PEG has also been used to improve the TFC membrane formation [Shih-Hsiung Chen, Dong-Jang Chang, Rey-May Liou, Ching-Shan Hsu, Shiow-Shyung Lin, “ Preparation and Separation Properties of Polyamide Nanofiltration Membrane”, J Appl Polym Sci, 83, 1112-1118, 2002]. Because of the poor hydrophilicity of the polysulfone support membrane, poly(ethylene glycol) (PEG) was added to the aqueous solution as a wetting agent. The effect of PEG concentration on the resulting membrane performance was also studied.
- PEG poly(ethylene glycol)
- the present invention provides composite membranes formed by interfacial polymerisation which are particularly suitable for nanofiltration in organic solvents.
- the present invention relates to the production and utilization of membranes for nanofiltration operations in polar aprotic solvents.
- the invention provides a membrane for nanofiltration of a feed stream solution comprising a solvent and dissolved solutes and showing preferential rejection of the solutes, wherein the membrane is a composite membrane formed from interfacial polymerisation of a thin polymeric film on a support membrane, wherein the support membrane is impregnated with a conditioning agent and is stable in polar aprotic solvents; and wherein the composite membrane is treated with an activating solvent prior to use in nanofiltration.
- the composite membrane is treated with an activating solvent during or after interfacial polymerisation.
- an activating solvent to treat the membrane is believed to flush out any debris and unreacted material from the pores of the membrane following the interfacial polymerisation reaction.
- the treatment of the composite membrane with an activating solvent provides a membrane with improved properties, including, but not limited to, membrane flux.
- the invention provides an interfacial polymerisation process for forming a composite membrane for solvent nanofiltration as defined herein, comprising the steps of:
- support membrane is stable in polar aprotic solvents
- the present invention provides a membrane obtainable by any one of the methods defined herein.
- the present invention provides a membrane obtained by any one of the methods defined herein.
- the present invention provides a membrane directly obtained by any one of the methods defined herein.
- Membranes of the invention can be used for nanofiltration operations in organic solvents. In particular, they can be used for nanofiltration operations in polar aprotic solvents. This is advantageous with respect to many of the prior art thin film composite nanofiltration membranes, which lose structure and dissolve in polar aprotic solvents such as dimethylacetimide (DMAc), dimethylformamide (DMF), dimethylsufoxide (DMSO), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), and dichloromethane (DCM).
- polar aprotic solvents such as dimethylacetimide (DMAc), dimethylformamide (DMF), dimethylsufoxide (DMSO), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), and dichloromethane (DCM).
- DMAc dimethylacetimide
- DMF dimethylformamide
- DMSO dimethylsufoxide
- THF tetrahydrofur
- FIG. 1 shows molecular weight cut off (MWCO) curves and fluxes of TFC membranes after treatment with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF has been performed at 30 bar and 30° C.
- FIG. 2 shows MWCO curves and fluxes of TFC membranes after treatment with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF has been performed at 30 bar and 30° C.
- FIG. 3 shows MWCO curves and fluxes of TFC membranes after contacting with DMF as an activating solvent. Nanofiltration of a feed solution comprising alkanes dissolved in THF has been performed at 30 bar and 30° C.
- FIG. 4 shows the MWCO curve and flux of a TFC membrane which has not been treated with an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone has been performed at 30 bar and 30° C.
- FIG. 5 shows the MWCO curve and flux of a TFC membrane which has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone has been performed at 30 bar and 30° C.
- FIG. 6 shows MWCO curve and flux of a TFC membrane which has not been treated with an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol has been performed at 30 bar and 30° C.
- FIG. 7 shows MWCO curve and flux of a TFC membrane which has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol has been performed at 30 bar and 30° C.
- FIG. 8 shows MWCO curve and flux of a TFC membrane which has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in toluene has been performed at 30 bar and 30° C.
- FIG. 9 shows MWCO curve and flux of a TFC membrane which has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in ethyl acetate has been performed at 30 bar and 30° C.
- FIG. 10 shows MWCO curves and fluxes of TFC membranes prepared on a crosslinked polyimide support membrane which was not impregnated with a conditioning agent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF has been performed at 30 bar and 30° C.
- FIG. 11 shows MWCO curve and flux of a TFC membrane prepared on a crosslinked polyimide support membrane which was impregnated with PEG as a conditioning agent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF has been performed at 30 bar and 30° C.
- FIG. 12 shows MWCO curves and fluxes for TFC membranes prepared on a PEEK support membrane.
- the TFC membrane has not been treated with DMF as an activating solvent.
- Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF has been performed at 30 bar and 30° C.
- FIG. 13 shows MWCO curves and fluxes for TFC membranes prepared on a PEEK support membrane.
- the TFC membrane has been treated with DMF as an activating solvent.
- Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF has been performed at 30 bar and 30° C.
- FIG. 14 shows MWCO curves and fluxes for TFC membranes containing hydrophobic groups added after the interfacial polymerisation reaction.
- the resulting composite membranes are treated with DMF as an activating solvent.
- Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF has been performed at 30 bar and 30° C.
- FIG. 15 shows MWCO curves and fluxes for TFC membranes containing hydrophobic groups added during the interfacial polymerisation reaction.
- the resulting composite membranes are treated with DMF as an activating solvent.
- Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF has been performed at 30 bar and 30° C.
- Thin film composite (also referred to as TFC) membranes formed by interfacial polymerisation will be familiar to one of skill in this art and include an entity composed of a dense ultra-thin film layer over a support membrane, where the support membrane is previously formed from a different material.
- Suitable support membranes can be produced from polymer materials including crosslinked polyimide, crosslinked polybenzimidazole, crosslinked polyacrylonitrile, Teflon, polypropylene, and polyether ether ketone (PEEK), or sulfonated polyether ether ketone (S-PEEK).
