GB1590813A - Multicomponent membranes - Google Patents
Multicomponent membranes Download PDFInfo
- Publication number
- GB1590813A GB1590813A GB47269/77A GB4726977A GB1590813A GB 1590813 A GB1590813 A GB 1590813A GB 47269/77 A GB47269/77 A GB 47269/77A GB 4726977 A GB4726977 A GB 4726977A GB 1590813 A GB1590813 A GB 1590813A
- Authority
- GB
- United Kingdom
- Prior art keywords
- membrane
- multicomponent
- gas
- separation
- coating
- 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.)
- Expired
Links
- 239000012528 membrane Substances 0.000 title claims description 961
- 238000000926 separation method Methods 0.000 claims description 734
- 239000007789 gas Substances 0.000 claims description 378
- 238000000576 coating method Methods 0.000 claims description 281
- 239000011248 coating agent Substances 0.000 claims description 263
- 239000000463 material Substances 0.000 claims description 252
- -1 poly(arylene ether Chemical compound 0.000 claims description 155
- 230000035699 permeability Effects 0.000 claims description 88
- 239000011148 porous material Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 81
- 229920002492 poly(sulfone) Polymers 0.000 claims description 73
- 239000008246 gaseous mixture Substances 0.000 claims description 68
- 239000012510 hollow fiber Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 42
- 229920002379 silicone rubber Polymers 0.000 claims description 34
- 239000004945 silicone rubber Substances 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229920002301 cellulose acetate Polymers 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 15
- 239000001307 helium Substances 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- 125000006839 xylylene group Chemical group 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000004417 polycarbonate Substances 0.000 claims description 14
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000011800 void material Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000001272 nitrous oxide Substances 0.000 claims description 5
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 229920006156 poly(arylene oxide) Polymers 0.000 claims 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- 239000012466 permeate Substances 0.000 description 35
- 230000004907 flux Effects 0.000 description 34
- 239000000203 mixture Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 29
- 239000000835 fiber Substances 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 26
- 208000012886 Vertigo Diseases 0.000 description 24
- 238000009987 spinning Methods 0.000 description 24
- 239000002131 composite material Substances 0.000 description 21
- 238000011282 treatment Methods 0.000 description 21
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 18
- 238000013178 mathematical model Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000010612 desalination reaction Methods 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 10
- 230000015271 coagulation Effects 0.000 description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 10
- 230000036961 partial effect Effects 0.000 description 10
- NWNCIXFIIDVRKE-UHFFFAOYSA-N 3-methyl-2-(4-methylphenyl)morpholine Chemical compound CC1NCCOC1C1=CC=C(C)C=C1 NWNCIXFIIDVRKE-UHFFFAOYSA-N 0.000 description 9
- 229920004511 Dow Corning® 200 Fluid Polymers 0.000 description 9
- 239000000701 coagulant Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000001747 exhibiting effect Effects 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 125000002950 monocyclic group Chemical group 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000010073 coating (rubber) Methods 0.000 description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920004142 LEXAN™ Polymers 0.000 description 2
- 239000004418 Lexan Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001603 poly (alkyl acrylates) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- CCHSBYTWTBIDLD-UHFFFAOYSA-N 1,1,1-trifluorohexadecane Chemical compound CCCCCCCCCCCCCCCC(F)(F)F CCHSBYTWTBIDLD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 101000831256 Oryza sativa subsp. japonica Cysteine proteinase inhibitor 1 Proteins 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- GIEOVLYOTBHPBV-UHFFFAOYSA-N [Na].BrC=C.C=CC#N Chemical compound [Na].BrC=C.C=CC#N GIEOVLYOTBHPBV-UHFFFAOYSA-N 0.000 description 1
- ZXQYGBMAQZUVMI-QQDHXZELSA-N [cyano-(3-phenoxyphenyl)methyl] (1r,3r)-3-[(z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@@H](\C=C(/Cl)C(F)(F)F)[C@H]1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-QQDHXZELSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001484 poly(alkylene) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 102220095348 rs876659304 Human genes 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D69/1212—Coextruded layers
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
(54) MULTICOMPONENT MEMBRANES
(71) We, MONSANTO COMPANY, a corporation organised under the laws
of the State of Delaware, United States of America, of 800 North Lindbergh
Boulevard, St. Louis, Missouri 63166 United States of America, do hereby declare
the invention, for which we pray that a patent may be granted to us, and the
method by which it-is to be performed, to be particularly described in and by the
following statement:- This invention relates to multicomponent membranes for separating at least
one gas from gaseous mixtures, to processes for selectively separating at least one
gas from gaseous mixtures by permeation utilizing these multicomponent
membranes, and to apparatus utilizing these multicomponent membranes.
Separating, including upgrading of the concentration of, at least one selected
gas from a gaseous mixture is an especially important procedure in view of the
demands on the supplies of chemical feedstocks. Frequently these demands are
met by separating one or more desired gases from gaseous mixtures and utilizing
the gaseous products for processing. Proposals have been made to employ
separation membranes for selectively separating one or more gases from gaseous
mixtures. To achieve selective separation the membrane exhibits less resistance to
the transport of one or more gases than that of at least one other gas of the mixture.
Thus, selective separation can provide preferential depletion or concentration of
one or more desired gases in the mixture with respect to at least one other gas and
therefore provide a product having a different proportion of the one or more
desired gases to the at least one other gas than that proportion in the mixture.
However, in order for selective separation of the one or more desired gases by the
use of separation membranes to be commercially attractive, the membranes must
not only be capable of withstanding the conditions to which they may be subjected
during the separation operation, but also must provide an adequately selective
separation of the one or more desired gases at a sufficiently high flux, i.e.,
permeation rate of the permeate per unit surface area, so that the use of the
separation procedure is on an economically attractive basis. Thus, separation .membranes which exhibit adequately high selective separation, but undesirably
low fluxes, may require such large separating membrane surface area that the use
of these membranes is not economically feasible. Similarly separation membranes which exhibit a high flux, but low selective separation, are also commercially
unattractive. Accordingly, work has continued to develop separation membranes which can provide both an adequately selective separation of the one or more desired gases and a sufficiently high flux such that the use of these separation
membranes on a commercial basis is economically feasible.
In general, the passage of a gas through a membrane may proceed through pores, i.e., continuous channels for fluid flow in communication with both feed and exit surfaces of the membrane (which pores may or may not be suitable for separation by Knudsen flow or diffusion); in another mechanism, in accordance with current views of membrane theory the passage of a gas through the membrane
may be by interaction of the gas with the material of the membrane. In this latter postulated mechanism, the permeability of a gas through a membrane is believed to involve the solubility of the gas in the membrane material and the diffusion of the gas through the membrane. The permeability constant for a single gas is presently viewed as being the product of the solubility and diffusivity of that gas in the membrane. A given membrane material has a particular permeability constant for passage of a given gas by the interaction of the gas with the material of the membrane. The rate of permeation of the gas, i.e., flux, through the membrane is related to the permeability constant, but is also influenced by variables such as membrane thickness, the physical nature of the membrane, the partial pressure differential of the permeate gas across the membrane, the temperature and the like.
Development of Membranes for Liquid Separation
Heretofore, various modification in membranes used for liquid separations have been proposed in attempts to solve particular problems associated with the separation operation. The following discussion is illustrative of specific modifications which have been made to membranes used for liquid separations to solve particular problems and provides a basis upon which the invention can by fully appreciated. For example, cellulosic membranes were first developed and utilized for the desalination of water, and these membranes could generally be described as "dense," or "compact," membranes. "Dense," or "compact," membranes are membranes which are essentially free of pores, i.e., fluid flow channels communicating between the surfaces of the membrane, and are essentially free of voids, i.e. regions within the thickness of the membrane which do not contain the material of the membrane. In the case of compact membranes, either surface is suitable for the feed contact surface, because properties of the compact membrane are the same from either surface direction, i.e., the membrane is symmetric. Since the membrane is essentially the same throughout the structure, it falls within the definition of isotropic membranes. Although some of these compact membranes are fairly selective, one of their main disadvantages is low permeate flux due to the relatively large thickness associated with the membranes.
It has therefore been uneconomical to build equipment installations necessary for the desalination of appreciable quantities of water using compact membranes.
Attempts to increase the flux of membranes for liquid separations have included, for example, adding fillers to the membrane to alter porosity and making the membranes as thin as possible to increase rates of permeate flow. Although improved permeation rates have been achieved to a limited degree, generally these improved rates have been obtained at the expense of the selectivity of the particular membranes.
In another attempt to improve membrane performances Loeb and his coworkers proposed a method for preparing a modified cellulose acetate membrane for desalination of water by first casting a solution of cellulose acetate as a thin layer, and then forming a dense membrane skin on the thin layer through various techniques such as solvent evaporation followed by quenching in cold water. The formation of these dense-skinned membranes generally involved a final annealing treatment in hot water. The membranes proposed by the Loeb method are composed of two distinct regions made of the same cellulose acetate material, a thin dense semi-permeable skin and a less dense, void-containing, non-selective support region. Since the membranes are not of essentially the same density throughout their structure, they fall within the definition of anisotropic membranes. Because of these distinct regions and the difference in membrane properties which can be observed depending on which surface of the membrane faces a brine feed solution, Loeb-type membranes can be describe as being asymmetric.
In, for instance, practical desalination tests, asymmetric dense-skinned membranes have been shown to have superior permeate flux when compared with the older style compact membranes. The improvement in the permeation rate of the Loeb-type membranes has been attributed to the decrease in the thickness of the dense selective region. The less dense region in such a membrane provides sufficient structural support to prevent rupture of the membrane under operating pressures but offers little resistance to permeate flow. Hence, the separation is essentially accomplished by the dense skin, and the primary function of the less dense support region is to physically support the dense skin. However, in such
Loeb-type membranes this less dense support region is frequently compacted by pressures such as those desirable for desalination of water and under such conditions the less dense support region loses some of its void volume.
Consequently, the free flow of permeate away from the effluent side of the dense skin is hindered, resulting in a reduced permeation rate. Moreover, the cellulose acetate membranes disclosed by Loeb et al, are also subject to fouling and various chemical degradations. Therefore, attention has been directed to developing Loebtype membranes of materials other than cellulose acetate which may provide stronger structural properties and increased chemical resistance. The "Loebing" of polymer materials to obtain a single component membrane exhibiting good selectivity and a good permeation rate has been found to be extremely difficult.
Most attempts result in producing membranes which are either porous, i.e., have fluid flow channels through the dense skin, and will not separate, or which have too thick a dense skin to give useful permeation rates. Thus, these asymmetric membranes often fail to meet with acceptance in liquid separation operations such as reverse osmosis. As hereinafter further described, it is even more difficult to provide Loeb-type membranes which exhibit good selectivity and permeation rates for gas separation operations.
Further proposals for providing advantageous separation membranes suitable for desalination of water and other liquid-liquid separations such as separations of organic materials from liquids have led to composite membranes comprising a porous support which, due to the presence of flow channels, can readily pass liquid, yet is sufficiently strong to withstand operating conditions and a thin semipermeable membrane supported thereon. Composite membranes which have b-en proposed include the so-called "dynamically-formed" membranes which re formed by continuously depositing a polymeric film material from a feed solution on to a porous support. This continuous deposition is required because the polymeric film material is subject to being carried into the pores and through the porous substrate and hence needs to be replenished. Moreover, the polymeric film material is frequently sufficiently soluble in the liquid mixture being subjected to separation that it is also usually subject to lateral erosion, i.e., it washes off the support.
It has also been proposed to prepare composite desalination membranes by providing an essentially solid diffusion, or separation, membrane on a porous support. The thickness of the separating membrane is relatively large, e.g. up to 60 microns, such that the separation membrane is sufficiently strong that it does not tend to flow into or rupture at the pores of the porous support. Other proposals have included the use of an anisotropic support having a denser region at the surface, i.e., skin, at the immediate support surface for the separation membrane.
For example, there have been proposed composite membranes for desalination of water which consist of anisotropic polysulfone hollow fibers which are coated with, e.g., polyethyleneimine which is cross-linked in situ or furfuryl alcohol which is polymerized in situ to provide a superimposed separation membrane. Another proposal has been tripartite separation membranes for reverse osmosis comprising an anisotropic porous substrate, an ultrathin adhesive layer over the porous substrate, and a thin semipermeable membrane bound to the substrate by the adhesive layer. Often, these ultrathin semipermeable membranes in composite form with porous support materials are proposedly prepared by separately fabricating the ultrathin membrane and a porous support followed by placing the two in surface-to-surface contact.
Other types of membranes which have been proposed for treating liquids are the so-called "ultrafiltration" membranes in which pores of a desired diameter are provided. Sufficiently small molecules can pass through the pores whereas larger, more bulky molecules are retained on the feed surface of the membrane. These membranes have an anisotropic support and a gel irreversibly compressed into the support to provide membranes having suitable pore sizes for the separation of caustic hydroxides from hemicellulose, and the ultrafiltration takes place through the gel.
Development of Membranes for Gas Separation
The above discussion of the background to this invention has been directed to membranes for the separation of a liquid from a liquid mixture such as in desalination of water. More recently emphasis has been placed on developing separation membranes which are suitable for separating a gas from a gaseous mixture. The permeation of gases through separation membranes has been the subject of various studies; however, gas separation membranes exhibiting both high flux and useful selective separations have apparently not been provided, at least commercially. The following discussion is illustrative of specific modifications which have been made to membranes used for gas separations and provides a basis upon which this invention can be fully appreciated.
Attempts have been made to draw on knowledge developed concerning liquidliquid separation membranes. There are, however, many different considerations in developing a suitable separation membrane for gaseous systems as compared with developing a suitable membrane for liquid systems. For instance, the presence of small pores in the membrane may not unduly adversely affect the performance of the membrane for liquid separations such as desalination due to absorption on and swelling of the membrane and the high viscosity and the high cohesive properties of the liquids. Since gases have extremely low absorption, viscosity and cohesive properties, no barrier is provided to prevent the gases from readily passing through the pores in such a membrane resulting in little, if any, separation of gases. An extremely important difference between liquids and gases which might affect selective separation by permeation through membranes is the generally lower solubility of gases in membranes as compared with the solubility of liquids in such membranes, thus resulting in lower permeability constants for gases as compared to those of liquids. Other differences between liquids and gases which might affect selective separation by permeation through membranes include density and internal pressure, the effect of temperature on the viscosity, surface tension, and the degree of order.
It has been realized that materials which exhibit good separation of gases often have lower permeability constants compared with those of materials exhibiting poor separation of gases. In general, efforts have been directed to providing the material of a gas separation membrane in as thin a form as possible, in view of the low permeabilities, in order to provide adequate flux yet provide a membrane as pore-free as possible, such that gases are passed through the membrane by interaction with the material of the membrane. One approach to developing separation membranes suitable for gaseous systems has been to provide composite membranes having a superimposed membrane supported on an anisotropic porous support wherein the superimposed membrane provides the desired separation, i.e., the superimposed membrane is semi-permeable. The superimposed membranes are advantageously sufficiently thin, i.e., ultrathin, to provide reasonable fluxes. The essential function of the porous support is to support and protect the superimposed membrane without harming the delicate, thin superimposed membrane. Suitable supports provide low resistance to permeate passage after the superimposed membrane has performed its function of selectively separating the permeate from the feed mixture. Thus, these supports are desirably porous to provide low resistance to permeate passage and yet sufficiently supportive, that is, having pore sizes sufficiently small to prevent the rupture of the superimposed membrane under separating conditions.
Such composite membranes for gas separations have not been without problems. For instance, one proposal is for the fabrication of composite membrane films for separation of oxygen from air comprising a support of microporous polycarbonate sheet and a separately formed, i.e., preformed, superimposed ultrathin separation membrane of 80 percent poly(phenylene oxide) and 20 percent organopolysiloxane-polycarbonate copolymer. In the fabrication of the membranes the exclusion from the manufacturing area of extremely small particulate impurities, i.e., particles below about 3000 Angstroms in size, is stated to be impractical or impossible. These fine particles may be deposited under or between preformed ultrathin membrane layers and, because of their large size in comparison to the ultrathin membranes, puncture the ultrathin membranes. Such breaches reduce the effectiveness of the membrane. The proposal was one of applying a performed organopolysiloxane-polycarbonate copolymer sealing material over the ultrathin membrane to cover the breaches caused by the fine particles, and also of employing a preformed layer of the organopolysiloxane-polycarbonate copolymer between the ultrathin membrane and the porous polycarbonate support as an adhesive. Thus the composite membranes of that proposal are complex in materials and techniques of construction.
In summary, apparently suitable anisotropic membranes have not been provided for gas separations which, in the absence of a superimposed membrane to provide the selective separation, exhibit sufficient flux and selectivity of separation for general commercial operations. It further appears that composite membranes for gas separation which have a superimposed membrane to provide the selective separation have achieved only slight or modest improvement in membrane performance, and there appears to be no successful, large scale commercial application of these gas separation membranes. Moreover, the superimposed membrane, although possibly ultrathin in order to provide the desired selectivity of separation, may significantly reduce the flux of the permeate gas through the composite membrane as compared with that of the porous support not having the superimposed membrane thereon.
Summary of the Invention
This invention pertains to particular multicomponent, or composite, membranes for gas separations comprising a coating in contact with a porous separation membrane wherein the separation properties of the- multicomponent membranes are principally determined by the porous separation membrane as opposed to the material of the coating, processes for gas separation employing the multicomponent membranes, and apparatus for gas separations utilizing the multicomponent membranes These multicomponent membranes for the separation of at least one gas from a gaseous mixture can exhibit a desirable selectivity and still exhibit a useful flux. This invention provides a multicomponent membranes for gas separation which can be fabricated from a wide variety of gas separation membrane materials and thus enable greater latitude than has heretofore existed in selecting such a membrane material which is advantageous for a given gas separation. This invention provides multicomponent membranes in which desired combinations of flux and selectivity of separation can be provided by the configuration and methods of preparation and combination of the components.
Thus, a material having high selectivity of separation, but a relatively low permeability constant, can be utilized to provide multicomponent membranes having desirable permeation rates and desirable selectivity of separation.
Moreover, the membranes of this invention can be relatively insensitive to the effects of contamination, i.e., fine particles, during their preparation which has previously caused difficulty in preparing composite membranes of a preformed ultrathin separating membrane superimposed on a support. Advantageously, the use of adhesives in preparing the multicomponent membranes of this invention may not be necessary. Hence, multicomponent membranes of this invention need not be complex in techniques of construction. Multicomponent membranes in accordance with this invention can be prepared to provide high structural strength, toughness, and abrasion and chemical resistances, yet exhibit commercially advantageous flux and selective separation. These multi-component membranes can also possess desirable handling characteristics such as low susceptibility to static electrical forces, low adhesion to adjacent multicomponent membranes and the like.
Definition of Terms
In accordance with this invention, the multicomponent membranes for gas separation comprise a porous separation membrane having feed and exit surfaces and a coating material in contact with the porous separation membrane. The porous separation membrane has essentially the same composition, or material, throughout its structure, i.e., the porous separation membrane is substantially chemically homogenous. The material of the porous separation membrane exhibits selective permeation for at least one gas of a gaseous mixture over that of at least one remaining gas of the mixture, and hence the porous separation membrane is, defined as a "separation" membrane. By describing the separation membrane as "porous" it is meant that the membrane has continuous channels for gas flow, i.e. pores, which communicate between the feed surface and exit surface. These continuous channels, if sufficiently large in number and in cross-section, can permit essentially all of a gaseous mixture to flow through the porous separation membrane with little, if any, separation due to interaction with the material of the porous separation membrane. This invention advantageously provides multicomponent membranes wherein the separation of at least one gas from a gaseous mixture by interaction with the material of the porous separation membrane is enhanced, as compared with that of the porous separation membrane alone.
The multicomponent membranes of this invention comprise porous separation membranes and coatings which have particular relationships. Some of these relationships can conveniently be stated in terms of relative separation factors with respect to a pair of gases for the porous separation membranes, coatings and the multicomponent membranes. A separation factor
a
(a )
b for a membrane for a given pair of gases a and b is defined as the ratio of the permeability constant (pus) of the membrane for gas a to the permeability constant (Pb) of the membrane for gas b. A separation factor is also equal to the ratio of the permeability (Pal) of a membrane of thickness 1 for gas a of a gas mixture to the permeability of the same membrane to gas b, (Pdl) wherein the permeability for a given gas is the volume of gas, standard temperature and pressure (STP), which passes through a membrane per square centimeter of surface area, per second, for a partial pressure drop of 1 centimeter of mercury across the membrane per unit of thickness, and is expressed as P = cm3/cm2-sec-cmHg/l.
In practice, the separation factor with respect to a given pair of gases for a given membrane can be determined employing numerous techniques which provide sufficient information for calculation of permeability constants or permeabilities for each of the pair of gases. Several of the many techniques available for determining permeability constants, permeabilities, and separation factors are disclosed by Hwang, et al., Techniques of Chemistry, Volume VII,
Membranes in Separations,
John Wiley & Sons, 1975 at Chapter 12, pages 296 to 322.
An intrinsic separation factor as referred to herein is the separation factor for
a material which has no channels for gas flow across the material, and is the highest
achievable separation factor for the material. Such a material may be referred to as
being continuous or non-porous. The intrinsic separation factor of a material can
be approximated by measuring the separation factor of a compact membrane of the
material. However, several difficulties may exist in the determination of an intrinsic
separation factor including imperfections introduced in the preparation of the
compact membrane such as the presence of pores, the presence of fine particles in the compact membrane, undefined molecular order due to variations in membrane preparation, and the like. Consequently, the determined intrinsic separation factor can be lower than the intrinsic separation factor. Accordingly, a "determined intrinsic separation factor" as employed herein refers to the separation factor of a dry compact membrane of the material.
Brief Statements of the Invention
The invention comprises a multicomponent membrane for gas separation comprising a coating material in contact with a porous support, in which the porous support is a porous separation membrane having a substantial void volume as hereinbefore defined and comprising a material, which material of the porous separation membrane exhibits selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture and the material of the coating is in occluding contact with the porous separation membrane wherein, with respect to at least one pair of gases, the material of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the material of the coating, and the multicomponent membrane exhibits a separation factor greater than the determined intrinsic separation factor of the material of the coating and greater than the separation factor of the porous separation membrane.
The process of the invention is one for separating at least one gas in a gaseous mixture from at least one other gas in the said gaseous mixture by selective permeation through a membrane and providing a permeated product containing at least one permeating gas, the process comprising contacting the gaseous mixture with at least one surface of the membrane, the said membrane being a multicomponent membrane according to the invention, which multicomponent membrane exhibits, with respect to at least one pair of gases of the gaseous mixture, selective permeation of one gas of the pair of gases over that of the remaining gas of the pair of gases; maintaining the opposite surface of the multicomponent membrane at a lower chemical potential for the said at least one permeating gas than the chemical potential at the said surface; permeating the said at least one permeating gas into and through the multicomponent membrane; and removing from the vicinity of the opposite surface a permeated product having a different proportion of the said at least one gas of the gaseous mixture to the said at least one other gas of the gaseous mixture than the proportion in the gaseous mixture of the said at least one gas to the said at least one other gas.
The invention also comprises an apparatus for selectively separating at least one gas in a gaseous mixture from at least one remaining gas, comprising an enclosure and a multicomponent membrane according to the invention within the enclosure for selectively separating the said at least one gas in the gaseous mixture and providing a permeated product, the multicomponent membrane having a feed surface and an opposing exit surface, and the enclosure having means to enable the gaseous mixture to be supplied to the feed surface, means to enable removal of gases from the vicinity of the feed surface, and means to enable the permeated product to be removed from the vicinity of the exit surface.
A multicomponent membrane for gas separations in accorance with this invention exhibits, with respect to at least one pair of gases, a separation factor which is greater than the determined intrinsic separation factor of the coating material. The difference in the separation factors is, e.g., generally at least about 10 percent greater. By the term "occluding contact," it is meant that the coating contacts the porous separation membrane such that in the multicomponent membrane the proportion of gases passing through the material of the porous separation membrane to gases passing through the pores is increased compared with that proportion in the porous separation membrane alone. Thus, the contact is such that in the multicomponent membrane an increased contribution of the material of the porous separation membrane to the separation factor exhibited by the multicomponent membrane for at least one pair of gases is obtained as compared with that contribution in the porous separation membrane alcne.
Accordingly, with respect to said at least one pair of gases, the separation factor which is exhibited by the multicomponent membrane will be greater than the separation factor exhibited by the porous separation membrane. Additionally, with respect to at least one pair of gases, the material of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the material of the coating. Also, with respect to said at least one pair of gases; the separation factor exhibited by the multicomponent membrane is often equal to or less than the determined intrinsic separation factor of the material of the porous separ thickness. Preferably the void volume is up to 90, say, 10 to 80, and sometimes 20 or 30 to 70, percent based on the superficial volume, i.e., the volume contained within the gross dimensions, of the porous separation membrane. One method for determining the void volume of a orous separation membrane is by a density comparison with a volume of the bulk material of the porous separation membrane which volume would correspond to a membrane of the same gross physical dimensions and configurations as the porous separation membrane. Hence, the bore of a hollow fiber porous separation membrane would not affect the density of the porous separation membrane.
The density of the porous separation membrane can be essentially the same throughout its thickness, i.e., isotropic, or the porous separation membrane can be characterized by having at least one relatively dense region within its thickness in barrier relationship to gas flow across the porous separation membrane, i.e., the porous separation membrane is anisotropic. The coating is preferably in occluding contact with the relatively dense region of the anisotropic porous separation membrane. Since the relatively dense region can be porous, it can more easily be made quite thin as compared to making a compact membrane of the same thickness. The use of porous separation membranes having relatively dense regions which are thin provides enhanced flux through the multicomponent membrane.
In a further aspect of the feature of the invention relating to multicomponent membranes, the multicomponent membranes comprise a coating in occluding contact with a porous separation membrane of a material, which material exhibits selective permeation of at least one gas in a gaseous mixture over that of one or more remaining gases in the gaseous mixture, wherein the coating is applied using an essentially liquid substance which is suitable for forming the coating, and wherein, with respect to at least one pair of gases, the multicomponent membrane exhibits a separation factor significantly greater than the determined intrinsic separation factor of the material of the coating. The substance for application to the porous separation membrane is essentially liquid in that it is incapable of maintaining a form in the absence of external support. The material of the coating may be liquid, or may be dissolved in or suspended as a finely divided solid (e.g., colloidal size) in a liquid menstruum, to provide the essentially liquid substance for application to the porous separation membrane. Advantageously, the material of the coating, or the material of the coating in the liquid menstruum, wets, i.e., tends to adhere to, the material of the porous separation membrane. Thus, the contact of the coating with the porous separation membrane is frequently facilitated. The use of an essentially liquid substance to provide the coating on the porous separation membrane enables simpler techniques to be employed than have been employed in providing composite membranes of separately formed, solid materials. Moreover, a wide range of materials for the coating can be employed, and the application techniques can readily be adapted to the use of porous separation membranes of various configurations.
In an additional aspect of the feature of this invention relating to the multicomponent membranes, the multicomponent membranes comprise a coating in occluding contact with a porous separation membrane comprising polysulfone wherein, with respect to at least one pair of gases, the multicomponent membrane exhibits a separation factor significantly greater than the determined intrinsic separation factor of the material of the coating. In another aspect of this feature the multicomponent membranes comprise a coating in occluding contact with a hollow fiber porous separation membrane of material, which material exhibits selective permeation of at least one gas in a gaseous mixture over that of one or more remaining gases in the gaseous mixture wherein, with respect to at least one pair of gases, the multicomponent membrane exhibits a separation factor greater than the determined intrinsic separation factor of the material of the coating. In hollow filaments (i.e., hollow fibers) the exterior surface can be the feed or exit surface of the porous separation membrane and the interior surface will be the exit or feed surface, respectively. Hollow filaments advantageously facilitate providing gas separation apparatus having high available surface areas for separation within the given volumes of the apparatus. Hollow filaments are known to be able to withstand greater pressure differentials than unsupported films of essentially the same total thickness and morphology.
A second feature of this invention pertains to processes for gas separation employing the multicomponent membranes. In this feature of the invention at least one gas in a gaseous mixture is separated from at least one other gas by selective permeation to provide a permeated product containing at least one permeating gas.
The process comprises: contacting the gaseous mixture with one surface (feed surface) of a multicomponent membrane, which with respect to at least one pair of gases in the gaseous mixture, multicomponent membrane exhibits selective permeation of one gas of the pair of gases over that of the remaining gas of the pair of gases; maintaining the opposite surface (exit surface) of the multicomponent membrane at a lower chemical potential for the at least one permeating gas than the chemical potential at the said one surface; permeating said at least one permeating gas into and through the multicomponent membrane; and removing from the vicinity of said opposite surface a permeated product having a different proportion of said at least one gas of the gaseous mixture to said at least one other gas of the gaseous mixture than the proportion in the gaseous mixture of said at least one gas to said at least one other gas. The separation processes of this invention include concentrating the said at least one gas on the feed side of the multicomponent membrane to provide a concentrated product and include permeating the said at least one gas through the multicomponent membrane to provide a permeated product wherein said different proportion is a higher proportion.
In one aspect of this feature, the multicomponent membrane comprises a coating in occluding contact with a porous separation membrane having a substantial void volume. In another aspect of this feature of the invention, hydrogen is selectively separated from a gaseous mixture also comprising at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitrous oxide, ammonia, and a hydrocarbon of 1 to 5 carbon atoms. In a further aspect of this feature of the invention, at least one gas in a gaseous mixture is separated from at least one other gas involving contacting the gaseous mixture with a multicomponent membrane comprising a coating in occluding contact with a porous separation membrane comprising polysulfone.
A further feature of this invention pertains to apparatus for gas separations which utilize multicomponent membranes in accordance with this invention. The apparatus comprise an enclosure having at least one multicomponent membrane in accordance with this invention therein, said multicomponent membrane having a feed surface and an opposing exit surface, and said enclosure having means to enable a gaseous mixture to be supplied to and means to enable removal of gases from the vicinity of the feed surface of the multicomponent membrane, and means to enable a permeated product to be removed from the vicinity of the exit surface of the multicomponent membrane.
It has surprisingly been found that a material for the coating which can have a low determined intrinsic separation factor can be provided on a porous separation membrane, which porous separation membrane can have a low separation factor, to provide a multicomponent membrane having a separation factor greater than either the coating or porous separation membrane. This result is quite surprising in contrast to previous proposals for gas separation composite membranes having a superimposed membrane supported on a porous support which have essentially required that the superimposed membrane exhibit a high separation factor in order to provide the selective separation for the membrane. The finding that coatings exhibiting low separation factors can be employed in conjunction with porous separation membranes to provide multicomponent membranes having a greater separation factor than each of the coating and porous separation membrane leads to highly advantageous multicomponent membranes for separating gases. For instance, materials having desirable intrinsic separation factors, but which were difficult to utilize as superimposed membranes, may be used as the material of the porous separation membrane in accordance with this invention with the selectivity of separation of the material of the porous separation membrane contributing significantly to the separation factor of the multicomponent membrane.
It can clearly be seen that the porous separation membrane of the multicomponent membranes can be anisotropic with a thin, but relatively dense, separating region. Thus, the porous separation membrane can take advantage of the low resistance to permeation offered by anisotropic membranes yet provide multicomponent membranes which exhibit desirable separation factors.
Furthermore, the presence of flow channels which can render unicomponent (noncomposite) anisotropic membranes unacceptable for gas separations, can be acceptable, and even desirable, in porous separation membranes used in the multicomponent membranes of this invention. The coating can preferably provide a low resistance to permeation, and the material of the coating exhibit a low determined intrinsic separation factor. In some multicomponent membranes, the coating may tend to selectively reject the desired permeate gas, yet the resulting multicomponent membrane using that coating can still according to the invention exhibit a separation factor greater than that of the porous separation membrane.
This invention is concerned with the multicomponent membranes formed through the combination of a preformed porous separation membrane, i.e., a porous separation membrane which is prepared prior to application of the coating, and a coating. The invention particularly relates to multicomponent gas separation membranes wherein the selectivity of separation of the material of the porous separation membrane contributes significantly to the selectivity of and relative permeation rates of the permeate gases through the multicomponent membrane.
The multicomponent membranes according to the invention can, in general, exhibit higher rates of permeation than do composite membranes which utilize superimposed membranes exhibiting high separation factors. In addition, the multicomponent membranes of this invention provide a separation factor which is superior to those of the coating and porous separation membrane. The multicomponent membranes of the invention may be in some ways analogous, but only superficially, to the gas separation membranes which have superimposed membranes exhibiting a high separation factor on a porous support, but the latter do not utilize a support or substrate which provides a substantial proportion of the separation.
The multicomponent membranes of the invention allow great flexibility for making specific separations because both the coating and the porous separation membrane contribute toward the overall separation performance. The result is an increased ability to tailor these membranes for specific separation requirements, e.g., for the separation of desired gas or gases from various gas mixtures at commercially desirable combinations of rate and selectivity of separation. The multicomponent membranes can be fabricated from a wide variety of gas separation materials and thus provide a greater latitude than has heretofore existed in selecting an advantageous membrane material for a given gas separation. In addition, these multicomponent membranes are capable of providing good physical properties such as toughness, abrasion resistance, strength and durability, and good chemical resistance.
Detailed Description of the Invention
The invention pertains to particular multicomponent membranes for gas separations which comprise a coating in contact with a porous separation membrane in which the separation properties of the multicomponent membrane are principally determined by the porous separation membrane as opposed to the coating, processes for gas separation employing the multicomponent membranes and apparatus for gas separations utilizing the multicomponent membranes.
The multicomponent membranes are widely applicable in gas separation operations. Gaseous mixtures suitable for feeds according to the invention are comprised of gaseous substances, or substances that are normally liquid or solid but are vapors at the temperature under which the separation is conducted. The invention as described in detail hereinafter pertains chiefly to the separation of, for example, oxygen from nitrogen; hydrogen from at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitrous oxide, ammonia, and a hydrocarbon of 1 to 5 carbon atoms, especially methane, ethane, and ethylene; ammonia from at least one of hydrogen, nitrogen, argon, and a hydrocarbon of 1 to 5 carbon atoms, e.g., methane; carbon dioxide from at least one of carbon monoxide and a hydrocarbon of 1 to 5 carbon atoms, e.g., methane; helium from a hydrocarbon of 1 to 5 carbon atoms, e.g., methane; hydrogen sulfide from a hydrocarbon of 1 to 5 carbon atoms, for instance, methane, ethane or ethylene; and carbon monoxide from at least one of hydrogen, helium, nitrogen, and a hydrocarbon of 1 to 5 carbon atoms. It is emphasized that the invention is not restricted to these particular separation applications or gases nor the specific multicomponent membranes in the examples.
The multicomponent membranes for gas separation, according to the invention, can be films or hollow filaments, or fibers, having a porous separation membrane, or substrate, and a coating in occluding contact with the porous separation membrane. Some factors which influence the behavior of the multicomponent membranes are the permeability constants of the materials of the coating and porous separation membranes, the total cross-sectional area of the holes (i.e. pores or flow channels) relative to the total surface area of the porous separation membrane, the relative thickness of each of the coating and the porous separation membrane of the multicomponent membrane, the morphology of the porous separation membrane, and most importantly the relative resistance to permeate flow of each of the coating and the porous separation membrane in a multicomponent membrane. In general, the degree of separation of the multicomponent membrane is influenced by the relative resistance to gas flow for each gas in the gas mixture of the coating and the porous separation membrane, which can be specifically chosen for their gas flow resistance properties.