- polymer materials including crosslinked polyimide, crosslinked polybenzimidazole, crosslinked polyacrylonitrile, Teflon, polypropylene, and polyether ether ketone (PEEK), or sulfonated polyether ether ketone (S-PEEK).
- the polymer used to form the support membrane includes but is not limited to polyimide polymer sources. The identities of such polymers are presented in the prior art, U.S. Pat. No. 0,038,306, the entire contents of which are incorporated herein by reference. More preferably, the support membrane of the invention is prepared from a polyimide polymer described in U.S. Pat. No. 3,708,458, assigned to Upjohn, the entire contents of which are incorporated herein by reference.
- the polymer available from HP polymers GmbH, Austria as P84, is a copolymer derived from the condensation of benzophenone 3,3′,4-4′-tetracarboxylic acid dianhydride (BTDA) and a mixture of di(4-aminophenyl)methane and toluene diamine or the corresponding diisocyanates, 4,4′-methylenebis(phenyl isocyanate) and toluene diisocyanate.
- BTDA benzophenone 3,3′,4-4′-tetracarboxylic acid dianhydride
- the obtained copolyimide has imide linkages which may be represented by the structural formulae:
- copolymer comprises from about 80% 1 and 20% II.
- Support membranes can be prepared following the methods described in GB 2,437,519, the entire contents of which are incorporated herein by reference, and comprise both nanofiltration and ultrafiltration membranes. More preferably, the membranes of the invention used as supports are within the ultrafiltration range.
- the membrane supports of the invention may be crosslinked using suitable amine crosslinking agents and the crosslinking method and time may be that described in GB 2,437,519.
- the support membrane is impregnated with a conditioning agent.
- conditioning agent is used herein to refer to any agent which, when impregnated into the support membrane prior to the interfacial polymerisation reaction, provides a resulting membrane with a higher rate of flux after drying. Any suitable conditioning agent may be used.
- the conditioning agent is a low volatility organic liquid.
- the conditioning agent may be chosen from synthetic oils (e.g., polyolefinic oils, silicone oils, polyalphaolefinic oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils and alkyl aromatic oils), mineral oils (including solvent refined oils and hydroprocessed mineral oils and petroleum wax isomerate oils), vegetable fats and oils, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols, and glycols (such as polypropylene glycols, polyethylene glycols, polyalkylene glycols).
- Suitable solvents for dissolving the conditioning agent include water, alcohols, ketones, aromatics, hydrocarbons, or mixtures thereof.
- the first and second conditioning agents referred to herein may be the same or different.
- the support membrane prior to the interfacial polymerization reaction, is treated with a first conditioning agent dissolved in a solvent to impregnate the support membrane.
- the first conditioning agent is a low volatility organic liquid as defined above.
- the support membrane is typically dried in air at ambient conditions to remove residual solvent.
- the interfacial polymerization reaction is generally held to take place at the interface between the first reactive monomer solution, and the second reactive monomer solution, which form two phases.
- Each phase may include a solution of a dissolved monomer or a combination thereof.
- Concentrations of the dissolved monomers may vary. Variables in the system may include, but are not limited to, the nature of the solvents, the nature of the monomers, monomer concentrations, use of additives in any of the phases, reaction temperature and reaction time. Such variables may be controlled to define the properties of the membrane, e.g., membrane selectivity, flux, top layer thickness.
- Monomers used in the reactive monomer solutions may include, but are not limited to, diamines and diacyl halides.
- the resulting reaction may form a polyamide selective layer on top of the support membrane.
- the polymer matrix of the top layer can comprise any three-dimensional polymer network known to those of skill in the art.
- the thin film comprises at least one of an aliphatic or aromatic polyamide, aromatic polyhydrazide, poly-benzimidazolone, polyepiamine/amide, polyepiamine/urea, poly-ethyleneimine/urea, sulfonated polyfurane, polybenzimidazole, polypiperazine isophtalamide, a polyether, a polyether-urea, a polyester, or a polyimide or a copolymer thereof or a mixture thereof.
- the polymer selected to form the thin film can be formed by an interfacial polymerization reaction.
- the film comprises a polyamide.
- the polyamide can be an aromatic polyamide or a non-aromatic polyamide.
- the polyamide can comprise residues of a phthaloyl (e.g. terephthaloyl or isophthaloyl) halide, a trimesyl halide, or a mixture thereof.
- the polyamide can comprise residues of diaminobenzene, triaminobenzene, piperazine, poly-piperazine, polyetherimine or a mixture thereof.
- the film comprises residues of a trimesoyl halide and residues of a diaminobenzene.
- the film comprises residues of trimesoyl chloride and m-phenylenediamine.
- the film comprises the reaction product of trimesoyl chloride and m-phenylenediamine.
- the first reactive monomer solution may comprise an aqueous solution of a polyamine.
- This aqueous amine solution may also contain other components, such as polyhydric compounds as disclosed in U.S. Pat. No. 4,830,885. Examples of such compounds include ethylene glycol, propylene glycol, glycerine, polyethylene glycol, polypropylene glycol, and copolymers of ethylene glycol and propylene glycol.
- the aqueous amine solution may also contain polar aprotic solvents.
- Aqueous monomer solutions may include, but are not limited to, an aqueous solution containing 1,6 hexenediamine, poly(ethyleneimine), an alternative aqueous monomer solution, and/or combinations thereof.
- Concentrations of solutions used in the interfacial polymerzation may be in a range from about 0.01 weight % to about 30 weight %.
- concentrations of the interfacial polymerization solutions may be in a range from about 0.1% weight % to about 5 weight %.