The material used for the porous separation membrane may be a solid natural or synthetic substance having useful gas separation properties. In the case of polymers, both addition and condensation polymers which can be cast, extruded or otherwise fabricated to provide porous separation membranes are included. The porous separation membranes can be prepared in porous form, for example, by casting from a solution comprised of a solvent for the polymeric material into a poor or nonsolvent for the material. The spinning and/or casting conditions and/or treatments subsequent to the initial formation, and the like, can influence the porosity and resistance to gas flow of the porous separation membrane.
Generally organic or organic polymers mixed with inorganic fillers are used to prepare the porous separation membrane. Typical polymers suitable for the porous separation membrane according to the invention can be substituted or unsubstituted polymers and may be selected from polysulfones; poly(styrenes), including styrene-containing copolymers such as acrylonitrile-styrene copolymers, styrene-butadiene copolymers and styrenevinylbenzylhalide copolymers; polycarbonates, cellulosic polymers, such as cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose, etc.; polyamides and polyimides, including aryl polyamides and aryl polyimides; polyethers; poly(arylene oxides) such as poly(phenylene oxide) and poly(xylylene oxide); poly(esteramide-diisocyanate); polyurethanes; polyesters such as poly(ethylene terephthalate), poly(alkyl methacrylates), poly(alkyl acrylates), poly(phenylene terephthalate), etc,; polysulfides; polymers from monomers having alpha-olefinic unsaturation other than mentioned above such as poly(ethylene), poly(propylene), poly(butene-l), poly(4-methyl pentene-l), polyvinyls, e.g., poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters) such as poly(vinyl acetate) and poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes) such as poly(vinyl formal) and polyvinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(vinyl urethanes), poly(vinyl ureas, poly(vinyl phosphates), and poly(vinyl sulfates); polyallyls; poly(benzobenzimidazole); polyhydrazides; polyoxadiazoles; polytriazoles; poly(benzimidazole); polycarbodiimides; polyphosphazines; etc., and interpolymers, including block interpolymers containing repeating units from the above such as terpolymers of acrylonitrile-vinyl bromide-sodium salt of parasulphophenylmethallyl ethers, and grafts and blends containing any of the foregoing. Typical substituents providing substituted polymers include halogens such as fluorine, chlorine and bromine; hydroxyl groups; lower alkyl groups; lower alkoxy groups; monocyclic aryl; lower acyl groups and the like.
Selection of the porous separation membrane for the present multicomponent membrane for gas separations may be made on the basis of the heat resistance, solvent resistance, and mechanical strength of the porous separation membrane, as well as other factors dictated by the operating conditions for selective permeation, as long as the coating and porous separation membrane have the prerequisite relative separation factors in accordance with the invention for at least one pair of gases. The porous separation membrane is preferably at least partially selfsupporting, and in some instances may be essentially self-supporting. The porous separation membrane may provide essentially all of the structural support for the membrane, or the multicomponent membrane may include a structural support member which can provide little, if any, resistance to the passage of gases.
One of the preferred porous separation membranes utilized in forming the multicomponent membranes comprises polysulfone. Among the polysulfones which may be utilized are those having a polymeric backbone comprised of the repeating structural unit:
where R and R' can be the same or different and are aliphatic or aromatic hydrocarbyl-containing moieties, say, of 1 to 40 carbon atoms, wherein the sulfur in the sulfonyl group is bonded to aliphatic or aromatic carbon atoms, and the polysulfone has an average molecular weight suitable for film or fiber formation, often at least 10,000. When the polysulfone is not cross-linked, the molecular weight of the polysulfone is generally less than 500,000, and is frequently less than 100,000.
The repeating units may be bonded, i.e., R and R' may be bonded, by carbon to carbon bonds or through various linking groups such as
Particularly advantageous polysulfones are those in which at least one of R and R' comprises an aromatic hydrocarbyl-containing moiety and the sulfonyl moiety is bonded to at least one aromatic carbon atom. Common aromatic hydrocarbylcontaining moieties comprise phenylene and substituted phenylene moieties; bisphenyl and substituted bisphenyl moieties, bisphenyl methane and substituted bisphenyl methane moieties having the nucleus
substituted and unsubstituted bisphenyl ethers of formula
wherein X is oxygen or sulfur; and the like. In the depicted bisphenyl methan and bisphenyl ether moieties R1 to R10 represent substituents which may be the same or different and have the structure
wherein X, and X2 are the same or different and are hydrogen or halogen (e.g., fluorine, chlorine, and bromine); p is 0 or an integer, e.g., of I to 6; and Z is hydrogen, halogen (e.g., fluorine, chlorine and bromine), ±Y4R1, (in which q is 0 or 1, Y is -0--S-, -55-,
and R" is hydrogen substituted or unsubstituted alkyl say, of 1 to 8 carbon atoms, or substituted or unsubstituted aryl, say, monocyclic or bicyclic of 6 to 15 carbon atoms), heterocyclic with the heteroatom being at least on of nitrogen, oxygen and sulfur and being monocyclic or bicyclic with 5 to 15 ring atoms, sulfato and sulfono, especially lower alkyl-containing or monocyclic or bicyclic aryl-containing sulfato or sulfono, phosphorous-containing moieties such as phosphino and phosphato and phosphono, especially lower alkyl-containing or monocyclic or bicyclic arylcontaining phosphato or phosphono, amine including primary, secondary, tertiary and quaternary amines in which the secondary, tertiary and quaternary amines often contain lower alkyl or monocyclic or bicyclic aryl moieties, isothioureyl, thioureyl, guanidyl, trialkylsilyl, trialkylstannyl, trialkylplumbyl, dialkylstibinyl, etc. Frequently, the substituents on the phenyl groups of the bisphenyl methane and bisphenyl ether moieties are often provided at the ortho position, i.e., R, to R10 are hydrogen. The polysulfones having aromatic hydrocarbyl-containing moieties in general possess good thermal stability, are resistant to chemical attack, and have an excellent combination of toughness and flexibility. Useful polysulfones are sold under trade names such as "P-1700," and "P-3500" by Union Carbide, both commercial products having a linear chain of the general formula
where n, representing the degree of polymerisation, is about 50 to 80.
Poly(arylene ether) sulfones are also advantageous. Polyether sulfones having the structure
and available from ICI, Ltd., are also useful. Still other useful polysulfones could be prepared through polymer modifications, for example, by cross-linking, grafting, quaternization, and the like.
In making hollow filament porous separation membranes, a wide variety of spinning conditions may be employed. One method for the preparation of polysulfone hollow filaments is disclosed by Cabasso, et al, in Research and
Development of NS-I and Related Polysulfone Hollow Fibers for Reverse Osmosis
Desalination of Seawater
Gulf South Research Institute, July, 1975, distributed by National Technical
Information Service, U.S. Department of Commerce, publication PB 248,666.
Particularly advantageous hollow fibers of polysulfones, e.g., of P-3500 polysulfone produced by Union Carbide (U.S.A. and polyether sulfones of ICI, Ltd., can be prepared by spinning the polysulfone in a solution comprised of solvent for the polysulfone. Typical solvents are dimethylformamide, dimethylacetamide and Nmethylpyrrolidone. The weight percent polymer in the solution may vary widely but is sufficient to provide a hollow fiber under the spinning conditions. Often, the weight percent of polymer in the solution is 15 to 50, e.g., 20 to 35. If the polysulfone and/or solvent contain contaminants, such as water, particulates, etc., the amount of contaminants should be sufficiently low to permit spinning. If necessary, contaminants can be removed from the polysulfone and/or solvent. The size of the spinning jet will vary with the desired inside and outside diameters of the product hollow filament. One class of spinning jets may have orifice diameters of 15 to 35 mils (0.38 to 0.88 millimeters) and pin diameters of 8 to 15 mils (0.2 to 0.38 millimeters) with an injection capillary within the pin. The diameter of injection capillary may vary within the limits established by the pin. The spinning solution is frequently maintained under a substantially inert atmosphere to prevent contamination and/or coagulation of the polysulfone prior to spinning and to avoid undue fire risks with volatile and flammable solvents. A convenient atmosphere is dry nitrogen. The presence of excessive amounts of gas in the spinning solution may result in the formation of large voids.
The spinning may be conducted using a wet jet or dry jet technique, i.e. the jet may be in or removed from the coagulating bath. The wet jet technique is often used for the sake of convenience. The spinning conditions are preferably not such that the filament is unduly stretched. Frequently, spinning speeds are within the range of 5 to 100 meters per minute although higher spinnings speeds can be employed providing the filament is not unduly stretched and sufficient residence time is provided in the coagulation bath. Any essentially non-solvent for the polysulfone can be employed for the coagulation bath. Conveniently, water is employed as the primary material in the coagulation bath. A fluid is commonly injected into the inside of the fiber. The fluid may comprise, e.g., air, isopropanol, water, or the like. The residence time for the spun fiber in the coagulation bath is at least sufficient to ensure solidification of the filament. The temperature of the coagulation bath may also vary widely, e.g., from -15" to 900C or more, and is most often 10 to 350C, say, 2" to 80 or 100C. The coagulated hollow fiber is desirably washed with water to remove solvent and may be stored in a water bath for periods of time of at least about two hours. The fibers are generally dried prior to application of the coating and assembly in an apparatus for gas separations. The drying may be conducted at 0 to 900 C, conveniently about room temperature, e.g., 15 to 35"C, and at about 5 to 95, preferably 40 to 60, percent relative humidity.
The foregoing description of methods for preparing hollow filament porous separation membranes of polysulfone is provided merely to illustrate techniques which are available for producing porous separation membranes and is not in limitation of the invention.
The coating may be in the form of an essentially non-interrupted membrane, i.e., an essentially non-porous membrane, in contact with the porous separation membrane, or the coating may be discontinuous, or interrupted. When the coating is interrupted, it is sometimes referred to as an occluding material since it may occlude channels for gas flow, i.e. pores. Preferably, the coating is not so thick as to adversely affect the performance of the multicomponent membrane, e.g., by causing an undue decrease in flux or by causing such a resistance to gas flow that the separation factor of the multicomponent membrane is essentially that of the coating. Often the coating may have an average thickness of up to 50 microns.
When the coating is interrupted, of course, there may be areas having no coating material. The coating may often have an average thickness ranging from 0.0001 to 50 microns. In some instances, the average thickness of the coating is less than I micron, and may even be less than 0.5 microns. The coating may comprise one layer or at least two separate layers which may or may not be of the same materials.
When the porous separation membrane is anisotropic, i.e., has a relatively dense region within its thickness in gas flow barrier relationship, the coating is desirably applied to be in occluding contact in the relatively dense region. A relatively dense region may be at either or both surfaces of the porous separation membrane or may be at a mid-portion of the thickness of the porous separation membrane. The coating is conveniently applied to at least one of the feed and exit surfaces of the porous separation membrane, and when the multicomponent membrane is a hollow fiber, the coating may be applied to the outside surface to also provide protection to and/or faci membrane is subjected to a lower absolute pressure. If the essentially liquid substance comprises polymerizable material and the polymerizable material is polymerized after application to the porous separation membrane to provide the coating, the other surface of the porous separation membrane is advantageously subjected to a lower absolute pressure during or before the polymerization.
However, the invention itself is not limited by the particular method by which the material of the coating is applied.
Particularly advantageous materials for the coating have relatively high permeability constants for gases such that the presence of a coating does not unduly reduce the permeation rate of the multicomponent membrane. The resistance to gas flow of the coating is preferably relatively small in comparison to the resistance of the multicomponent membrane. As stated previously, the selection of materials for the coating depends on the determined intrinsic separation factor of the material of the coating relative to the determined intrinsic separation factor of the material of the porous separation membrane to provide a multicomponent membrane exhibiting a desired separation factor. The material of the coating should be capable of providing occluding contact with the porous separation membrane. For instance, when applied it should sufficiently wet and adhere to the porous separation membrane to enable occluding contact to occur.
The wetting properties of the material of the coating can be easily determined by contacting the material of the coating, either alone or in a solvent, with the material of the porous separation membrane. Moreover, based on estimates of the average pore diameter of the porous separation membrane materials for the coating of appropriate molecular size can be chosen. If the molecular size of the material of the coating is too large to be accommodated by the pores of the porous separation membrane, the material may not be useful to provide occluding contact. If, on the other hand, the molecular size of the material for the coating is too small, it may be drawn through the pores of the porous separation membrane during coating and/or separation operations. Thus with porous separation membranes having larger pores, it may be desirable to employ materials for coating having larger molecular sizes than with smaller pores. When the pores are in a wide variety of sizes, it may be desirable to employ a polymerizable material for the coating material which is polymerized after application to the porous separation membrane, or to employ two or more coating materials of different molecular sizes, e.g., by applying the materials of the coating in order of their increasing molecular sizes.
The materials for the coating may be natural or synthetic substances, and are often polymers, and advantageously exhibit the appropriate properties to provide occluding contact with the porous separation membrane. Synthetic substances include both addition and condensation polymers. Typical of the useful materials which can comprise the coating are polymers which can be substituted or unsubstituted, and which are solid or liquid under gas separation conditions, and include but are not limited to synthetic rubbers; natural rubbers; relatively high molecular weight and/or high boiling liquids; organic prepolymers; poly(siloxanes) (silicone polymers); polysilazines; polyurethanes; poly(epichlorohydrin); polyamines; polyimines; polyamides (including polylactams) acrylonitrilecontaining copolymers such as poly(a-chloroacrylonitrile) copolymers; polyesters, e.g., polylactones, poly(alkyl acrylates) and poly (alkyl methacrylates) wherein the alkyl groups have, say I to about 8 carbons, polysebacates, polysuccinates, and alkyd resins; terpinoid resins such as linseed oil; cellulosic polymers; polysulfones, especially aliphatic-containing polysulfones; poly(alkylene glycols) such as poly(ethylene glycol), poly(propylene glycol), etc.; poly(alkylene) polysulfates; polypyrrolidones; polymers from monomers having a-olefinic unsaturation such as poly(olefins), e.g., poly(ethylene), poly(propylene), poly(butadiene), poly(2,3- dichlorobutadiene), poly(isoprene), poly(chloroprene), poly(styrene) including poly(styrene) copolymers, e.g., styrene-butadiene copolymer, polyvinyls such as poly(vinyl alcohols), poly(vinyl aldehydes) (e.g., poly(vinyl formal) and poly(vinyl butyral)), poly(vinyl ketones) (e.g., poly(methylvinylketone)), poly(vinyl esters) (e.g., poly(vinyl benzoate)), poly(vinyl halides) (e.g., poly(vinyl bromide)), poly(vinylidene halides), poly(vinylidene carbonate), poly(N-vinylmaleimide), etc., poly(l,5-cyclooctadiene), poly(methylisopropenylketone), fluorinated ethylene copolymer; poly(arylene oxides), e.g., poly(xylylene oxide); polycarbonates; polyphosphates, e.g., poly(ethylenemethylphosphate); and any interpolymers including block interpolymers containing repeating units from the above, and grafts and blends containing any of the foregoing. The polymers may if desired be polymerized after application to the porous separation membrane.
Particularly useful materials for coatings comprise poly(siloxanes). Typical poly(siloxanes) can comprise aliphatic or aromatic moieties and often have repeating units containing I to 20 carbon atoms. The molecular weight of the poly(siloxanes) may vary widely, but is generally at least 1000. Often, the poly(siloxanes) have a molecular weight of 1,000 to 300,000 when applied to the porous separation membrane. Common aliphatic and aromatic poly(siloxanes) include the poly(monosubstituted and disubstituted siloxanes), e.g., wherein the substituents are lower aliphatic, for instance, lower alkyl, including cycloalkyl, especially methyl, ethyl, and propyl, lower alkoxy; aryl including mono or bicyclic aryl including biphenylene, naphthalene, etc.; lower mono and bicyclic aryloxy; acyl including lower aliphatic and lower aromatic acyl; and the like. The aliphatic and aromatic substituents may be substituted, e.g., with halogens, e.g., fluorine, chlorine and bromine, hydroxyl groups, lower alkyl groups, lower alkoxy groups, lower acyl groups and the like. The poly(siloxane) may be cross-linked in the presence of a cross-linking agent to provide a silicone rubber, and the poly(siloxane) may be a copolymer with a cross-linkable comonomer such as amethylstyrene to assist in the cross-linking. Typical catalysts to promote crosslinking include the organic and inorganic peroxides. The cross-linking may be prior to application of the poly(siloxane) to the porous separation membrane, but preferably the poly(siloxane) is cross-linked after being applied to the porous separation membrane. Frequently, the poly(siloxane) has a molecular weight of 1,000 to 100,000 prior to cross-linking. Particularly advantageous poly(siloxanes) comprise poly(dimethylsiloxane), poly(phenylmethylsiloxane), poly(trifluoropropylmethylsiloxane), copolymer of a-methylstyrene and dimethylsiloxane, and post-cured poly(dimethylsiloxane)-containing silicone rubber having a molecular weight of 1,000 to 50,000 prior to cross-linking. Some poly(siloxanes) do not sufficiently wet a polysulfone porous separation membrane to provide as much occluding contact as is desired. However, dissolving or dispersing the poly(siloxane) in a solvent which does not substantially affect the polysulfone can facilitate obtaining occluding contact. Suitable solvents include normally liquid alkanes, e.g., pentaner, cyclohexane, etc.; aliphatic alcohols, e.g., methanol; some halogenated alkanes; and dialkyl ethers; and the like; and mixtures thereof.
The following materials for porous separation membranes and coating are representative of useful materials and their combinations to provide the multicomponent membranes of this invention and gas separations for which they may be employed. These materials, combinations, and applications, however, are only representative of the wide range of materials useful in the invention and, are not provided in limitation of the invention, but only serve to illustrate the broad application of the benefits thereof. Typical materials for porous separation membranes for separation of oxygen from nitrogen include but are not-limited to cellulose acetate, e.g., cellulose acetate having a degree of substitution of about 2.5; polysulfone; styrene-acrylonitrile copolymer, e.g., having 20 to 70 weight percent styrene and 30 to 80 weight percent acrylonitrile, blends of styrenearylonitrile copolymers. Suitable coating materials include poly(siloxanes) (polysilicones), e.g., poly(dimethylsiloxane), poly(phenylmethylsiloxane), poly (trifluoropropylmethylsiloxane), pre-vulcanized and post-vulcanized silicone rubbers, etc.; a.methylstyrene-dimethylsiloxane block copolymer; Poly(styrene), e.g., poly(styrene) having a degree of polymerization of 2 to 20; poly(isoprene), e.g., isoprene prepolymer and poly(cis- 1 ,4-isoprene); aliphatic hydrocarbylcontaining compounds having 14 to 30 carbon atoms, e.g., hexadecane, linseed oil, especially raw linseed oil, etc.; and the like.
Typical materials for porous separation membranes for separation of hydrogen from gaseous mixtures containing hydrogen include cellulose acetate, e.g., cellulose acetate having a degree of substitution of about 2.5; polysulfone; styreneacrylonitrile copolymer, e.g., having 20 to 70 weight percent styrene and 30 to 80 weight percent acrylonitrile, blends of styrene-acrylonitrile copolymers, etc.; polycarbonates; poly(arylene oxides) such as poly(phenylene oxide), poly(xylylene oxide), brominated poly(xylylene oxide), brominated poly(xylylene oxide) post treated with trimethylamine, thiourea, etc.; and the like. Suitable coating materials include poly(siloxane) (polysilicones); e.g., poly(dimethylsiloxane), pre-vulcanized and post-vulcanized silicone rubber, etc.; poly(isoprene); a-methylstyrenedimethylsiloxane block copolymer; aliphatic hydrocarbyl-containing compounds having 14 to 30 carbon atoms; and the like.
The porous separation membranes used in this invention are advantageously not unduly porous and thus provide sufficient area of the porous separation membrane material for effecting separation on a commercially attractive basis. The porous separation membranes significantly effect the separation of the multicomponent membranes of this invention, and accordingly, it is desirable to provide a large ratio of total surface area to total pore cross-sectional area in the porous separation membrane. This result is clearly contrary to the objectives of previous proposals in preparing composite membranes wherein the superimposed membrane substantially achieves the separation, and the supports are desirably provided as porous as possible consistent with their primary function, i.e., supporting the superimposed membrane, and advantageously the support does not interfere with the permeate gas either in slowing or inhibiting the gas flow from the superimposed membrane.
Clearly, the amount of gas passing through the material of the porous separation membrane and its influence on the performance of the multicomponent membranes of the invention is affected by the ratio of total surface area to total pore cross-sectional area and/or the average pore diameter of the porous separation membrane. Frequently, the porous separation membranes have ratios of total surface area to total pore cross-sectional area of at least 10:1, preferably at least 103:1, to 108:1, and some porous separation membranes may have ratios of 103:1 to 108:1 or 1012:1. The average pore cross-sectional diameter may vary widely and may often be in the range of 5 to 20,000 angstroms, and in some porous separation membranes, particularly in some polysulfone porous separation membranes, the average pore cross-sectional diameter may be 5 to 1000 to 5000, even 5 to 200, angstroms.
The coating is in occluding contact with the porous separation membrane such that, with respect to the models which have been developed based on observation of the performance of the multicomponent membranes of this invention, increased resistance to the passage of gases through the pores of the separation membrane is provided, and the proportion of gases passing through the material of the porous separation membrane to gases passing through the pores is enhanced over that proportion using the porous separation membrane not having the coating.
A useful characteristic with respect to gas separation membranes is the effective separating thickness. The effective separating thickness as employed herein is the thickness of a continuous (non-porous) and compact membrane of the material of the porous separation membrane which would have the same permeation rate for a given gas as the multicomponent membrane, i.e., the effective separating thickness is the quotient of the permeability constant of the material of the porous separation membrane for a gas divided by the permeability of the multicomponent membrane for the gas. By providing lower effective separating thicknesses, the rate of permeation for a particular gas is increased.
Often the effective separating thickness of the multicomponent membranes is substantially less than the total membrane thickness, especially when the multicomponent membranes are anisotropic. Frequently, the effective separating thickness of the multicomponent membranes with respect to a gas, which can be demonstrated by at least one of carbon monoxide, carbon dioxide, nitrogen, argon, sulfur hexafluoride, methane and ethane, is less than 100,000, preferably less than 15,000, say, 100 to 15,000 angstroms.
In multicomponent membranes comprising, e.g., polysulfone porous separation membranes, the effective separating thickness of the multicomponent membrane for at least one of said gases is desirably less than 5000 Angstroms. In some multicomponent membranes the effective separating thickness, especially with respect to at least one of said gases is less than 50, preferably less than 20, percent of the thickness of the multicomponent membrane.
Prior to the invention, one method for preparing membranes for gas separations trom membranes containing pores has been to treat at least one surface of the membrane containing the pores to densify the surface and thereby decrease the presence of pores, which pores decrease the selectivity of separation of the membrane. This densification has been by, for instance, chemical treatment with solvents or swelling agents for the material of the membrane or by annealing which can be conducted with or without the contact of a liquid with the membrane. Such densification procedures usually result in a substantial decrease in flux through the membrane. Some particularly advantageous multicomponent membranes of this invention exhibit a greater permeability than that of a membrane substantially the same as the porous separation membrane used in the multicomponent membrane except that at least one surface of the membrane has been treated to sufficiently densify the membrane or sufficiently annealed, with or without the presence of a liquid to provide, with respect to at least one pair of gases, a separation factor equal to or greater than the separation factor exhibited by the multicomponent membrane. Another method for increasing the selectivity of separation of a membrane is to modify the conditions of its manufacture such that it is less porous than a membrane produced under the unmodified conditions.
Generally, the increase in selectivity of separation due to the conditions of manufacture is accompanied by a substantially lower flux through the membrane.
Some particularly advantageous multicomponent membranes of this invention, for instance, those in which the porous separation membrane is an anisotropic hollow fiber, exhibit a greater permeability than an anisotropic hollow fiber membrane consisting of the material of the porous separation membrane, which membrane is capable of maintaining the configuration of the hollow fiber under gas separation conditions, e.g., absolute pressure differentials of at least about 10 kilograms per square centimeter, and which anisotropic hollow fiber membrane exhibits, with respect to at least one pair of gases, a separation factor equal to or greater than the separation factor of the multicomponent membrane.
Advantageously, the porous separation membrane is sufficiently thick that no special apparatus is required for its handling. Frequently, the porous separation membrane has a thickness of 20 to 500, say, 50 to 200, or 300 microns. When the multicomponent membrane is in the configuration of a hollow fiber, the fiber may often have an outside diameter of 200 to 1000, say, 200 to 800, microns and wall thicknesses of 50 to 200 or 300 microns.
In conducting gaseous separations, including concentrations, employing the multicomponent membranes of this invention the exit side of the multicomponent mebrane is maintained at a lower chemical potential for at least one permeating gas than the chemical potential at the feed side. The driving force for the desired permeation through the multicomponent membrane is a differential in chemical potential across the multicomponent membrane such as described by Olaf A.
Hougen and K. M. Watson in Chemical Process Principles, Part II, John Wiley, New York (1947), for instance, as provided by a differential in partial pressure.
Permeating gas passes into and through the multicomponent membrane and can be removed from the vicinity of the exit side of the multicomponent membrane to maintain the desired driving force for the permeating gas. The functionality of the multicomponent membrane does not depend upon the direction of gas flow or the surface of the membrane which is first contacted by a gaseous feed mixture.
In addition to providing a process for separating at least one gas from gaseous mixtures which does not require costly refrigeration and/or other costly energy inputs, the present invention provides numerous benefits with a high degree of flexibility in selective permeation operations. The multicomponent gas separation membranes, whether in sheet or hollow fiber form, are useful in the separation of industrial gases, oxygen enrichment for medical applications, pollution control devices, and any need where it is desired to separate at least one gas from gaseous mixtures. Relatively infrequently does a single component membrane possess both a reasonably high degree of selectivity of separation and good permeation rate characteristics, and even then these single component membranes are suitable for separating only a few specific gases. The multicomponent gas separation membranes according to the invention may employ a wide variety of materials for the porous separation membranes which previously have not been desirable as single component membranes for gas separation due to undesirable combinations of permeation rates and separation factor. Since the selection of the material of the porous separation membrane can be based on its selectivity and permeability constants for given gases rather than its ability to form thin and essentially porefree membranes, the multicomponent membranes of this invention can advantageously be tailored for separations of a wide variety of gases from gaseous mixtures.
MATHEMATICAL MODEL
The cross-sectional diameter of pores in a porous separation membrane may be on the order of Angstroms, and accordingly the pores of the porous separation membrane and the interface between the coating and the porous separation membrane are not directly observable employing presently available optical microscopes. Presently available techniques which can offer larger magnification of a specimen such as scanning electron microscopy and transmission electron microscopy, involve special specimen preparations which limit their viability in accurately depicting features of the specimen, particularly an organic specimen.
For instance, in scanning electron microscopy, an organic specimen is coated, e.g., with at least 40 or 50 Angstrom thick layer of gold, in order to produce the reflectance which provides the perceived image. Even the manner in which the coating is applied can affect the perceived image. Furthermore, the mere presence of the coating required for scanning electron microscopy can obscure, or apparently change, features of the specimen. Moreover, in both scanning electron microscopy and transmission electron microscopy the methods used for obtaining a sufficiently small portion of the specimen may substantially alter features of the specimen. Consequently, the complete structure of a multicomponent membrane can not be visually perceived, even with the best microscopic techniques available.
The multicomponent membranes of this invention do perform uniquely, and mathematical models can be developed which, as demonstrated by various techniques, generally correlate with the observed performance of a multicomponent membrane of this invention. The mathematical models, however, are not in limitation of the invention, but rather serve to further illustrate the benefits and advantages provided by the invention.
For a better understanding of the following mathematical model of multicomponent membranes of this invention, reference can be made to the depicted models provided as Figures 1,2, 3,4,6 and 7 of the drawings. The depicted models are only intended to facilitate the understanding of the concepts developed in the mathematical model and do not, and are not intended to depict actual structures of the multicomponent membranes of the invention. Furthermore, consistent with the purpose of assisting in understanding the concepts of the mathematical model, the depicted models illustrate the presence of features involved in the mathematical model; however, the depicted models are greatly exaggerated with respect to the relative relationships among these features in order to facilitate observing the features. Figure 5 is provided to assist in demonstrating the analogy between the concept of resistance to permeate flow of the mathematical model and resistance to electrical flow.
Figures 1, 2 and 4 are depicted models for purposes of understanding the mathematical model and illustrate an interface of coating and a porous separation membrane, i.e., an enlarged region, indicated in Figure 6 as that region between lines A-A and B-B, but not necessarily on the same scale. Figure 3 is an enlarged depicted model of the region indicated in Figure 7 as that region between lines C-C and D-D. In the depicted models, like designations refer to the same features.
Figure 1 is an enlarged cross-sectional view, for illustrative purposes, of one depicted model of an essentially continuous and non-interrupted overlay 1 of the material X of the coating in contact with material Y of a porous separation membrane with solid portions 2 having pores 3 filled or partially filled by the material of X;
Figure 2 is an enlarged illustration of another depicted model, wherein material Y of the porous separation membrane is in the form of curved surface interface areas either being void or partially filled with material X of the coating in a uniform contact, i.e., uninterrupted, fashion;
Figure 3 is an enlarged illustration of a depicted model having material X within pores 3, but no uninterrupted overlay 1 is present.
Figure 4 is still another depicted model to assist in describing concepts in accordance with the mathematical model of the invention. Figure 4 in cooperation with Figure 5 demonstrates an analogy with the well-known electrical current resistance circuit illustrated in Figure 5;
Figure 6 is yet another cross-sectional view of a depicted model in which material X of the coating is provided as a pore-blocking film cast on a denser surface of the porous separation membrane, which is characterized by a reciprocally graduated density and porous structure through the membrane thickness; and
Figure 7 is a cross-sectional view of a depicted model of an occluded anisotropaic separation membrane which does not of necessity require a continuous or uninterrupted overlay 1.
The following equations illustrate a mathematical model which has been developed to explain the observed performances of the multicomponent membranes of this invention. By appropriate use of this mathematical model, porous separation membranes and materials for coatings can be chosen which will provide advantageous multicomponent membranes of this invention.
As will be demonstrated below, the flux, QT.a, for gas a through a multicomponent membrane can be represented as a function of the resistance to flow of gas a through each portion (see, for instance the depicted model of Figure 4) of the multicomponent membrane by analogy to the mathematically equivalent electrical circuit of Figure 5.
where #pT.a is the pressure differential for gas a across the multicomponent membrane and R1a, R2.a, and R3.a represent the resistance to flow of gas a of the overlay 1, the solid portions 2 of the porous separation membrane, and the pores 3 of the porous separation-membrane, respectively. The flux, QT.b, of a second gas b through the same multicomponent membrane can be expressed In the same manner, but with the appropriate terms for the pressure differential of gas b and the resistances to flow of gas b through the overlay lithe solid portions 2 of the porous preparation membrane and the pores 3. Each of these resistances for gas b can be different than each of those for gas a. Thus selective permeation can be achieved by the multicomponent membrane. Advantageous multicomponent membranes can be modeled by varying R1, R2, and R3 relative to each other for each of gases a and b to produce desirable calculated fluxes for each of gases a and b, and by varying the resistances for gas a relative to those for gas b to provide a calculated selective permeation of gas a over gas b.
Other equations which are useful in understanding the mathematical model are listed below.
For any given separating material, the separation factor for two gases a and b, a:, is defined by Equation 2 for a membrane of material n of a given thickness I and surface area A: 2)
Pn.a Qa # Pb aba= =
Pn.b Qb # Pa where Pn.a and Pn.b are the respective permeability constants of material n for gases a and b, and Qa and Qb are respective fluxes of gases a and b through the membrane when #pa and #pb are the driving forces, i.e., partial pressure drops, for gases a and across the membrane. The flux Qa through a membrane of material n for gas a can be expressed as 3) #paPn.aAn #pa Qa = =
ln Rn.a where An is the surface area of the membranes of material n ln is the thickness of the membrane of material n, and Rn,a is defined for the purposes of the model as the resistance of a membrane of material n to the flow of gas a.
From Equation 3 it can be seen that the resistance Rn.a is represented mathematically by Equation 4.
4)
ln Rn.a =
Pn.a An This resistance is analogous in a mathematical sense to the electrical resistance of a material to current flow.
For the purposes of illustrating this mathematical model, reference can be made to the depicted model of, for instance, Figure 4. The porous separation membrane is represented as comprising solid portions 2 of material Y and pores, or holes 3. Material X is present in the depicted model of Figure 4 as overlay 1 and as the material which enters into the pores 3 of the porous separation membrane.
Each of these regions, the overlay 1, the solid portions 2 of the porous separation membrane, and the pores 3 containing material X, has a resistance to gas flow such that the total multicomponent membrane can be compared to the analogous electrical circuit represented in Figure 5, in which a resistance, to decrease the diffusion rate of gases through the pores.
Upon obtaining an estimation of the resistance to gas flow through the pores and having knowledge of the resistance to gas flow of the material of the porous separation membrane, the desired increase in resistance to gas flow through the pores necessary to provide a multicomponent membrane having a desired separation factor can be estimated. Conveniently, but not necessarily, it can be assumed that the depth of the material of the coating in the pores (13) and the distance (12) of minimum permeation of the gas through the material of the porous separation membrane are the same. Then, based on knowledge of the permeability constants of materials for coatings, a material for the coating can be selected to provide the desired resistance. The material for the coating can also be selected for other properties, in addition to increasing R3, as will be described below. If the material for the coating also forms an overlay on the porous separation membrane, as illustrated in Figure 4, it can decrease the flux. Such a situation is described according to the mathematical model by Equation 1. In such a case the properties of the material of the coating should also be such that the flux is not unduly reduced.
The selection of a material for the coating depends on its determined intrinsic separation factor relative to the determined intrinsic separation factor of the material of the porous separation membrane and its ability to provide the desired resistance in. the multicomponent membrane. The material of the coating should be capable of occluding contact with the porous separation membrane. Based on the average pore size of the porous separation membrane, materials for the coating of appropriate molecular size can be chosen. If the molecular size of the coating is too large, or if the coating material bridges the pores at the surface, the model provides that the resistance of the pores, R3, would not be increased relative to the resistance, R2, of the solid portions of the porous separation membrane, and in such a case, the proportion of gases permeating through the solid portions 2 relative to gases diffusing through the pores would not be increased with respect to that proportion in the porous separation membrane alone. If, on the other hand, the molecular size of the material of the coating is too small, it may be drawn through the pores during coating and/or separation operations.
Frequently, the coating is provided in the form of an overlay I (see the depicted model of Figure 4) in addition to the material of the coating which enters the pores. In these instances, the overlay I represents a resistance to gas flow, R, which is in series with the combined resistances of the porous separation membrane. When this situation occurs, the material of the coating should be advantageously selected such that the overlay in the multicomponent membrane will not provide too great a resistance to gas flow (while the coating still provides sufficient resistance in the pores), in order that the porous separation membrane substantially effects the separation of at least one pair of gases in the gaseous mixture. This might be accomplished, for example, by providing a material for the coating which exhibits high permeability constants for gases and low selectivity.
The thickness 1, of the overlay, as represented by the model, can also have some effect on the flux and selectivity exhibited by the multicomponent membrane, since the resistance (R,) of the overlay lisa function of its thickness 11.
If a suitable material X and a material Y have been chosen, various configurations of multicomponent membranes comprising these materials can be modeled, using Equations 1, 2, and 4. Information concerning, for example, more desirable ratios of total pore cross-sectional area (A3) to total surface area (A2 + A3) for the porous separation membrane and more desirable thicknesses for the separating layer 13 of the porous separation membrane can result from this mathematical modeling. This information may be useful, for example, in determining procedures for the production ofi the porous separation membranes having desirable area ratios, A,/(A3 + A3), and desirable separating thicknesses 12 as well as desirable overlay thicknesses 1,. In the case of anisotropic hollow fiber porous separation membranes, this might be accomplished by appropriate choice of spinning conditions and/or post-treatment conditions.