- the second reactive monomer solution may contain di- or triacyl chlorides such as trimesoyl chloride or other monomers, dissolved in a nonpolar solvent such as hexane, heptane, toluene or xylene. Further, the second reactive monomer solution may include, but is not limited to, a xylene solution of iso-phthaloyl dichloride, sebacoyl chloride, an alternative organic monomer solution, and/or combinations thereof.
- the disclosed interfacial polymerization reaction time of step (b) may vary.
- an interfacial polymerization reaction time may be in a range from about 5 seconds to about 2 hours.
- the quenching step (c) includes contacting or treating the membrane after the interfacial polymerisation reaction with a quenching medium.
- the quenching medium quenches any un-reacted functional groups present following the interfacial polymerisation reaction.
- the quenching medium is water.
- the quenching medium may also comprise an alcohol.
- Suitable alcohols include, but are not limited to, R—OH, Ar—OH, alcohols optionally with one or more siloxane-substituents, alcohols with one or more halo-substituents (including fluorinated alcohols R F OH, where R F is an alkyl group with one or more hydrogen atoms replaced by fluorine atoms), where R includes but is not limited to alkyl, alkene, haloalkyl (e.g. R F ), or Si—O—Si; and Ar is aryl (e.g. phenyl).
- the quenching medium may also comprise one or more capping monomers as quenching agents.
- capping monomers may include amines.
- Suitable amines include but are not limited to R—NH 2 , Ar—NH 2 , amines with siloxane-substituents, alkylamines with halo-substituents including fluorine R F NH 2 (where R F is an alkyl group in which one or more hydrogen atoms are replaced by fluorine atoms), where R includes but is not limited to alkyl, alkene, R F , Si—O—Si.
- the quenching medium may also comprise a solution containing R-acyl halides or Ar-acyl halides, where R includes but is not limited to alkyl, alkene, R F , Si—O—Si.
- suitable alkyl groups or moieties comprise 1-20 carbon atoms and suitable alkene groups or moieties comprise 2-20 carbon atoms.
- a post treatment step (d) includes contacting the composite membranes prior to use for nanofiltration with an activating solvent, including, but not limited to, polar aprotic solvents.
- activating solvents include DMAc, NMP, DMF and DMSO.
- the activating solvent in this art is defined as a liquid that enhances the composite membrane flux after treatment.
- the choice of activating solvent depends on the top layer and membrane support stability. Contacting may be effected through any practical means, including passing the composite membrane through a bath of the activating solvent, or filtering the activating solvent through the composite membrane.
- the second conditioning agent optionally applied in step (e) may be impregnated into the membrane by immersing the TFC membrane in a water or organic solvent bath or baths comprising the second conditioning agent.
- the resultant high flux semipermeable TFC membranes of the invention can be used for nanofiltration operations, particularly in organic solvents, and more particularly nanofiltration operations in polar aprotic solvents.
- membrane rejection it is meant a membrane process which will allow the passage of solvents while retarding the passage of larger solute molecules, when a pressure gradient is applied across the membrane. This may be defined in terms of membrane rejection R i , a common measure known by those skilled in the art and defined as:
- C P,i concentration of species i in the permeate, permeate being the liquid which has passed through the membrane
- C R,i concentration of species i in the retentate, retentate being the liquid which has not passed through the membrane.
- a membrane is selectively permeable for a species i if R i >0.
- nanofiltration is a process in which at least one solute molecule i with a molecular weight in the range 100-2,000 g mol ⁇ 1 is retained at the surface of the membrane over at least one solvent, so that R i >0.
- Typical applied pressures in nanofiltration range from 5 bar to 50 bar.
- solvent will be well understood by the average skilled reader and includes an organic or aqueous liquid with molecular weight less than 300 Daltons. It is understood that the term solvent also includes a mixture of solvents.
- solvents include aromatics, alkanes, ketones, glycols, chlorinated solvents, esters, ethers, amines, nitriles, aldehydes, phenols, amides, carboxylic acids, alcohols, furans, and polar protic and polar aprotic solvents, water, and mixtures thereof.
- solvents include toluene, xylene, benzene, styrene, anisole, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, methyl acetate, ethyl acetate, butyl acetate, methyl ether ketone (MEK), methyl iso butyl ketone (MIBK), acetone, ethylene glycols, ethanol, methanol, propanol, butanol, hexane, cyclohexane, dimethoxyethane, methyl tert butyl ether (MTBE), diethyl ether, adiponitrile, N,N dimethylformamide, dimethylsulfoxide, N,N dimethylacetamide, dioxane, nitromethane, nitrobenzene, pyridine, carbon disulfide, tetrahydrofuran
- solvent an organic molecule present in a liquid solution comprising a solvent and at least one solute molecule such that the weight fraction of the solute in the liquid is less than the weight fraction of the solvent, and where the molecular weight of the solute is at least 20 g mol ⁇ 1 higher than that of the solvent.
- the membrane of the present invention can be configured in accordance with any of the designs known to those skilled in the art, such as spiral wound, plate and frame, shell and tube, and derivative designs thereof.
- membrane performance was evaluated according to flux profiles and molecular weight cut off (MWCO) curves. All nanofiltration experiments were carried out at 30 bar using a cross-flow filtration system. Membrane discs, of active area 14 cm 2 , were cut out from flat sheets and placed into 4 cross flow cells in series. Permeate samples for flux measurements were collected at intervals of 1 h, and samples for rejection evaluations were taken after steady permeate flux was achieved. The MWCO was determined by interpolating from the plot of rejection against molecular weight of marker compounds. The solute rejection test was carried out using two standard solutions. The first was a standard feed solution comprised of a homologous series of styrene oligomers (PS) dissolved in the selected solvent.