The above discussion is illustrative of the way in which various configurations of multicomponent membranes can be mathematically modeled. Several methods have been discussed for varying, with respect to at least one pair of gases, the relative resistances of the overlay I, the solid portions 2 and the pores 3 of the porous separation membrane to provide advantageous multicomponent membranes exhibiting high flux and high selectivity for at least one pair of gases.
The following is the mathematical derivation which, in combination with
Equations 3 and 4, will yield Equation 1.
From the well-known Ohm's law of electrical resistances a mathematical expression for the total resistance, RT, of the electrical circuit illustrated in Figure 5 can be obtained.
R2R3 5) RT=Rl +R23=R1 +
R2 + R3 where R23 is the combined resistance of R3 and R3 in parallel and is equal to the last term in Equation 5.
By analogy, the mathematical model described above utilizes this same mathematical equation to express the total resistance to flow of a given gas for a multicomponent membrane, as illustrated in an exaggerated way by the depicted model of Figure 4. The resistance, R23, represents the combined resistance of both portions of the porous separation membrane, the solid portions 2 and the pores 3 filled with material X. If the coating is not provided as an essentially continuous overlay 1, but only as material X which enters the pores 3, a situation illustrated in the depicted model of Figure 3, then the resistance of the overlay R1 is zero, and the term is dropped from Equation 5 and all subsequent equations derived from
Equation 5.
The total flux of a given gas a through the multicomponent membrane is equivalent to the current in electrical flow and, at steady state, is given by Equation 6.
6) QT.a = Q1.a = Q23.a where Q1.1 is the flux of gas a through the overlay 1, and Q23.a is the combined flux of gas a through both the solid portions 2 and pores 3 (filled with material X) of the porous separation membrane.
7) Q23.a = A2,a + Q3.a
The total partial pressure drop for gas a across the multicomponent membrane is the sum of the partial pressure drop across the overlay 1, #p1.a and the partial pressure drop across the solid portions 2 and the filled pores 3 of the porous separation membrane, #p23.a 8) #pt.a = #p1.a + #p23.a The flux of gas a through each portion of the multicomponent membrane can be expressed by Equation 3, using the resistances and partial pressure drops specific to each portion.
#p1.a 9) Q1,a =
R1,5 #23.a AP23,a(R2,a + R3.a) 10) Q23.a = =
R23.a R2.a R3.a
From Equations 6, 8, 9, and 10, an expression for #p23.a in terms of resistances and total partial pressure drop can be derived.
Equation 11, in combination with Equations 6 and 10, yield Equation 1.
In accordance with this invention a coating is in occluding contact with the porous separation membrane to provide a multicomponent membrane. This mathematical model, which has been developed to explain the phenomena exhibited by the multicomponent membranes of this invention, provides that pores 3 in the porous separation membrane contain material X. The resistance to gas flow, R3, of the pores containing material X is much greater than the resistance to gas flow of pores not filled with material X, since the permeability for gases of any material is much less than the permeability of an open flow channel. Accordingly,
R3 is increased in the multicomponent membrane, and with reference to Equation 10, R3 becomes more significant in affecting R33. Since R3 is increased relative to
R2 in the multicomponent membrane, an increased proportion of gas passes through the solid portions of the porous separation membrane as compared with that through pores 3 filled with material X than that proportion in the porous separation membrane alone. Consequently, the separation factor of at least one gas pair is enhanced in the multicomponent membrane by interaction with the material Y, as compared to that separation factor in the porous separation membrane alone.
The following examples are illustrative of the invention but are not in limitation thereof. All parts and percentages of gases are by volume, and all parts and percentages of liquids and solids are by weight, unless otherwise indicated.
Examples 1-3 Examples 1 through 3 in Table I represent multicomponent membranes comprised of cellulose acetate porous separation membranes and a coating.
Examples 2 and 3 show the same composite hollow fiber membranes separating two different gas mixtures. It is seen in these two examples that the porous substrate membrane separates both gas mixtures to some degree even in the absence of a coating, but in both cases the separation factor is much less than the determined intrinsic separation factor of the cellulose acetate. In such porous separation membranes most of the gas passes through the pores and relatively little permeate flow is through the cellulose acetate.
After coating, the separation factor for the gases exhibited by the multicomponent membranes of Examples 2 and 3 is greater than either the determined intrinsic separation factor of the coating material or the separation factor of the porous separation membrane. Thus, in the multicomponent membrane a greater proportion of the gas flow is through the cellulose acetate as compared with that through the pores; hence, the separation factor of the multicomponent membrane is much closer to the determined intrinsic separation factor of the cellulose acetate.
Example 1 shows a different sample of cellulose acetate hollow fiber with somewhat different coated and uncoated properties and can be compared to
Example 2. Although the porous separation membrane has a higher permeability for O3 and a lower separation factor, the multicomponent membrane exhibits a higher separation factor than each of the material of the coating and the porous separation membrane separately.
TABLE I.
Permeabilitya of oxygen from air and hydrogen from carbon monoxide/hydrogen mixtures through multicomponent membranes utilizing cellulose acetateb porous separation membranes.
Example No. 1 2 3
Coatingc Poly(dimethylsiloxane), Poy(dimethylsiloxane), Poly(dimethylsiloxane),
Dow Corning 200, Dow Corning 200, Dow Corning 200, viscosity = 100 cps viscosity = 100 cps viscosity = 100 cps
Coating Procedured A B B
Gas Feed Air Air CO/H2
Enriched Gas (permeate) O2 O2 H2
Coating Material Determined 2.33 2.33 1.9
Intrinsic Separation Factore (O2 over N2 or H2 over CO)
Porous Separation Membrane 5.9 x 10-6 4.4 x 10-6 2.7 x 10-5
Permeabilitya (O2 or H2)
Porous Separation Membrane 2.2 1.6 9.2
Separation Factore (O2 over N2 or H2 over CO)
Multicomponent Membrane 4.09 5.03 22.0
Separation Factore (O2 over N2 or H2 over CO)
Multicomponent Membrane 2.2 x 10-6 1.6 x 10-6 1.5 x 10-5
Permeabilitya (O2 or H2)
Cellulose Acetate Determined 5.9 5.9 ~50
Intrinsic Separation Factore (O2 over N2 or H2 over CO) Notes to Table I
(a) The permeability of the membrane to a given gas is the amount of gas (expressed
in cubic centimeters under normal temperature and pressure conditions) which has
passed through the said membrane, per square centimeter of surface area, per
second, for a partial pressure drop of 1 cm of mercury between the upstream and
downstream side of the membrane per unit of thickness. (Units of Permeability
- cm3/cmz-sec-cm Hg).
(b) Cellulose acetate (degree of substitution about 2.5) obtained from Eastman Kodak
and spun in accordance with OSW Final Report #14-30-3066, "Development of
High Flux Hollow Reverse Osmosis For Brackish Water Softening (1973)."
The fiber of Example 2 is post treated in warm water.
(c) All coatings are liquids when applied and are not further cured, polymerized, or
cross-linked after coating.
(d) The key to the coating procedure methods is listed (Table XVI) following the
examples.
(e) The separation factor of a membrane for a pair of gases is defined as the
permeability of the membrane for a first gas divided by the permeability for a
second gas of the pair
Examples 4-10 Examples 4 to 10 illustrate various liquid coatings on porous polysulfone
hollow fiber separation membranes for selectively separating oxygen from air and
are presented in Table II. The porous separation membranes do not separate
oxygen from nitrogen. The coating materials used are representative of high
molecular weight organic and silicone liquids which have sufficiently low vapor
pressures that they will not readily evaporate from the coated surface and have
separation factors for oxygen over nitrogen which are generally less than about 2.5.
The molecular sizes of the coatings are sufficiently small to provide occluding
contact with the porous separation membrane but are not unduly small such that
the coating material can pass through the pores under coating and/or separating
conditions. The observed separation factors for the multicomponent membranes
are greater than each of the separation factor of the porous separation membrane
(1.0 in all Examples) and the coating material (2.5 or less for the coating materials
of the Examples).
TABLE II.
Permeabilitiesa of O2 from air feed through multicomponent membrane utilizing polysulfoned porous separation membranes and liquid coatings.
Example No. 4 5 6 7 8 9 10
Coating c,f Poly (trifluoro- Hexadecane Dow Corning Dow Corning Squalane Raw Polystyrene propyl methyl- Poly(phenyl- Sylgard 51, (isoprene Linseed (degree of siloxane) methyl sil- silicone prepolymer) Oil polymerization oxane) rubber = 2.9) prepolymer
Coating Procedured A A A C A A B
Porous Separation Membrane 1.8 x 10-4 2.5 x 10-4 7.4 x 10-4 1.8 x 10-4 9.2 x 10-4 2.3 x 10-4 9.5 x 10-4
Permeabilitya (Air)
Porous Separation Membrane 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Separation Factor e,g (O2/N2)
Multicomponent Membrane 4.1 4.0 4.4 4.0 4.1 4.5 4.8
Separation Factore (O2/N2)
Multicomponent Membrane 9.4 x 10-6 6.5 x 10-6 4.9 x 10-6 1.0 x 10-5 6.1 x 10-6 7.0 x 10-6 2.5 x 10-6
Permeabilitya (O2) (a) As in Table I. (b) Polysulfone, Union Carbide, P-3500, and unless otherwise indicated, the polysulfone in following Examples is P-3500.
(c) All coatings are liquids when applied and are not further cured, polymerized or cross-linked after coating. (d) As in Table I. (e) As in
Table I. (f) Measurement of separation factors through liquids is difficult but it is believed that the determined intrinsic separation factors of the coating materials is below about 2.5 for O2/N2. In Example 5 the liquid coating separation factor was measured as about 2. In all other examples, similar materials, when polymerized or as liquids, are reported in the literature to have determined intrinsic separation factors ranging from 2.0-2.4. (g) The determined intrinsic separation factor for O2/N2 for polysulfone is about 6.0 as measured from compact non-porous films.
Examples 11-15
Examples 11 to 15 illustrate various coatings which are either applied to the porous separation membranes as liquids and reacted in place to become solid polymer coatings (post-vulcanized) or are applied as normally solid polymers dissolved in a solvent. The results are reported in Table III. In the Examples oxygen is enriched from an air feed by the multicomponent membrane, and a variety of treated polysulfone hollow fiber porous separation membranes is utilized.
TABLE III
Permeabilitiesa of O2 from air feed, through multicomponent membranes utilizing polysulfoneb porous separation membranes and polymerized coatings.
Example No. 11 12 13 14 15
Coating Dow Corning Dow Corning Poly(cis-1, Dow Corning Dow Corning
Sylgard 184, Sylgard 185, 4-isoprene) Sylgard 184 Sylgard 184, post-vulcanized post-vulcanized post-vulcanized post-vulcanized silicone rubber silicone rubber silicone rubber silicone rubber
Coating Procedurec E E D F F
Coating Material 2.3 2.3 2.5-2.7 2.3 2.3
Determined Intrinsic
Separation Factord
Porous Separation 1.8 x 10-4 1.8 x 10-4 6.2 x 10-4 2.1 x 10-4 1.2 x 10-5
Membrane Permeabilitya (Air)
Porous Separation 1.0 1.0 1.0 1.0 about 1
Membrane Separation
Factord,e (O2 over N2)
Multicomponent Membrane 4.8 3.4 4.6 5.9 5.4
Separation Factord (O2 over N2)
Multicomponent Membrane 1.2 x 10-5 1.4 x 10-5 5.8 x 10-6 8.9 x 10-6 9.7 x 10-6
Permeabilitya (O2) (a) As in Table I (b) As in Table II (c) As footnote d in Table I (d) As footnote e in Table I (e) As footnote g in Table II Examples 16-18 Examples 16, 17 and 18 show that the multicomponent membranes utilizing polysulfone hollow fiber porous separation membranes can also effectively separate H2 from CO/H2 mixtures according to the invention. The porous separation membrane separation factor was not measured prior to coating for
Examples 16 and 18, but numerous experiments with similar porous separation membranes indicate that the separation factors can be expected to be between about 1.3 and about 2.5. This expectation is verified in Example 17, where the porous separation membrane separation factor for H3 over CO was measured as 1.3. These porous separation membranes thus exhibit some separation between H2 and CO due to Knudsen diffusion. These examples illustrate the use of different coatings, coating procedures, permeabilities and separation factors of the multicomponent and porous separation membranes in providing the multicomponent membranes of the invention. Examples 14 and 17 and Examples 15 and 18 are carried out with the same multicomponent mebrane and comparison of these examples shows that use of a multicomponent membrane for one separation or with one mixture of gases will not prevent it from later functioning with another set of gases. The Examples are reported in Table IV.
TABLE IV
Permeabilitiesa of H2 from CO/H2 mixtures through multicomponent membranes utilizing polysulfoneb porous separation membranes.
Example No. 16 17 18
Coating poly(cis-1,4-isoprene) Dow Corning Sylgard Dow Corning Sylgard 184 post-vulcanized 184 post-vulcanized silicone rubber silicone rubber
Coating Procedurec D F F
Coating Material 3.5 1.9 1.9
Determined Intrinsic
Separation Factord (H2/CO)
Porous Separation Membrane - 9 x 10-5
Permeabilitya (H2)
Multicomponent Membrane 15.4 30.2 31
Separation Factord,e (H2/CO)
Multicomponent Membrane 3.4 x 10-5 5.9 x 10-5 6.0 x 10-5
Permeabilitya (H2) (a) As in Table I.
(b) As in Table II, (c) As footnote d in Table I.
(d) As footnote e in Table I, (e) Polysulfone has a determined intrinsic separation factor of about 40 for H2 over CO, when measured as a continuous compact film.
Examples 19-21 Examples 19, 20, and 21 (Table V) show permeation properties of multicomponent membranes composed of various coating materials on porous hollow fiber copoly(styrene-acrylonitrile) separation membranes for air and CO/H2 separtion. In each example, the multicomponent membrane has a higher separation factor than each of the coating and the porous separation membrane alone. Example 21 demonstrates a porous separation membrane which exhibits a separation factor for H2 over CO of 15 before applying the coating. i.e., there are relatively few pores in the porous separation membrane and the average pore diameter may be small. A comparison of Examples 20 and 21 shows that the multicomponent membrane of Example 20 has a higher permeation rate and a higher separation factor than the porous separation membrane of Example 21, even though that membrane has a greater separation factor than that of the porous separation membrane of Example 20. Thus multicomponent membranes in accordance with the invention can have a superior rate of permeation than a membrane of equal or greater separation factor consisting essentially of the material of the porous separation membrane.
TABLE V:
Permeabilitya of H2 from CO/H2 mixtures and O2 from air through multicomponent membranes employing copoly(styrene-acrylonitrile) porous separation membranese
Example No. 19 20 21
Coating Dow Corning Poly(dimethyl siloxane) Poly(dimethyl siloxane),
Sylgard 184 Dow Corning 200-viscosity Dow Corning 200-viscosity post-vulcanized = 100 cps = 100 cps silicone rubber
Coating Procedureb F B B
Gas Feed Air H2/CO H2/CO
Enriched Gas (Permeate) O2 H2 H2
Coating Material Determined 2.3 1.9 1.9
Intrinsic Separation Factorc (O2/N2 or H2/CO)
Porous Separation Membrane 6.5 x 10-6 6.5 x 10-5 5.6 x 10-6
Permeabilitya (Air of H2)
Porous Separation Membrane 1.0 3.9 15
Separation Factorc (O2/N2 or H2/Co)
Multicomponent Membrane Separation 3.8 25 45
Factorc (O2/N2 or H2/CO)
Multicomponent Membrane Permeabilitya 3.4 x 10-6 6.2 x 10-6 2.3 x 10-6 (O2 or H2)
Determined Intrinsic Separation 7.0 80. 80.
Factord of Material of Porous
Separation Membrane (a) As in Table I.
(b) As footnote d in Table I.
(c) As footnote e in Table I.
(d) The determined intrinsic separation factor of the substrate is the separation factor exhibited by a continuous compact film composed of the material.
(e) 33% acrylonitrile-67% styrene copolymers, Ex. 20 and 21 of higher molecular weight than Ext. 19, all spun in hollow fiber form from a 27.5% solids dope in dimethylformamide into a water coagulant at 0-10 C.
Example 22
A five component gas stream is utilized as the feed to a multicomponent membrane of Examples 15 and 18. The feed stream is comprised of hydrogen, carbon dioxide, carbon monoxide, nitrogen, and methane with amounts of water and methanol up to saturation values. The feed stream at 4.5 kg/cm2 pressure and at a temperature of 40"C, is introduced to the shell side of the multicomponent membrane. The bore pressure is one atmosphere. The following gas permeabilities and separation factors relative to hydrogen are observed:
Permeability* For: Separation Factor, H2 over
H2(.5 x 10-B) CO2(3.7 x 10-B) CO2 2.3 CO(.27x 10-B) CO 31.0 N2(.68 x 10-6) N2 12.4
CH4 (.23 x loB) CH4 36.9
*in cm3(STP)/cm2-sec-cm Hg.
It is clear in this example that the separation of hydrogen from gaseous mixtures containing at least one of CO, N2 and CH4 can be easily effected. The presence of one or more additional gases in the gaseous mixture, such as saturated water and methanol vapor, apparently does not hinder the multicomponent membrane from effecting the separation. Also it is clear that various of the other gases in the mixture can be separated from each other, e.g., the separation factor for CO2 over CO would be the ratios of permeabilities, i.e., about 14. Example 22 also illustrates the effect of the Porous separation membrane in providing the relative permeation rates through the multicomponent membrane. Thus, the coating material (Sylgard 184) exhibits a determined intrinsic separation factor of about 0.3 to 0.4 for H2 over CO2 (i.e., CO2 is faster than H2), yet the multicomponent membrane exhibits a separation factor of 2.3 for H2 over CO2.
This value is essentially equal, within experimental error, to the determined intrinsic separation factor of the polysulfone for H2 over CO2.
Example 23
Example 23 (Table VI) shows the permeabilities (P/I) for a number of gases through a-multicomponent membrane utilizing a hollow fiber polysulfone porous separation membrane. Example 23 shows the same values for the same gases through a continuous compact film of the polysulfone material. The ratio of any two P or P/I values defines an approximate separation factor for those gases through the compact film or the multicomponent membrane, respectively. The
Example illustrates a clear trend in that the permeabilities for the multicomponent membrane generally vary from gas to gas in the same order as those for the polysulfone compact film. This trend indicates that the material of the porous separation membrane is providing a significant portion of the separation exhibited by the multicomponent membrane. This example also shows that a multicomponent membrane may be used to separate any of a number of gases from each other. For example, from the table it is seen that NH2 could be readily separated from H2 or N2, He from CH4, N2O from N2, O2 from N2, or H2S from CH4, using this multicomponent membrane. The advantage of high permeation rates of the multicomponent membranes is indicated by the data represented in Table VI.
TABLE VI.
Permeabilitiesa of fixed gases throughaulticomponent membrane utilizing poly
sulfone porous separation membrane and compact polysulfone0 film.
Example 23
Multicomponent Membraneb Polysulfonec Continuous Compact Film
Gas P /I(x 106)a P (x l01l)a NH3 210 530
H2 55 130*
He 55 50 N20 45 82
CO2 38 69
H2S 31 31 O2 8.3 11
Ar 3.3 4.5
CH4 2.3 2.5
CO 2.4 3.2
N2 1.4 1.8
C2H4 1.7 2.2
(a) Permeabilities for the multicomponent membrane are P/i values and have units
described in footnote a in Table I. Permeabilities for the polysulfone film are
P values, since the I or thickness of the compact film is easily measured. The
units of P are cc (STP)-cm/cm2-sec cmHg.
*(b) The multicomponent membrane in this example is comprised of a Dow Sylgard 184
post-vulcanized silicone rubber coated on a porous polysulfone separation membrane
such as in Example 15 using coating procedure F in Table XVI.
(c) As footnote b in Table II.
* A different compact film employed for determination of H2 permeability than that used
for the determination of the permeabilities of the other gases.
Comparative Examples 24 to 26
(not in accordance with the invention)
Examples 24 through 26 are reported in Table VII and illustrate that not all
composite membranes will fall within the scope of the invention, i.e., provide a
multicomponent membrane exhibiting a separation factor significantly greater than
the determined intrinsic separation factor of the coating material, even though they
are comprised of porous separation membranes and coating materials each of
which may be employed with other coating materials or porous separation
membranes to provide multicomponent membranes in accordance with this
invention.
Example 24 provides a multicomponent membrane having a pre-vulcanized
silicone rubber coating on a porous polysulfone separation membrane. Since the
pre-vulcanized silicone rubber may have too large molecular dimensions to be
expected to occlude the pores in accordance with the model, e.g., the molecules
can only bridge the pores, the coating will not alter the resistance of the pores to
gas flow. In Example 24, the coating compound is a pre-vulcanized polymer with
the same essential polymeric backbone as the Sylgard 184 illustrated, for instance,
in Examples 11, 14 and 15 in Table III. However, the pre-vulcanized silicone rubber has a much higher molecular weight and size due to pre-vulcanization than does
Sylgard 184, and thus apparently cannot fill the pores, and consequently the composite membrane exhibits a separation factor equal (within experimental error) to that of the coating material.
Example 25 illustrates a multicomponent membrane wherein Sylgard 184 is used as the coating material and a porous polyacrylonitrile separation membrane is utilized. ("Sylgard" is a registered Trade Mark). Polyacrylonitrile exhibits a very low permeability for gases when in continuous, non-porous form. With reference to the model, such a porous separation membrane will have a very high resistance to flow through the solid portions thereof, such that when a coating material of high permeability such as Sylgard 184 is in occluding contact therewith, the gas flow occurs predominantly through the coating and the plugged ores, and thus the multicomponent membrane exhibits a separation factor which is equal to or less than that of the coating membrane.
A multicomponent membrane which is illustrated in Example 26 exhibits a separation factor that is lower than the determined intrinsic separation factor of the coating material. This situation is similar to that of Example 24 in that the poly(vinylbutyral) used as the coating material has a high molecular weight. In addition, it does not wet polysulfone as well as many silicones and other preferred coatings. Moreover, the poly(vinylbutyral) has a relatively low permeability. The observation that the separation factor exhibited by the multicomponent membrane is less than that expected of the coating material suggests imperfections in the coating itself.
TABLE VII (not in accordance with the invention)
EXAMPLE 24
General Electric 4164
Coating Pre-vulcanized Silicone Rubber
Porous Hollow Fiber Membrane Polysulfone P-3500 Union Carbide
Gas Feed Air
Enriched Gas (Permeate) O2 Coating Procedurea E
Coating Material
Determined Intrinsic
Separation Factorb O2 over N2 1.7
Porous Separation
Membrane Permeability" For Air 1.8 x 10-4
Porous Separation
Membrane Separation Factorb O2 over N2 1.0
Multicomponent Membrane
Separation Factorb O2 over N2 1.61
Multicomponent Membrane
Permeability" For O2 4.1 x 10-5 TABLE VII- Continued EXAMPLE 25.
Dow Corning Sylgard 184
Coating post-vulcanized Silicone Rubber
Porous Hollow Fiber Membrane Polyacrylonitrile
Gas Feed Air
Enriched Gas (Permeate) O2 Coating Procedure' F
Coating Material
Determined Intrinsic Separation
Factorb O2 over N2 2.3
Porous Separation Membrane Permeabilityc For Air 2 x 10-3
Porous Separation Membrane
Separation Factorb O2 over N2 1.0
Multicomponent Membrane
Separation Factorb O2 over N2 1.9
Multicomponent Membrane Permeabilitye For O2 1.7 x 10-5 EXAMPLE 26.
Coating Poly-(vinylbutyral)
Porous Hollow Fiber Membrane Polysulfone P-3500 Union Carbide
Gas Feed Air
Enriched Gas (Permeate) o2 Coating Procedure' C
Coating Material
Determined Intrinsic Separation
Factorb O2 over N2 4.7
Porous Separation
Membrane Permeability" For Air 1.8 x 10-4
Porous Separation Membrane
Separation Factorb O2 over N2 1.0
Multicomponent Membrane
Separation Factorb O2 over N2 4.0
Multicomponent Membrane
Permeabilityc For 02 1.4 x 10-B (a) As footnote d in Table I.
(b) As footnote e in Table I.
(c) As footnote a in Table I.
EXAMPLES 27-34.
Examples 27 through 34 are reported in Table VIII and illustrate a series of porous separation membrane post-spinning treatments and the way in which these treatments affect the separation properties of multicomponent membranes made from such post-treated porous separation membranes. In Table VIII the coating material and the method of application are essentially the same in order to emphasize that changes in the permeation rate and separation factor of the multicomponent membranes (for both air and CO/H2 gas mixture feed) are apparently due to changes in the relatively dense regions of the porous separation membrane. The treatments are believed to affect the available pore cross-sectional area (A3) relative to total surface area (A2 + A3) of porous separation membrane. A decrease in A3 relative to the total surface area will cause an increase in the relative resistance to flow through the pores in the porous separation and multicomponent membranes. This, in turn, will force more of the permeate gas to flow through the porous separation membrane material, and the separation factor exhibited by the multicomponent membrane will move closer to the intrinsic separation factor of the material of the porous separation membrane.
In all of the examples in Table VIII, the porous separation membrane utilized is a porous hollow fiber membrane of polysulfone (Union Carbide, P-3500) from the same bobbin, which was wet-spun from a dope of 25% solids in dimethylformamide solvent into a coagulant of water at approximately 3"C through a tubein-oriffice jet through which water was injected to the bore and the fiber taken up at a speed of 21.4 mpm. The porous separation membrane used in each example is stored in deionized water at room temperature after spinning until the posttreatment process is applied.
TABLE VIII.
Examples 27 through 34
Hollow Fiber Membrane Post Treatment
The multicomponent membranes of Examples 27 to 34 utilize a coating of
Dow Corning Sylgard 184 post-vulcanized silicone rubber following coating procedure F as in Table XVI. Post treatment was performed on the hollow fiber membrane after spinning but before the coating was applied.
EXAMPLE 27.
Post Treatment Air evaporation of the water
Gas Feed Air
Enriched Gas (Permeate) O3 Multicomponent Membrane
Permeabilitya For O2 1.5 x 10-5 Multicomponent Membrane
Separation Factorb O2 over N2 4.7
Post-treated Porous Separation
Membrane Permeability" For air 3.7 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb O2 over N2 1.0
EXAMPLE 28.
Post Treatment Air evaporation of the water
Gas Feed CO,
H2
Enriched Gas (Permeate) H2
Multicomponent Membrane
Permeability5 For H2 7.6 x 10-5
EXAMPLE 28-Continued Multicomponent Membrane
Separation Factorb H2 over CO 23.1
Post-treated Porous Separation
Membrane Permeability' For H2 2.0 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb H2 over CO 2.6 EXAMPLE 29.
Post Treatment Air evaporation of the water; followed
by exposure to acetone vapor at 250C
with bore vacuum; followed by
alternating water immersion and
methanol immersion with bore vacuum
(3 cycles); followed by alternating
water immersion and isopropyl alcohol
immersion (2 cycles).
Gas Feed Air
Enriched Gas (Permeate) O2
Multicomponent Membrane
Permeabilitya For 027.7 x 10-a Multicomponent Membrane
Separation Factorb O2 over N25.3
Post-treated Porous Separation
Membrane Permeability' For 023.5 x 10-5 Post-treated Porous Separation
Membrane Separation Factorb O2 over N2 1.0 EXAMPLE 30.
Post Treatment Air evaporation of the water; followed
by exposure to acetone vapor at 250C
with bore vacuum; followed by
alternating water immersion and
methanol immersion with bore vacuum
(3 cycles); followed by alternating
water immersion and isopropyl alcohol
immersion (2 cycles).
Gas Feed CO,
H2
Enriched Gas (Permeate) H2
Multicomponent Membrane
Permeabilitya For H2 4.5 x 10-5
Multicomponent Membraneb
Separation Factor H2 over CO 30.4
EXAMPLE 30 -- Continued Post-treated Porous Separation
Membrane Permeability" For H2 1.5 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb H2 over CO 5.1
EXAMPLE 31.
Post Treatment Air evaporation of the water; followed
by heating in hot air oven to 80-950 for approximately 3 hours.
Gas Feed Air
Enriched Gas (Permeate) O2 Multicomponent Membrane
Permeabilitya For O2 1.6 x 10-5 Multicomponent Membrane
Separation Factorb O2 over N2 5.0
Post-treated Porous Separation
Membrane Permeability" For air 3.7 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb O2 over N2 1.0
EXAMPLE 32.
Post Treatment Air evaporation of the water; followed
by heating in hot air oven to 80-950 for approximately 3 hours.
Gas Feed CO,
H2
Enriched Gas (Permeate) H2
Multicomponent Membrane
Permeabilitya For H2 9.8 x 10-5
Multicomponent Membrane
Separation Factorb H2 over CO 23
Post-treated Porous Separation
Membrane Permeability" For H2 2.5 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb H2 over CO -1.3 EXAMPLE 33.
Post Treatment Dry by exchanging water with isopropyl
alcohol; followed by exchanging the
isopropyl alcohol with pentane;
followed by air evaporation of the
pentane
Gas Feed Air
Enriched Gas (Permeate) O2
EXAMPLE 33 - Continued
Multicomponent Membrane
Permeabilitya For O2 2.0 x 10-5
Multicomponent Membrane
Separation Factorb O2 over N2 4.2
Post-treated Porous Separation
Membrane Permeabilitye For air 1.5 x 10-3
Post-treated Porous Separation
Membrane Separation Factorb O2 over N2 1.0
EXAMPLE 34.
Post Treatment Dry by exchanging water with isopropyl
alcohol; followed by exchanging the
isopropyl alcohol with pentane;
followed by air evaporation of the
pentane
Gas Feed CO,
H2
Enriched Gas (Permeate) H2
Multicomponent Membrane
Permeabilitya For H2 1.2 x 10-4
Multicomponent Membrane
Separation Factorb H2 over CO 15.9
Post-treated Porous Separation
Membrane Permeabilitya For H2 2.5 x 10-4
Post-treated Porous Separation
Membrane Separation Factorb H2 over CO -1.3 (a) As footnote a in Table I.
(b) As footnote e in Table I.
EXAMPLES 35-39.
Examples 35 to 39 reported in Table IX illustrate the effect which additives in the coating material have on the separation factor of a multicomponent membrane for two gas mixture feedstreams (air and CO/H2). These additives are incorporated into the coating material in small amounts before the coating is applied to the porous separation membrane. Such additives can change the separating properties of the multicomponent membranes, for example, by changing the wetting properties of the coating material and thereby affecting its ability to be in occluding contact with the porous separation membrane. If the additive enhances occluding contact the separation factor of a multicomponent membrane with such an additive is expected to be closer to the intrinsic separation factor of the porous separation membrane material than the separation factor of a similar multicomponent membrane without such an additive.
The porous separation membrane hollow fibers utilized in Examples 35 to 39 were all from the same bobbin and were made of polysulfone (P-3500) in a highly porous form (see footnote a), by spinning according to the same procedure as the hollow fibers of Examples 27-34. The determined intrinsic separation factor of polysulfone for O2 over N2 from an air feed is about 6.0 and for H2 over CO from a
CO/H2 mixture is about 40.
TABLE IX.
Effect of additives in the coating material on the separation factor of the multicomponent membranea.
Example No. 35 36 37 38e 39e
Coating poly(dimethyl- poly(dimethyl- poly(dimethyl- Dow Corning Dow Corning siloxane) Dow siloxane) Dow siloxane) Dow RTV 3144 pre- RTV 3144 pre
Corning 200 Corning 200 Corning 200 vulcanized vulcanized silicone rubber silicone rubber
Additive to coating materialb - 0.2% galvinoxyl 0.4% phenan- - 4.3% Dow Corning thene Sylgard 184 curing radicald agent (silicone prepolymer)
Multicomponent Membrane 3.0 to 3.3 4.9 4.8 3.9 4.5
Separation Factorc (O2 over N2)
Multicomponent Membrane 3.8 16.5 10.7 14.6 20.5
Separation Factorc (H2 over CO) a) All multicomponent membranes in Examples 35-39 are composed of polysulfone (Union Carbide, 3500) separation membranes and are highly porous before applying the coating. b) All percentages are by weight. c. As footnote e in Table 1. d. Galvinoxyl radical obtained e. Both silicone rubber from Aldrich Chemical. compositions have
Structure listed below. determined intrinsic
r -ct Cd o CZNU dc3 OC I u C(CH3)a C(C3 for 02 and N2 and 1.1 .McHŏ for H2 over CO.
C(CHs)a c(cH3)3 EXAMPLES 40-43.
Examples 40 to 43 in Table X illustrate multicomponent membranes in which the porous separation membranes are prepared under different spinning conditions. The multicomponent membranes of Examples 40 to 43 employ a Dow
Corning Sylgard 184 post-vulcanized silicone rubber coating (Coating Procedure F,
Table XVI) on porous polysulfone (Union Carbide, P-3500) separation membranes. The porous polysulfone hollow fiber substrate membranes are wet jet spun from the indicated dopes into a water coagulant at the indicated temperature and spinning rate by means of a hollow spinnerette having an orifice to provide for injection of coagulant into the fiber bore as formed. The range of permeabilities (02 and H2) and separation factors of the multicomponent membranes (02 over N2 and H2 over CO) exhibited in Examples 40 to 43 for either air feed or CO/H2 mixture feed can be related to the variability in relative resistances of the pores and material of the porous separation membranes to gas flow. The conditions under which the porous substrate material is spun determine to a great extent the porosity characteristics and the effective separating thickness which that substrate will possess. In addition, these characteristics can be altered with post-spinning treatments of the porous substrate (see Examples 27 to 34).
TABLE X.
Spinning Conditions for P-3500 Polysulfone
Hollow Fiber Porous Separation Membranes
EXAMPLE 40.
Solvent Dimethylformamide
Coagulation
Temp. "C 3 Spin Rate, mpm 21.4 mpm
Dope Concentration-wt. % polymer 25%
Multicomponent Membrane
Separation Factor, O2 over N2b 4.5
Permeability for O28 7.7 x 10-B Multicomponent Membrane
Separation Factor, H2 over COb 16.7
Permeability for H2a 5.0 x 10-5
Porous Separation Membrane
Permeability" for Air 6 x 10-4
EXAMPLE 41.
Solvent Dimethylformamide
Coagulation
Temp. "C 5 Spin Rate, mpm 21.4 mpm
Dope Concentration-wt. % polymer 25%
Multicomponent Membrane
Separation Factor, O2 over N2b 5.09
Permeability for O2a 6.2 x 10-B TABLE X - Continued
Multicomponent Membrane
Separation Factor, H2 over COb 25
Permeability for H25 4.9 x 10-5
Porous Separation Membrane
Permeabilitya for Air 9 x 10-4
EXAMPLE 42.
Solvent Dimethylformamide
Coagulation
Temp. C 4
Spin Rate, mpm 33 mpm
Dope Concentration-wt. % polymer 28%
Multicomponent Membrane
Separation Factor, 02 over N2b 5.9
Permeability for O2 8.0 x 10-6 Multicomponent Membrane
Separation Factor, H2 over COb 30
Permeability for H25 5.9 x 10-5 Porous Separation Membrane
Permeability" for Air 2 x 10-4
EXAMPLE 43.
Solvent Dimethylacetamide
Coagulation
Temp. C 5
Spin Rate, mpm 33 mpm
Dope Concentration-wt. % polymer 27%
Multicomponent Membrane
Separation Factor, O2 over N2b 5.6
Permeability for O2 6.0 x 10-B Multicomponent Membrane
Separation Factor, H2 over COb 27
Permeabilitya for H2 3.8 x 10-5 Porous Separation Membrane
Permeability" for Air 4.5 x 10-4
a) As in Table I
b) As footnote e in Table I
EXAMPLES 44-51.