- PS styrene oligomers
- the styrene oligomer mixture contained 1-2 g L ⁇ 1 each of PS 580 and PS 1090 (Polymer Labs, UK), and 0.01 g L ⁇ 1 of ⁇ -methylstyrene dimer (Sigma-Aldrich, UK). Analysis of the styrene oligomers was done using an Angilent HPLC system with UV/Vis detector set at a wavelength of 264 nm. Separation was achieved using a reverse phase column (C18-300, 250 ⁇ 4.6 mm). The mobile phase consisted of 35 vol % analytical grade water and 65 vol % tetrahydrofuran with 0.1 vol % trifluoroacetic acid.
- the second standard marker solution consisted of a solution of alkanes containing 0.1% (w/v) of each alkane.
- the alkanes used were: decane, n-hexadecane, n-tetradecane, eicosan, tetracosane, hexacosane. Their MWs are 142.3 Dalton, 198.4 Dalton, 226.4 Dalton, 280.5 Dalton, 338.7 Dalton, and 366.7 Dalton respectively. Analysis of the alkanes was via gas chromatography.
- Solvent flux (J) was determined by measuring permeate volume (V) per unit area (A) per unit time (t) according to the following equation:
- R i ( 1 - C P , i C F , i ) ⁇ 100 ⁇ % ( 2 )
- membranes of the present invention are formed through interfacial polymerisation to form a polyamide on a crosslinked polyimide support membrane, as follows:
- a polymer dope solution was prepared by dissolving 24% (w/w) polyimide (P84 from Evonik AG) in DMSO and stiffing overnight until complete dissolution. A viscous solution was formed, and allowed to stand for 10 hours to remove air bubbles. The dope solution was then cast on a polyester or polypropylene (Viledon, Germany) non-woven backing material taped to a glass plate using a casting knife (Elcometer 3700) set at a thickness of 250 Immediately after casting, the membrane was immersed in a water bath where phase inversion occurred. After 15 minutes, it was changed to a new water bath and left for an hour. The wet membrane was then immersed in a solvent exchange bath (isopropanol) to remove any residual water and preparation solvents.
- a solvent exchange bath isopropanol
- the support membrane was then crosslinked using a solution of hexanediamine in isopropanol, by immersing the support membrane in the solution for 16 hours at room temperature.
- the support membrane was then removed from the crosslinking bath and washed with isopropanol for 1 h to remove any residual hexanediamine (HDA).
- HDA hexanediamine
- the final step for preparing the crosslinked polyimide support membrane involved immersing the membrane overnight into a conditioning agent bath consisting of a volume ratio of 3:2 polyethylene glycol 400/isopropanol. The membrane was then wiped with tissue paper and air dried.
- TFC membranes were hand-cast on the crosslinked polyimide support membrane through interfacial polymerization.
- the support membrane was taped to a glass plate and placed in an aqueous solution of 2% (w/v) m-phenylenediamine (MPD, >99%, Sigma-Aldrich) for approximately 2 min.
- MPD m-phenylenediamine
- the MPD loaded support membrane was then rolled with a roller to remove excess solution.
- the MPD saturated membrane support was then immersed in a solution of 0.1% (w/v) trimesoyl chloride (TMC, 98%, Sigma-Aldrich) in hexane.
- TMC trimesoyl chloride
- Membrane code 1 TFC membrane prepared on crosslinked PI as support MPD-n impregnated with polyethylene glycol (PEG) Where n identifies membranes made in independent batch n.
- PEG polyethylene glycol
- a post-formation treatment step was carried out on the composite membranes in which the membranes were contacted with an activating solvent.
- the activating solvent was DMF.
- the contact time was 10 minutes via either filtration or immersion.
- FIGS. 1 and 2 The rejection curves and fluxes for the TFC membranes in DMF/PS solution and in THF/PS solution after post-treatment with DMF are shown in FIGS. 1 and 2 .
- FIG. 3 shows rejection curves and flux for the TFC membranes in THF/Alkanes solution.
- the TFC membranes showed no flux with THF before post-treatment with an activating solvent. It is clear that contacting the membrane with the activating solvent enhances flux.
- TFC membranes were fabricated as per EXAMPLE 1.
- Post-formation step (d) (contacting with DMF as an activating solvent) was only performed for some of the membranes.
- the performance of TFC membranes with and without the activation step (d) contacting with DMF was evaluated in different solvents, including acetone, methanol, ethyl acetate and toluene.
- FIG. 4 shows rejection curves and flux for TFC membranes in acetone/PS without treating the membrane with an activating solvent.
- FIG. 5 shows rejection curves and flux for TFC membranes during nanofiltration of acetone/PS solution after treating the membranes with DMF.
- FIG. 6 shows rejection curves and flux for TFC membranes during nanofiltration of MeOH/PS without treating the membrane with an activating solvent.
- FIG. 7 shows rejection curves and flux for TFC membranes during nanofiltration of MeOH/PS solution after treating the membranes with DMF.
- FIG. 8 shows rejection curves and flux for TFC membranes in Toluene/PS solution after treating the membranes with DMF.
- FIG. 9 shows rejection curves and flux for TFC membranes during nanofiltration of ethyl acetate/PS solution. Without DMF treatment the TFC membranes showed no flux in toluene or ethyl acetate.
- Membrane supports were fabricated as per EXAMPLE 1 but were not conditioned with PEG. TFC membranes were fabricated on these non-conditioned support membranes as per EXAMPLE 1. The performance of TFC membranes prepared on membrane supports with and without PEG was then evaluated and compared.
- FIG. 10 shows rejection curves and flux for TFC membranes prepared on membrane supports without PEG in DMF/PS solution.
- FIG. 11 shows rejection curves and flux for TFC membranes prepared on membrane supports with PEG in DMF/PS solution. An increase in flux can be observed when TFC membranes are prepared on membrane supports containing PEG.
- TFC membranes were prepared on PEEK support membranes, as follows:
- a polymer dope solution was prepared by dissolving 12.3% (w/w) PEEK in 79.4% methane sulfonic acid (MSA) and 8.3% sulfuric acid (H 2 SO 4 ). The solution was stirred overnight until complete dissolution. A viscous solution was formed, and allowed to stand for 10 hours to remove air bubbles. The solution was then cast on a polyester non-woven backing material taped to a glass plate using a casting knife (Elcometer 3700) set at a thickness of 250 ⁇ m. Immediately after casting, the membrane was immersed in a water bath where phase inversion occurred. After 15 minutes, it was changed to a new water bath and left for an hour. The wet membrane was then immersed in a water bath to remove any residual preparation solvents.
- MSA methane sulfonic acid
- H 2 SO 4 sulfuric acid
- the final step for preparing the PEEK support membrane involved immersing the membrane overnight into a conditioning agent bath consisting of a volume ratio of 3:2 polyethylene glycol 400/isopropanol. The membrane was then wiped with tissue paper and air dried. TFC membranes were fabricated as per EXAMPLE 1, section 1.2 on top of the PEEK support membrane. The TFC membranes were treated with DMF as an activating solvent as per EXAMPLE 1. Some of the TFC membranes were not treated with an activating solvent for comparison.
- FIG. 12 shows rejection curves and flux for TFC membranes during nanofiltration of THF/PS solution without treating the membrane with an activating solvent.
- FIG. 13 shows rejection curves and flux for TFC membranes during nanofiltration of THF/PS solution after treating the membranes with DMF as an activating solvent.
- TFC membranes were fabricated as per EXAMPLE 1. After the interfacial polymerisation reaction the membranes were treated in a quenching medium comprising a reactive monomer dissolved in a solvent (step c).
- a post-formation treatment step was carried out on the composite membranes in which the membranes were contacted with a quenching medium.
- the quenching medium was a solution of a fluoroamine or aminosiloxane in hexane.
- the contact time was 1 minute via immersion.
- the reactive monomer end-caps the free acyl chloride groups left in the polyamide film.
- the quenching step modifies the membrane chemistry, making it more hydrophobic by capping the unreacted acyl chloride groups with amines comprising halo-, silyl- or siloxane-substituents.
- the chemical structures of the monomers used for the interfacial polymerisation reaction are shown in Scheme 2.
- Membrane Membrane code 4 TFC membrane prepared on crosslinked PI as MPD-n support impregnated with PEG.
- TFC membrane prepared on crosslinked PI as Fluoroamine- support impregnated with PEG.
- the TFC MPD-n membrane is post-treated with a solution of 2,2,3,3,3-pentafluoropropylamine in hexane.
- 6 TFC membrane prepared on crosslinked PI as Aminosiloxane- support impregnated with PEG.
- the TFC MPD-n membrane is post-treated with a solution of poly[dimethylsiloxane-co-(3-aminopropyl)- methylsiloxane] in hexane.
- n identifies membranes made in independent batch n.
- FIG. 14 shows rejection curves and flux for these hydrophobic TFC membranes in Toluene/PS solution.
- Crosslinked polyimide supports were fabricated as per EXAMPLE 1 and impregnated with PEG. During the interfacial polymerisation reaction the trimesoyl chlode was blended with a fluoromonoacyl chloride to make the membrane more hydrophobic and more open.
- TFC membranes were hand-cast on the crosslinked polyimide support membrane containing PEG through interfacial polymerization.
- the support membrane was taped to a glass plate and placed in an aqueous solution of 2% (w/v) m-phenylenediamine (MPD, >99%, Sigma-Aldrich) for approximately 2 min.
- MPD m-phenylenediamine
- the MPD loaded support membrane was then rolled with a roller to remove excess solution.
- the MPD saturated membrane support was then immersed in a solution of 0.1% (w/v) trimesoyl chloride (TMC, 98%, Sigma-Aldrich) blended with perfluorooctanoylchloride (7:1) in hexane.
- TMC trimesoyl chloride
- Membrane Membrane code 7 TFC membrane prepared on crosslinked PI MPD-n as supportimpregnated with PEG.
- 8 TFC membrane prepared on crosslinked PI Fluoroacylchloride- as support impregnated with PEG.
- the TMC is blended with Perfluorooctanoylchloride to render the membrane more hydrophobic and with higher MWCO
- n identifies membranes made in independent batch n.