Examples 44 to 47 in Table XI illustrate multicomponent membranes wherein the porous separation membrane is in the form of an anisotropic film comprising an acrylonitrile/styrene copolymer having a determined intrinsic separation factor for
H2 over CO of 76. The films had been cast from solvents comprising dimethylformamide and non-solvents as indicated in the Table onto a plate, desolvated in air for 5--45 seconds, coagulated as indicated below then submerged in water at 25"C to wash, removed and dried. Examples 48 to 51 illustrate multicomponent membranes in the form of films which are dense. These examples illustrate multicomponent membranes according to the invention which are in the form of films, and may include porous separation membranes that have coatings on both surfaces.
TABLE XI.
Multicomponent Membranes in Film Form
EXAMPLE 44.
Dow Corning Sylgard 184
Coating post-vulcanized silicone rubber
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 32%/68% by weightc
Gas Feed H2,CO
Coating Procedures B
Coating Material Determined
Intrinsic Separation Factorb
H2 over CO 1.9
Porous Separation Membrane
Separation Factorb H2 over CO 13
Multicomponent Membrane
Separation Factorb, H2 34.8
EXAMPLE 45.
Dow Corning 200 poly(dimethyl
Coating siloxane)
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 32%/68% by weight
Gas Feed H2, CO
Coating Procedures B
Coating Material Determined
Intrinsic Separation Factorb
H2 over CO 1.9
Porous Separation Membrane
Separation Factorb H2 over CO 12.2
Multicomponent Membrane
Separation Factorb H2 over CO 23.8
TABLE Xl -Continued EXAMPLE 46.
Dow Corning Sylgard 184 vulcanized
Coating Silicone Rubber
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 32%/68% by weight
Gas Feed H2, CO
Coating Procedure B
Coating Material Determined
Intrinsic Separator Factorb
H2 over CO 1.9
Porous Separation Membrane
Separation Factorb H2 over CO 4.0
Multicomponent Membrane
Separation Factorb H2 over CO 23.5
EXAMPLE 47.
Dow Corning 200 poly(dimethyl
Coating siloxane)
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 32%/68% by weight
Dow Corning 200 poly(dimethyl
Coating siloxane)
Gas Feed H2, CO
Coating Procedurea B
Coating Material Determined
Intrinsic Separation Factorb
H2 over CO 1.9
Porous Separation Membrane
Separation Factorb H2 over CO 3.4
Multicomponent Membrane
Coating on One Side
Separation Factorb, H2 over CO 7.6
Multicomponent Membrane
Coating on Both Sides
Separation Factorb, H2 over CO 34
a) As explained in Table XVI
b) As footnote e in Table I
c) Coagulated in 50/50 by volume ethylene glycol/water for 30 min. at 250C
d) Coagulated in 90/10 by volume isopropyl alcohol/water for 30 min. at 250C
e) Coagulated in 10/90 by volume isopropyl alcohol/water for 30 min. at 250C
f) Coagulated in water at 250C
TABLE XI - Continued EXAMPLE 48.
Dow Corning Sylgard 184
Coating post-vulcanized silicone rubber
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 25%/75% by weight
Gas Feed Air
Enriched Gas (Permeate) O2
Coating Procedurea E
Coating Material Determined
Intrinsic Separation Factorb 2.3
Porous Separation Membrane
Separation Factorb O2 over N2 3.6
Multicomponent Membrane
Separation Factorb O2 over N2 5.4
EXAMPLE 49.
Dow Corning 200 poly(dimethyl
Coating siloxane)
Polyblend of two acrylonitrile/styrene
Porous Separation Membrane copolymers
Gas Feed Air
Enriched Gas (Permeate) O2 Coating Procedurea A
Coating Material Determined
Intrinsic Separation Factor 2.3
Porous Separation Membrane
Separation Factorb O2 over N2 4.9
Multicomponent Membrane
Separation Factorb O2 over N2 6.1
TABLE XI - Continued EXAMPLE 50.
Dow Corning 200 poly(dimethyl
Coating siloxane)
Copoly(acryionitrile/styrene) 32%/68% by weight, suspension
Porous Separation Membrane polymerized
Gas Feed Air
Enriched Gas (Permeate) O2
Coating Procedurea A
Coating Material Determined
Intrinsic Separation Factorb 2.3
Porous Separation Membrane
Separation Factorb O2 over N2 1.0
Multicomponent Membrane
Separation Factorb O2 over N2 6.3
EXAMPLE 51.
Dow Corning 200 poly(dimethyl
Coating siloxane)
Copoly(acrylonitrile/styrene)
Porous Separation Membrane 32%/68% by weight, mass polymerized
Gas Feed Air
Enriched Gas (Permeate) O2 Coating Procedure5 A
Coating Material Determined
Intrinsic Separation Factorb 2.3
Porous Separation Membrane
Separation Factorb O2 over N2 3.6
Multicomponent Membrane
Separation Factorb O2 over N2 4.9
a) As explained in Table XVI
b) As footnote e in Table I
EXAMPLES 52-57.
Examples 52 through 57 illustrate several multicomponent membranes in hollow fiber form. The porous hollow fibers can be produced by wet-spinning as generally described above. The polycarbonate fiber of Examples 52 and 53 was wet-jet spun from a dope of 27.5 wt. percent polycarbonate in N-methylpyrrolidone into a water coagulant at 250C at a rate of 21.4 mpm. The polysulfone hollow fiber of Example 54 was spun from a dope of 27.5 wt. percent polysulfone (P-3500) in a mixed 80/20 dimethylacetamide/acetone solvent into a water coagulant at 2"C at a rate of 21.4 mpm. The acrylonitrile-styrene copolymer fiber of Example 55 was spun from a dope of 27.5 wt. percent copolymer in a mixed solvent of 80/20 dimethylformamide/formamide into a water coagulant at 30C at a rate of 21.4 mpm. The acrylonitrile-styrene copolymer fiber of Examples 56 and 57 was spun from a dope of 25 wt. percent copolymer in the same mixed solvent as in Example 55 into a water coagulant at about 20 C at a rate of 21.4 mpm. The results of testing the multicomponent hollow fibres in separating a hydrogen/carbon monoxide gas mixture are set out in Table XII below.
TABLE XII
Example No. 52 53 54 55 56 57
Dow Corning Dow Corning Dow Corning Dow Corning Dow Corning Dow Corning
Sylgard 184 X-4258 X-4258 Sylgard 184 Sylgard 184 Sylgard 184 post-vulcan- α-methyl α-methyl post-vulcan- post-vulcan- post-vulcanized silicone styrene/di- styrene/di- ized silicone ized silicone ized silicone rubber methylsilo- methylsilo- rubber rubber rubber xane block xane block
G.E. Lexan 151 copolymer copolymer 33/67 Acrylo- VHAN Copoly- VHAN Copoly
Polycarbonate nitrile/styrene mer 44/56 mer 44/56
G.E. Lexan 151 P-3500 copolymer Post Acrylonitrile Acrylonitrile
Polycarbonate Polysulfone treated in /styrene Post /styrene No methanol, dried treated in Post treatment methanol, dried
Gas Feed H2,CO H2,CO H2,CO H2,CO H2,CO H2,CO
Coating Procedure F D D F F F
Coating Material 1.9 2.1 2.1 1.9 1.9 1.9
Determined Intrinsic
Separation Factor
H2 over CO
Porous Separation Membrane 3.29 1.3 3.0 3.0 - 3.2
Separation Factor
H2 over CO
Multicomponent Membrane 7.5 9.4 15.6 32 67.5 17
Separation Factor
H2 over CO
Multicomponent Membrane 4.41 x 10-5 9.95 x 10-5 6.7 x 10-5 3.2 x 10-5 1.9 x 10-5 4.46 x 10-5
Permeability for H2
Porous Separation Membrane 2.58 x 10-4 5.3 x 10-4 4.8 x 10-4 2.9 x 10-4 - 3.4 x 10-4
Permeability for H2
Determined Intrinsic 23.2 23.2 40 85 ~100 ~100
Separation Factor, H2 over CO for Material of Porous Separation
Membrane EXAMPLE 58.
This example illustrates a multicomponent membrane having multiple coatings to achieve a desired separation factor. A porous hollow fiber separation membrane composed of a copolymer of 63% acrylonitrile and 37% styrene was wetspun from a solution of 27.5 wt. percent copolymer in 93/7 dimethylformamide/formamide mixed solvent into 20C water at a rate of 21.4 mpm. This fiber was first treated by dipping in methanol while a vacuum was pulled on the bore, dried and the methanol treatment and drying repeated. The dried substrate fiber was then coated by procedure D with poly(cis-isoprene) in pentane solvent, cured for 30 minutes at 850C and then coated with 10% solution of Sylgard 184 in pentane by procedure F. The coated substrate was then recoated with the poly(cisisoprene) solution, dried and recoated with the Sylgard 184 solution and thereafter cured 30 minutes at 900 C, 30 minutes at 1000C and finally 30 minutes at 1050C. The results of testing the uncoated porous and the multiply coated multicomponent membrane are set out in Table XIII.
TABLE XIII.
Coating Material Determined Cis-Isoprene 3.5
Intrinsic Separation Factor, H2 over CO Sylgard 184 1.9
Porous Separation Membrane
Separation Factor, H2 over CO 5.09
Multicomponent Membrane
Separation Factor, H2 over CO 82
Multicomponent Membrane
Permeability to H2 6.5 x 10-7
Porous Separation Membrane
Permeability to H2 2.65 x 10-5 Determined Intrinsic Separation
Factor, H2 over CO 320 of Material of Porous Separation
Membrane
EXAMPLES 59 and 60.
Examples 59 and 60 illustrate multicomponent membranes utilizing a brominated poly(xylylene oxide) porous separation membrane in hollow fiber form with a coating. The hollow fiber was wet-spun from a dope of 30 wt. percent polymer in N-methylpyrrolidone into a water coagulant at 850C at a rate of 14.8 mpm. In Example 59 the brominated poly(xylylene oxide) in which the bromination is essentially upon methyl groups is coated without a post-spinning treatment. In
Example 60 the brominated poly(xylylene oxide) is post-treated by soaking for 20 hours in a solution of 10% trimethylamine in water. The coating in each instance was Dow Corning Sylgard 184 silicone rubber applied by procedure B (see Table
XVI). The results are set out in Table XIV below.
TABLE XIV.
59 60
Dow Corning Dow Corning
Sylgard 184 Sylgard 184
post-vulcanized post-vulcanized si]icone rubber silicone rubber
Brominated Poly- Brominated Poly
(xylylene oxide) (xylylene oxide)
Post-treated with (CH2)3N Coating Material Determined
Intrinsic Separation Factor,
H2 over CO 1.9 1.9
Porous Separation Membrane
Separation Factor, H 2 over CO 1.48 2.85
Multicomponent Membrane
Separation Factor, H2 over CO 11.1 9.59
Multicomponent Membrane
Permeability to H2 9.58 x 10-5 1.27 x 10-5
Porous Separation Membrane Permeability to H2 1.25 x 10-3 3.83 x 10-6 Determined Intrinsic Separation
Factor, H2 over CO, for Material 15 34 of Porous Separation Membrane
EXAMPLE 61.
This example illustrates a multicomponent membrane utilizing a different modified brominated poly(xylylene oxide) porous separation membrane in hollow fiber form. The hollow fiber of brominated poly(xylylene oxide) of Example 59 was post-treated by soaking for about 70 hours at 500 C in a solution of 5% by weight thiourea dissolved in 95/5 by volume water/methanol. After drying, the hollow fiber membrane was coated with a 5% solution of Dow Corning Sylgard 184 in pentane by procedure F (see Table XVI). Testing of the post-treated hollow fiber porous separation membrane and of the coated multicomponent membrane gave the following results:
Coating Material Determined
Intrinsic Separation Factor,
H2 over CO 1.9 Porous Separation Membrane
Separation Factor, Hover CO 5.6
Multicomponent Membrane
Separation Factor, H2 over CO 46.1
Multicomponent Membrane
Permeability to H2 7.2 x 10-6
Porous Separation Membrane
Permeability to H2
EXAMPLES 62 and 63.
These examples serve to illustrate the flexibility of the invention wherein the coating may be present on the interior and both interior and exterior surfaces of a hollow fiber porous separation membrane. They also illustrate the invention in a process wherein the gaseous feed stream is contacted at the surface of the multicomponent membrane opposite the coating. In Example 62 a porous polysulfone hollow fiber separation membrane was coated on the interior with a 3% solution of Sylgard 184 post-vulcanized silicone rubber in pentane by pumping such solution slowly through the bore of the hollow fiber substrate and allowing the fiber to air dry. The permeability was determined by permeation of an H2-CO mixture from the exterior into the bore of the resulting composite membrane. In Example 63 the bore coated fiber of Example 62 was additionally coated with the same
Sylgard 184 solution by procedure F. The results of testing these multicomponent membranes are set out in Table XV below.
TABLE XV.
62 63
Dow Corning Dow Corning
Sylgard 184 Sylgard 184
post-vulcanized post-vulcanized
silicone rubber silicone rubber Polysulfonç'al Polysulfone'8'
(bore only coated) (bore and outside
coated)
Coating Material Determined
Intrinsic Separation Factor,
H2 over CO 2.3 2.3
Porous Separation Membrane
Separation Factor, H2 over CO 3.23 3.23
Multicomponent Membrane
Separation Factor, H2 over CO 22.0 21.2
Multicomponent Membrane Permeability to H2 3.6 x 10-6 2.31 x 10-6
Porous Separation Membrane
Permeability to H2 2.06 x 10-4 2.06 x 10-4 (a) Polysulfone, Union Carbide, P-3500, wet-spun from a 30 wt. percent dope in a
50/50 dimethylformamide/N-methyl pyrrolidone solvent mixture into water at
2 C at a rate of 21.4 mpm and taken up, after washing and stretching, at 33
mpm.
EXAMPLE 64.
This example illustrates a procedure for making a multicomponent membrane in hollow fiber form which utilizes a polysulfone porous separation membrane and a coating of Sylgard 184. Polysulfone polymer (P-3500 available from Union
Carbide) is dried at 1000C at 125 mm. of mercury pressure for about 25 hours. The dried polysulfone is admixed at a temperature of about 65" to 700C with dimethylacetamide (moisture content less than about 0.1 weight percent) to provide a solution containing 27.5 weight percent polysulfone. The solution is transported to a holding tank having a nitrogen atmosphere at about 1.4 kilograms per square centimeter. The solution is not heated while in the holding tank and thus can cool to ambient temperature.
The polymer solution is pumped from the holding tank to a hollow fiber spinnerette which is immersed in an aqueous bath at a temperature of about 4 C.
The spinnerette has an outer orifice diameter of .0559 cm, an inner pin of .0229 cm and an injection orifice in the pin of .0127cm. The The polymer solution is pumped and metered to the spinnerette at a rate of about 7.2 milliliters per minute and is drawn from the spinnerette at a rate of about 33 meters per minute. The polymer solution coagulates in the form of a hollow fiber upon contacting the aqueous bath.
Through the injection orifice of the spinnerette is provided distilled water to coagulate the inside of the hollow fiber. The fiber passes through the aqueous bath for a distance of about one meter. A quantity of the aqueous bath is continuously purged to maintain a dimethyl acetamide concentration of less than about 4 weight percent in the bath.
The fiber is then immersed in a second aqueous bath which is maintained at a temperature of about 4"C for a distance of about five meters. Upon leaving the second aqueous bath the fiber contains some dimethylacetamide.
The fiber from the second aqueous bath is immersed in two additional aqueous baths at room temperature, each for a distance of about five meters, and the fiber is wound on a bobbin under only sufficient tension to effect the winding. The fiber is maintained wet with water during winding, and after winding the bobbin is immersed in an aqueous vat and stored at room temperature. Thereafter, the fiber is dried under ambient conditions, preferably at about 20"C and 50 percent relative humidity. The dried fiber is then coated with a solution of about 5 percent dimethylsiloxane-containing silicone rubber prepolymer (Sylgard 184 available from Dow Corning) and a curing agent in n-pentane. The application of the coating is conducted by immersing the fiber in the prepolymer solution while maintaining the solution under a positive pressure. The fiber is allowed to air dry and cross-link to provide the silicone rubber coating.
TABLE XVI - Coating Procedures
A. The porous hollow fiber membrane was dipped in undiluted liquid coating
material. The excess liquid was allowed to drip off.
B. The porous hollow fiber membrane was dipped in undiluted liquid coating
material while a vacuum was applied to the bore of the porous hollow fiber.
After the fiber was removed the vacuum was broken and excess liquid was
allowed to drip off.
C. The porous hollow fiber membrane was dipped in liquid coating material
diluted with a hydrocarbon solvent. The solvent was allowed to evaporate.
D. The porous hollow fiber membrane was dipped in liquid coating material with a
hydrocarbon solvent, while a vacuum was applied to the bore of the hollow
fiber. After the fiber was removed the vacuum was broken and the solvent was
allowed to evaporate.
E. The porous hollow fiber membrane was dipped in a solution containing coating
material in the form of a polymerizable prepolymer, appropriate curing agent,
and hydrocarbon solvent. The solvent was allowed to evaporate and the
membrane prepolymer was cured in place.
F. The coating procedure was used as described in E, except that a vacuum was
applied to the bore of the hollow fiber while it was dipped in the coating
solution.
Claims (67)
- WHAT WE CLAIM IS: 1. A multicomponent membrane for gas separation comprising a coating material in contact with a porous support, in which the porous support is a porous separation membrane having a substantial void volume as hereinbefore defined and comprising a material, which material of the porous separation membrane exhibits selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture and the material of the coating is in occluding contact with the porous separation membrane wherein, with respect to at least one pair of gases, the material of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the material of the coating, and the multicomponent membrane exhibits a separation factor greater than the determined intrinsic separation factor of the material of the coating and greater than the separation factor of the porous separation membrane.