- FIG. 15 shows rejection curves and flux for these hydrophobic TFC membranes in ethyl acetate/PS solution.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050000899A1 (en) * | 2003-04-15 | 2005-01-06 | Koros William J. | Dithiolene functionalized polymer membrane for olefin/paraffin separation |
EP1707255A2 (en) * | 2005-03-30 | 2006-10-04 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
US20080257818A1 (en) * | 2004-10-01 | 2008-10-23 | Nitto Denko Corporation | Semipermeable Composite Membrane and Process for Producing the Same |
US20100038306A1 (en) * | 2006-04-28 | 2010-02-18 | Imperial Innovations Limited | Asymmetric membranes for use in nanofiltration |
US20100181253A1 (en) * | 2007-05-14 | 2010-07-22 | Evonik Fibres Gmbh | Cross-linked polyimide membranes |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US38306A (en) | 1863-04-28 | Improvement in dyeing wool, silk | ||
US517391A (en) | 1894-03-27 | noble | ||
US2742003A (en) | 1953-06-17 | 1956-04-17 | Crawford Albert | Tile laying apparatus |
US3708458A (en) | 1971-03-16 | 1973-01-02 | Upjohn Co | Copolyimides of benzophenone tetracarboxylic acid dianhydride and mixture of diisocyanates |
US4039440A (en) | 1972-09-19 | 1977-08-02 | The United States Of America As Represented By The Secretary Of The Interior | Reverse osmosis membrane |
US4259183A (en) | 1978-11-07 | 1981-03-31 | Midwest Research Institute | Reverse osmosis membrane |
US4277344A (en) | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
JPS5849412A (ja) * | 1981-09-19 | 1983-03-23 | Nitto Electric Ind Co Ltd | 管状膜分離モジユ−ル |
CA1254007A (en) * | 1983-08-29 | 1989-05-16 | Bernard A. Koenitzer | Preswelling of regenerated cellulose membranes for organic separations and the use thereof |
US4529646A (en) | 1984-07-30 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
US4765897A (en) | 1986-04-28 | 1988-08-23 | The Dow Chemical Company | Polyamide membranes useful for water softening |
US4824574A (en) | 1986-04-28 | 1989-04-25 | The Dow Chemical Company | Novel water softening process using membranes |
US4812270A (en) | 1986-04-28 | 1989-03-14 | Filmtec Corporation | Novel water softening membranes |
JPS62284095A (ja) | 1986-06-02 | 1987-12-09 | Permelec Electrode Ltd | 耐久性を有する電解用電極及びその製造方法 |
US4830885A (en) | 1987-06-08 | 1989-05-16 | Allied-Signal Inc. | Chlorine-resistant semipermeable membranes |
US4853122A (en) | 1987-09-15 | 1989-08-01 | Bend Research, Inc. | P-xylylenediamide/diimide composite RO membranes |
US4859384A (en) | 1987-11-18 | 1989-08-22 | Filmtec Corp. | Novel polyamide reverse osmosis membranes |
US4769148A (en) | 1987-11-18 | 1988-09-06 | The Dow Chemical Company | Novel polyamide reverse osmosis membranes |
US4876009A (en) | 1988-10-21 | 1989-10-24 | Bend Research, Inc. | Tetrakis-amido high flux membranes |
DE3842819A1 (de) | 1988-12-20 | 1990-06-21 | Hoechst Ag | Verfahren zur abtrennung von metallorganischen verbindungen und/oder metallcarbonylen aus ihren loesungen in organischen medien |
US4950404A (en) | 1989-08-30 | 1990-08-21 | Allied-Signal Inc. | High flux semipermeable membranes |
US5173191A (en) * | 1989-10-05 | 1992-12-22 | Exxon Research And Engineering Company | Interfacially polymerized membranes for the reverse osmosis separation of organic solvent solutions |
NL9100307A (nl) | 1991-02-21 | 1992-09-16 | X Flow Bv | Semi-permeabel composietmembraan, werkwijze voor de bereiding ervan, alsmede toepassing van dergelijke membranen voor het scheiden van componenten in een organische vloeistoffase of in de dampfase. |
US5288818A (en) | 1991-08-20 | 1994-02-22 | Exxon Chemical Patents Inc. | Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
US5215667A (en) | 1991-08-20 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
US5151182A (en) | 1991-08-30 | 1992-09-29 | Membrane Products Kiryat Weizmann Ltd. | Polyphenylene oxide-derived membranes for separation in organic solvents |
US5290452A (en) | 1991-12-05 | 1994-03-01 | Exxon Research & Engineering Co. | Crosslinked polyester amide membranes and their use for organic separations |
US5246587A (en) | 1991-12-23 | 1993-09-21 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
US5234598A (en) | 1992-05-13 | 1993-08-10 | Allied-Signal Inc. | Thin-film composite membrane |
US5395979A (en) | 1993-02-25 | 1995-03-07 | Exxon Chemical Patents Inc. | Method for separating catalyst from a hydroformylation reaction product using alkylated ligands |
US5298669A (en) | 1993-03-23 | 1994-03-29 | Exxon Chemical Patent Inc. | Perstraction sweep stream for a membrane reactor |
US5264166A (en) | 1993-04-23 | 1993-11-23 | W. R. Grace & Co.-Conn. | Polyimide membrane for separation of solvents from lube oil |
JP3006976B2 (ja) | 1993-06-24 | 2000-02-07 | 日東電工株式会社 | 高透過性複合逆浸透膜の製造方法 |
JP3489922B2 (ja) | 1994-12-22 | 2004-01-26 | 日東電工株式会社 | 高透過性複合逆浸透膜の製造方法 |
US5614099A (en) | 1994-12-22 | 1997-03-25 | Nitto Denko Corporation | Highly permeable composite reverse osmosis membrane, method of producing the same, and method of using the same |
US5582725A (en) | 1995-05-19 | 1996-12-10 | Bend Research, Inc. | Chlorine-resistant composite membranes with high organic rejection |
US5989426A (en) | 1995-07-05 | 1999-11-23 | Nitto Denko Corp. | Osmosis membrane |
US5755965A (en) | 1995-10-16 | 1998-05-26 | Hdr Engineering, Inc. | Cyclonic de-gasser |
JP3681214B2 (ja) | 1996-03-21 | 2005-08-10 | 日東電工株式会社 | 高透過性複合逆浸透膜 |
JPH1128466A (ja) * | 1997-07-14 | 1999-02-02 | Nitto Denko Corp | 逆浸透複合膜による水の逆浸透処理方法 |
US5876602A (en) | 1997-11-04 | 1999-03-02 | The Dow Chemical Company | Treatment of composite polyamide membranes to improve performance |
EP1013337B1 (en) | 1998-12-21 | 2005-03-09 | Nitto Denko Corporation | Highly permeable composite reverse osmosis membrane and method of producing the same |
US6623639B2 (en) | 1999-03-19 | 2003-09-23 | Bend Research, Inc. | Solvent-resistant microporous polybenzimidazole membranes |
US6245234B1 (en) | 1999-06-03 | 2001-06-12 | Saehan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
TWI287556B (en) | 1999-09-13 | 2007-10-01 | Teijin Ltd | Polymetaphenyleneisophthalamide-based polymer porous film, process for preparing same and separator for battery |
GB2369311B (en) | 2000-11-24 | 2002-12-11 | Membrane Extraction Tech Ltd | Separating phase transfer agents |
JP2002204912A (ja) | 2001-01-05 | 2002-07-23 | Teijin Ltd | 耐熱性濾布 |
GB2373743B (en) | 2001-03-27 | 2004-11-03 | Membrane Extraction Tech Ltd | Solvent exchange process |
KR100447932B1 (ko) * | 2001-10-19 | 2004-09-08 | 한국화학연구원 | 실리콘이 함유된 내유기용매성 폴리아미드 나노복합막과 이의 제조방법 |
TW200417563A (en) * | 2002-09-12 | 2004-09-16 | Teijin Ltd | Porous membrane of poly(metaphenylene isophthalamide) and process for producing the same |
GB0229423D0 (en) | 2002-12-18 | 2003-01-22 | Avecia Ltd | Process |
JP2007144414A (ja) * | 2005-10-27 | 2007-06-14 | Toray Ind Inc | 中空糸膜およびその製造方法 |
US20080197070A1 (en) | 2006-10-30 | 2008-08-21 | New Jersey Institute Of Technology | Composite Membranes and Membrane Systems and Methods For Production and Utilization Thereof |
US8231013B2 (en) | 2006-12-05 | 2012-07-31 | The Research Foundation Of State University Of New York | Articles comprising a fibrous support |
US20080312349A1 (en) | 2007-02-22 | 2008-12-18 | General Electric Company | Method of making and using membrane |
US20080207822A1 (en) | 2007-02-22 | 2008-08-28 | General Electric Company | Composition and associated method |
GB0817563D0 (en) | 2008-09-25 | 2008-11-05 | Membrane Extraction Tech Ltd | Membrane module |
GB201012083D0 (en) | 2010-07-19 | 2010-09-01 | Imp Innovations Ltd | Thin film composite membranes for separation |
-
2010
- 2010-07-19 GB GBGB1012083.0A patent/GB201012083D0/en not_active Ceased
-
2011
- 2011-07-19 MX MX2013000771A patent/MX2013000771A/es unknown
- 2011-07-19 KR KR1020137004121A patent/KR101944772B1/ko active IP Right Grant
- 2011-07-19 JP JP2013520216A patent/JP2013535319A/ja active Pending
- 2011-07-19 AU AU2011281329A patent/AU2011281329B2/en active Active
- 2011-07-19 EP EP11751923.1A patent/EP2595732B1/en active Active
- 2011-07-19 UA UAA201302002A patent/UA109549C2/uk unknown
- 2011-07-19 US US13/810,935 patent/US20130112619A1/en not_active Abandoned
- 2011-07-19 CN CN2011800404298A patent/CN103068476A/zh active Pending
- 2011-07-19 MY MYPI2013700115A patent/MY166547A/en unknown
- 2011-07-19 BR BR112013001377A patent/BR112013001377B8/pt active IP Right Grant
- 2011-07-19 EA EA201390134A patent/EA030909B1/ru not_active IP Right Cessation
- 2011-07-19 CA CA2805782A patent/CA2805782C/en active Active
- 2011-07-19 WO PCT/GB2011/051364 patent/WO2012010889A1/en active Application Filing
- 2011-07-19 CN CN201710421759.0A patent/CN107174971A/zh active Pending
- 2011-07-19 SG SG2013004023A patent/SG187557A1/en unknown
-
2013
- 2013-01-17 CL CL2013000168A patent/CL2013000168A1/es unknown
- 2013-01-23 IL IL224376A patent/IL224376B/en active IP Right Grant
- 2013-02-04 ZA ZA2013/00931A patent/ZA201300931B/en unknown
-
2016
- 2016-11-18 US US15/355,276 patent/US10357746B2/en active Active
-
2017
- 2017-05-31 JP JP2017107922A patent/JP6643624B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050000899A1 (en) * | 2003-04-15 | 2005-01-06 | Koros William J. | Dithiolene functionalized polymer membrane for olefin/paraffin separation |
US20080257818A1 (en) * | 2004-10-01 | 2008-10-23 | Nitto Denko Corporation | Semipermeable Composite Membrane and Process for Producing the Same |
EP1707255A2 (en) * | 2005-03-30 | 2006-10-04 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
US20100038306A1 (en) * | 2006-04-28 | 2010-02-18 | Imperial Innovations Limited | Asymmetric membranes for use in nanofiltration |
US20100181253A1 (en) * | 2007-05-14 | 2010-07-22 | Evonik Fibres Gmbh | Cross-linked polyimide membranes |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10357746B2 (en) | 2010-07-19 | 2019-07-23 | Ip2Ipo Innovations Limited | Solvent resistant polyamide nanofiltration membranes |
US9382381B2 (en) * | 2012-06-29 | 2016-07-05 | Nissan Chemical Industries, Ltd. | Aromatic polyamide and film-forming composition containing same |
US9056284B2 (en) * | 2012-08-10 | 2015-06-16 | The United States Of America, As Represented By The Secretary Of The Interior | Chlorine resistant amides, polyamides, and membranes made from the same |
US20140042082A1 (en) * | 2012-08-10 | 2014-02-13 | Andrew P. Murphy | Chlorine resistant amides, polyamides, and membranes made from the same |
US20140054228A1 (en) * | 2012-08-21 | 2014-02-27 | General Electric Company | Novel Flux Enhancing Agent for Improving Composite Polyamide Reverse Osmosis Membrane Performance |
US9346023B2 (en) * | 2012-08-21 | 2016-05-24 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
US9914098B2 (en) | 2012-08-21 | 2018-03-13 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
US10532320B2 (en) | 2014-09-22 | 2020-01-14 | Evonik Degussa Gmbh | Method for improved reactive monomer production with membrane filtration |
US10479864B2 (en) | 2014-09-30 | 2019-11-19 | Lg Chem, Ltd. | Method for manufacturing polyamide-based water-treatment separator having excellent permeation flux characteristics and water-treatment separator manufactured by same |
US9920168B2 (en) | 2015-03-17 | 2018-03-20 | Dow Global Technologies Llc | Polymers of intrinsic microporosity |
US10239990B2 (en) | 2015-05-29 | 2019-03-26 | Dow Global Technologies Llc | Isatin copolymers having intrinsic microporosity |
US10189948B2 (en) | 2015-06-24 | 2019-01-29 | Dow Global Technologies Llc | Isatin copolymers having intrinsic microporosity |
US10414866B2 (en) | 2015-11-24 | 2019-09-17 | Dow Global Technologies Llc | Troger's base polymers having intrinsic microporosity |
US20190176092A1 (en) * | 2016-06-06 | 2019-06-13 | Imperial Innovations Limited | Process for the production of solvent stable polymeric membranes |
US10913033B2 (en) * | 2016-06-06 | 2021-02-09 | Ip2Ipo Innovations Limited | Process for the production of solvent stable polymeric membranes |
US10590239B2 (en) | 2016-09-12 | 2020-03-17 | Dow Global Technologies Llc | Polymer including Troger'S base and isatin moieties and having intrinsic microporosity |
US10472467B2 (en) | 2016-09-20 | 2019-11-12 | Dow Global Technologies Llc | Polymers having intrinsic microporosity including sub-units with troger's base and spirobisindane moieties |
US20210031151A1 (en) * | 2018-01-22 | 2021-02-04 | Korea University Research And Business Foundation | Method for manufacturing high-performance thin film composite membrane through the solvent activation process |
CN110292867A (zh) * | 2019-07-10 | 2019-10-01 | 王哲 | 一种高通量耐有机溶剂纳滤凝胶复合膜及其制备方法 |
CN112569788B (zh) * | 2019-09-27 | 2023-02-28 | 中国石油化工股份有限公司 | 利用复合纳滤膜对橡胶聚合用粗溶剂除水的方法 |
CN112569788A (zh) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | 利用复合纳滤膜对橡胶聚合用粗溶剂除水的方法 |
CN113117536A (zh) * | 2019-12-30 | 2021-07-16 | 滁州学院 | 一种复合纳滤膜及其制备方法和应用 |
CN113856467A (zh) * | 2020-06-30 | 2021-12-31 | 宁波方太厨具有限公司 | 低压软化复合纳滤膜及其制备方法 |
CN112452168A (zh) * | 2020-09-14 | 2021-03-09 | 南京工业大学 | 聚酰亚胺纳米纤维复合膜、制备方法及其在有机溶剂纳滤过程中的用途 |
CN114642968A (zh) * | 2020-12-18 | 2022-06-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | 具有可溶性中间层的高通量复合纳滤膜、其制法及应用 |
US11505671B1 (en) | 2021-06-16 | 2022-11-22 | Avanpore LLC | Preparation of mesoporous poly (aryl ether ketone) articles and use thereof |
US11629239B2 (en) | 2021-06-16 | 2023-04-18 | Avanpore LLC | Preparation of mesoporous poly (aryl ether ketone) articles and use thereof |
US11673099B2 (en) | 2021-07-14 | 2023-06-13 | Avanpore LLC | Composite poly (aryl ether ketone) membranes, their preparation and use thereof |
US11786871B2 (en) | 2021-07-14 | 2023-10-17 | Avanpore LLC | Composite poly (aryl ether ketone) membranes, their preparation and use thereof |
CN114682105A (zh) * | 2022-06-02 | 2022-07-01 | 天津大学 | 一种耐强极性有机溶剂纳滤膜的制备方法及应用 |
CN115318108A (zh) * | 2022-07-14 | 2022-11-11 | 武汉工程大学 | 一种氨基硅烷偶联剂与多酚超分子结构的复合纳滤膜及其制备方法 |
CN115253728A (zh) * | 2022-08-25 | 2022-11-01 | 山东纳飞博科技发展有限公司 | 一种聚酰亚胺纤维耐溶剂纳滤膜的制备方法 |
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KR20140085373A (ko) | 2014-07-07 |
KR101944772B1 (ko) | 2019-04-17 |
US20170157567A1 (en) | 2017-06-08 |
EP2595732B1 (en) | 2019-04-03 |
EA030909B1 (ru) | 2018-10-31 |
BR112013001377B8 (pt) | 2022-08-02 |
IL224376B (en) | 2018-10-31 |
CA2805782C (en) | 2020-06-16 |
CN107174971A (zh) | 2017-09-19 |
CN103068476A (zh) | 2013-04-24 |
SG187557A1 (en) | 2013-03-28 |
CL2013000168A1 (es) | 2013-12-06 |
ZA201300931B (en) | 2019-08-28 |
AU2011281329B2 (en) | 2015-06-25 |
GB201012083D0 (en) | 2010-09-01 |
MY166547A (en) | 2018-07-16 |
BR112013001377A2 (pt) | 2016-05-17 |
JP2013535319A (ja) | 2013-09-12 |
EA201390134A1 (ru) | 2013-11-29 |
MX2013000771A (es) | 2013-07-05 |
EP2595732A1 (en) | 2013-05-29 |
AU2011281329A1 (en) | 2013-02-21 |
WO2012010889A1 (en) | 2012-01-26 |
US10357746B2 (en) | 2019-07-23 |
JP6643624B2 (ja) | 2020-02-12 |
JP2017213559A (ja) | 2017-12-07 |
UA109549C2 (xx) | 2015-09-10 |
BR112013001377B1 (pt) | 2020-06-09 |
CA2805782A1 (en) | 2012-01-26 |
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