- 2. A multicomponent membrane of Claim 1, in which the said at least one pair of gases consists of one of hydrogen, helium, ammonia and carbon dioxide and one of carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane, and ethane and the said void volume is 10 to 80 percent.
- 3. A multicomponent membrane of Claim 1, which with respect to the said at least one pair of gases exhibits a separation factor equal to or less than the determined intrinsic separation factor of the material of the porous separation membrane.
- 4. A multicomponent membrane of- Claim 3, in which the separation factor exhibited by the multicomponent membrane is at least 35 percent greater than the determined intrinsic separation factor of the material of the coating, the coating contacts at least one surface of the porous separation membrane and the porous separation membrane is anisotropic with a relatively dense region.
- 5. A multicomponent membrane for gas separation comprising a coating material in contact with a porous support, in which the porous support is an anisotropic porous separation membrane having a relatively dense region and comprising a material, which material of the porous separation membrane exhibits selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture and the material of the coating is in occluding contact with the relatively dense region of the porous separation membrane wherein, with respect to at least one pair of gases, the material of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the material of the coating, and the multicomponent membrane exhibits a separation factor greater than the determined intrinsic separation factor of the material of the coating and at least 35 percent greater than the separation factor of the porous separation membrane.
- 6. A multicomponent membrane of Claim I in which the porous separation membrane comprises at least one of polysulfone, copolymer of styrene and acrylonitrile, polycarbonate, and cellulose acetate.
- 7. A multicomponent membrane of any of Claims 3 to 5, in which the porous separation membrane comprises at least one of polysulfone, copolymer of styrene and acrylonitrile, polycarbonate, and cellulose acetate.
- 8. A multicomponent membrane of any of Claims 1 to 5, in which the porous separation membrane comprises a poly(arylene oxide).
- 9. A multicomponent membrane of any of Claims 1 to 7, in which the porous separation membrane comprises a polysulfone that has a repeating unit represented bywherein each of R and Rx are aliphatic or aromatic hydrocarbyl-containing moieties of 1 to 40 carbon atoms.
- 10. A multicomponent membrane of Claim 7, in which the porous separation membrane comprises a polysulfone that has a repeating unit represented bywherein n is 50 to 80.
- 11. A multicomponent membrane of Claim 7, in which the porous separation membrane comprises a poly(arylene ether) sulfone.
- 12. A multicomponent membrane of any of Claims 1 to 11, in which with respect to at least one gas selected from carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane, ethane and carbon dioxide, the effective separating thickness of the multicomponent membrane is less than 15,000 Angstroms based on the permeability constant of the material of the porous separation membrane for said gas, and the ratio of total surface area to total pore cross-sectional area of the porous separation membrane is at least 103:1.
- 13. A multicomponent membrane of any of Claims 9 to 11, in which with respect to at least one gas selected from carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane, ethane and carbon dioxide, the effective separating thickness of the multicomponent membrane is less than 5,000 Angstroms based on the permeability constant of the polysulfone for the said gas; the porous separation membrane has a total surface area to total pore cross-sectional area ratio of at least 10J:1; the porous separation membrane has an average pore diameter less than 20,000 angstroms, and the polysulfone has a molecular weight of at least 10,000.
- 14. A multicomponent membrane of Claim 8, in which the poly(arylene oxide) comprises a poly(xylylene oxide).
- 15. A multicomponent membrane of Claim 14, in which the poly(xylylene oxide) comprises a brominated poly(xylylene oxide).
- 16. A multicomponent membrane of any of Claims I to 5, in which the porous separation membrane comprises a copolymer of styrene and acrylonitrile containing 20 to 70 weight percent styrene and 30 to 80 weight percent acrylonitrile.
- 17. A multicomponent membrane of either of Claims 1 and 6, in which the coating comprises at least one of poly(siloxane), poly(isoprene), and poly(styrene) having a degree of polymerization of 2 to 20.
- 18. A multicomponent membrane of any of Claims 2, 8, 9, 12, 13, 14, 15 and 16 in which the coating comprises at least one of poly(siloxane), poly(isoprene), and poly(styrene) having a degree of polymerization of 2 to 20.
- 19. A multicomponent membrane of any of Claims 3, 4, 5, 7, 10 and 11, in which the coating comprises at least one of poly(siloxane), poly(isoprene), and poly(styrene) having a degree of polymerization of 2 to 20.
- 20. A multicomponent membrane of any of Claims 1 to 16, in which the coating comprises at least one of a copolymer of a-metllylstyrene and poly(siloxane), and aliphatic hydrocarbyl-containing organic compounds having 14 to 30 carbon atoms.
- 21. A multicomponent membrane of any of the preceding claims, in which the coating is applied using an essentially liquid substance suitable for forming the coating and the coating on each surface of the porous separation membrane to which it is supplied is up to 50 microns thick.
- 22. A multicomponent membrane of Claim 21, in which the essentially liquid substance is applied to one surface of the porous separation membrane, and the other surface is subjected to a lower absolute pressure during application.
- 23. A multicomponent membrane of either of Claim 21 or Claim 22, in which the essentially liquid substance comprises polymerizable material and is applied to the porous separation membrane, and the polymerizable material is polymerized after application to the porous separation membrane to provide the coasting.
- 24. A multicomponent membrane of any of Claims 1, 6 and 17, in which the coating comprises a poly(siloxane) and the coating is substantially non-interrupted.
- 25. A multicomponent membrane of any of Claims 3, 4, 5, 7, 10, 11 and 19, in which the coating comprises a poly(siloxane) and the coating is substantially noninterrupted.
- 26. A multicomponent membrane of any of Claims 2, 8, 9, 12, 13, 14, 15, 16, 18, 20, 21, 22 and 23, in which the coating comprises a poly(siloxane) and the coating is substantially non-interrupted.
- 27. A multicomponent membrane of any of the preceding claims, in which the coating comprises an aliphatic or aromatic poly(siloxane) having repeating units containing 1 to 20 carbon atoms.
- 28. A multicomponent membrane of either Claim 26 or Claim 27, in which the poly(siloxane) is cross-linked to provide silicone rubber and has a molecular weight of 1,000 to 100,000 prior to cross-linking.
- 29. A multicomponent membrane of any of Claims 1, 6, 17, and 24, in which, with respect to at least one gas of the said pair of gases, the material of the coating has a higher permeability constant than does the material of the porous separation membrane.
- 30. A multicomponent membrane of any of Claims 2, 8, 9, 12 to 16, 18, 20 to 23, and 26 to 28, in which, with respect to at least one gas of the said pair of gases, the material of the coating has a higher permeability constant than does the material of the porous separation membrane.
- 31. A multicomponent membrane of any of Claims 3-5,7, 10, 11, 19 and 25, in which, with respect to at least one gas of the said pair of gases, the material of the coating has a higher permeability constant than does the material of the porous separation membrane.
- 32. A multicomponent membrane of any of the preceding claims, in which the multicomponent membrane exhibits a greater permeability than that of a reference membrane substantially the same as the porous separation membrane except that at least one surface of the reference membrane has been sufficiently annealed, with or without the presence of a liquid, to provide, with respect to the said at least one pair of gases, a separation factor equal to or greater than the separation factor of the multicomponent membrane.
- 33. A multicomponent membrane of any of Claims 1 to 31, in which the multicomponent membrane exhibits a greater permeability than that of a reference membrane substantially the sarne as the porous separation membrane except that at least one surface of the reference membrane has been treated to densify it sufficiently to provide, with respect to the said at least one pair of gases, a separation factor equal to or greater than the separation factor of the multicomponent membrane.
- 34. A multicomponent membrane of any of the preceding claims, that is a film.
- 35. A multicomponent membrane of any of Claims 2, 8, 9, 12 to 16, 18, 20 to 23, 26 to 28, 30, 32 and 33 that is a hollow fiber.
- 36. A multicomponent membrane of any of Claims 1, 3 to 7, 10,11,17, 19, 24, 25 and 31 that is a hollow fiber.
- 37. A multicomponent membrane of either Claim 35 or Claim 36, in which the porous separation membrane is capable of maintaining the configuration of the hollow fiber under gas separation conditions and in which the multicomponent membrane exhibits a greater permeability than a reference anisotropic hollow fiber membrane consisting of the material of the porous separation membrane, which reference anisotropic hollow fiber membrane is capable of maintaining the configuration of the hollow fiber under gas separation conditions, and which, with respect to the said at least one pair of gases, exhibits a separation factor equal to or greater than the separation factor of the multicomponent membrane.
- 38. A multicomponent membrane of any of the preceding claims, in which both the separation factor and the permeability of the multicomponent membrane are influenced by the ratio of total surface area to total pore cross-sectional area and/or by the average pore cross-sectional diameter of the porous separation membrane.
- 39. A multicomponent membrane of any of Claims 1 to 37, in which both the separation factor and the permeability of the multicomponent membrane are influenced by the relative resistances to gas flow through the pores of the porous separation membrane and through the solid portions of the porous separation membrane.
- 40. A multicomponent membrane of Claim 35, in which the coating contacts at least the outside surface of the hollow fiber.
- 41. A multicomponent membrane of Claim 36, in which the coating contacts at least the outside surface of the hollow fiber.
- 42. A multicomponent membrane of any of Claims 2, 8,9, 12 to 16, 18, 20 to 23, 26 to 28, 30, 32, 33, 35, and 37 to 39, in which the coating contacts at least the feed surface of the porous separation membrane.
- 43. A multicomponent membrane of any of Claims 1, 3 to 7, 10, 11,17, 19, 24, 25, 29, 31 and 36, in which the coating contacts at least the feed surface of the porous separation membrane.
- 44. A multicomponent membrane of any of the preceding claims, in which the coating is in contact with both surfaces of the porous separation membrane, and the coating in contact with each surface has an average thickness up to 50 microns.
- 45. A multicomponent membrane of any of the preceding claims, in which the coating comprises at least two layers.
- 46. A multicomponent membrane of any of the preceding claims, in which the material of the coating has a sufficiently large molecular size such that the material of the coating is not drawn through the pores of the porous separation membrane during gas separation.
- 47. A process for separating at least one gas in a gaseous mixture from at least one other gas in the said gaseous mixture by selective permeation through a membrane and providing a permeated product containing at least one permeating gas, the process comprising contacting the gaseous mixture with at least one surface of the membrane, the said membrane being a multicomponent membrane as defined in any of Claims 1, 6, 17, 24, 29, 36, 41, and 43, which multicomponent membrane exhibits, with respect to at least one pair of gases of the gaseous mixture, selective permeation of one gas of the pair of gases over that of the remaining gas of the pair of gases; maintaining the opposite surface of the multicomponent membrane at a lower chemical potential for the said at least one permeating gas than the chemical potential at the said surface; permeating the said at least one permeating gas into and through the multicomponent membrane; and removing from the vicinity of the opposite surface a permeated product having a different proportion of the said at least one gas of the gaseous mixture to the said at least one other gas of the gaseous mixture than the proportion in the gaseous mixture of the said at least one gas to the said at least one other gas.
- 48. A process of Claim 47, in which the multicomponent membrane is a membrane of any of Claims 2, 8, 9, 12 to 16, 18, 20 to 23, 26 to 28, 30, 32, 33, 35, 37 to 39, 42 and 44 to 46.
- 49. A process of Claim 47, in which the multicomponent membrane is a membrane of any of Claims 3 to 5, 7, 10, 11, 19, 25 and 31.
- 50. A process of Claim 47, in which the said at least one gas comprises oxygen and the gaseous mixture comprises air.
- 51. A process of Claim 48, in which the said at least one gas comprises oxygen and the gaseous mixture comprises air.
- 52. A process of Claim 49, in which the said at least one gas comprises oxygen and the gaseous mixture comprises air.
- 53. A process of Claim 47, in which the said at least one gas comprises hydrogen and the said at least one other gas comprises at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitrous oxide, amm(mia, and methane.
- 54. A process of Claim 48. in which the said at least one gas comprises hydrogen and the said at least one other gas comprises at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitrous oxide, ammonia, and a hydrocarbon of 1 to 5 carbon atoms.
- 55. A process of Claim 49, in which the said at least one gas comprises hydrogen and the said at least one other gas comprises at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitrous oxide, ammonia, and methane.
- 56. A process of any of Claims 47 to 49, in which the said at least one gas comprises ammonia and the gaseous mixture comprises ammonia and at least one of hydrogen, nitrogen, methane and argon.
- 57. A process of any of Claims 47 to 49, in which the said at least one gas comprises carbon dioxide and the gaseous mixture comprises carbon dioxide and at least one of carbon monoxide, a hydrocarbon of 1 to 5 carbon atoms, and nitrogen.
- 58. A process of Claim 47, in which the said at least one gas comprises helium and the gaseous mixture comprises helium and methane.
- 59. A process of Claim 48, in which the said at least one gas comprises helium and the gaseous mixture comprises helium and methane.
- 60. A process of Claim 49, in which the said at least one gas comprises helium and the gaseous mixture comprises helium and methane.
- 61. A process of any of Claims 47 to 49, in which the said at least one gas comprises hydrogen sulfide and the gaseous mixture comprises hydrogen sulfide and at least one hydrocarbon of 1 to 5 carbon atoms.
- 62. A process of any of Claims 47 to 49, in which the said at least one gas comprises carbon monoxide and the gaseous mixture comprises carbon monoxide and at least one of hydrogen, helium, nitrogen, and a hydrocarbon of 1 to 5 carbon atoms.
- 63. An apparatus for selectively separating at least one gas in a gaseous mixture from at least one remaining gas, comprising an enclosure and a multicomponent membrane according to any of Claims 1 to 46 within the enclosure for selectively separating the said at least one gas in the gaseous mixture and providing a permeated product, the multicomponent membrane having a feed surface and an opposing exit surface, and the enclosure having means to enable the gaseous mixture to be supplied to the feed surface, means to enable removal of gases from the vicinity of the feed surface, and means to enable the permeated product to be removed from the vicinity of the exit surface.
- 64. A multicomponent membrane substantially as described in any one of Examples 1 to 23, 27 to 43 and 48 to 51.
- 65. A multicomponent membrane substantially as described in any one of Examples 44 to 47 and 52 to 64.
- 66. A process for separating gases substantially as described in any one of Examples I to 23, 27 to 43 and 48 to 51.
- 67. A process for separating gases substantially as described in any one of Examples 44 to 47 and 52 to 64.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74215976A | 1976-11-15 | 1976-11-15 | |
US05/832,481 US4230463A (en) | 1977-09-13 | 1977-09-13 | Multicomponent membranes for gas separations |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1590813A true GB1590813A (en) | 1981-06-10 |
Family
ID=27113975
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB47269/77A Expired GB1590813A (en) | 1976-11-15 | 1977-11-14 | Multicomponent membranes |
Country Status (28)
Country | Link |
---|---|
JP (1) | JPS5951321B2 (en) |
AR (1) | AR224102A1 (en) |
AT (1) | AT374375B (en) |
AU (1) | AU504016B2 (en) |
BE (1) | BE860811A (en) |
BR (1) | BR7707583A (en) |
CA (1) | CA1107203A (en) |
CS (1) | CS257751B2 (en) |
DD (1) | DD133298A5 (en) |
DE (1) | DE2750874C2 (en) |
DK (1) | DK148735C (en) |
EG (1) | EG13082A (en) |
ES (3) | ES464048A1 (en) |
FI (1) | FI61636C (en) |
FR (1) | FR2410501A1 (en) |
GB (1) | GB1590813A (en) |
IL (1) | IL53379A (en) |
IT (1) | IT1089058B (en) |
MX (2) | MX148173A (en) |
NL (1) | NL175387C (en) |
NO (1) | NO149019C (en) |
PH (1) | PH14682A (en) |
PL (1) | PL125022B1 (en) |
PT (1) | PT67269B (en) |
RO (1) | RO76391A (en) |
SE (1) | SE440744B (en) |
TR (1) | TR19886A (en) |
YU (1) | YU41572B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2151597A (en) * | 1983-12-16 | 1985-07-24 | Petrocarbon Dev Ltd | Recovery of carbon dioxide from gas mixtures |
GB2154600A (en) * | 1984-02-23 | 1985-09-11 | British Gas Corp | Producing and purifying methane |
US4639257A (en) * | 1983-12-16 | 1987-01-27 | Costain Petrocarbon Limited | Recovery of carbon dioxide from gas mixture |
US6085549A (en) * | 1998-04-08 | 2000-07-11 | Messer Griesheim Industries, Inc. | Membrane process for producing carbon dioxide |
US6128919A (en) * | 1998-04-08 | 2000-10-10 | Messer Griesheim Industries, Inc. | Process for separating natural gas and carbon dioxide |
GB2445078A (en) * | 2006-12-19 | 2008-06-25 | Gen Electric | Inert gas sequestrationn unit allowing the efficient use of a low heating value fuel |
ITUB20159436A1 (en) * | 2015-12-28 | 2017-06-28 | Medica S P A | USE OF A MEMBRANE FOR BIOGAS PURIFICATION |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5416378A (en) * | 1977-07-08 | 1979-02-06 | Asahi Chem Ind Co Ltd | Polysulfone semipermeable membrane |
CA1127472A (en) * | 1977-11-25 | 1982-07-13 | Robert L. Riley | Gas separation membranes and process for the preparation thereof |
US4181675A (en) * | 1978-09-19 | 1980-01-01 | Monsanto Company | Process for methanol production |
IL59581A0 (en) * | 1979-03-28 | 1980-06-30 | Monsanto Co | Methods for preparing anisotropic membranes and membranes prepared therefrom |
DE3061132D1 (en) * | 1979-04-03 | 1982-12-30 | Monsanto Co | Gas recovery process |
US4238204A (en) * | 1979-06-18 | 1980-12-09 | Monsanto Company | Selective adsorption process |
EP0024718A3 (en) * | 1979-09-04 | 1981-10-14 | Friedrich Wolff | Device for increasing or decreasing the oxygen content of air, and method of producing and of operating it |
DE3006880C2 (en) * | 1980-02-23 | 1986-10-09 | Akzo Gmbh, 5600 Wuppertal | Plasmaphoresis membrane |
FR2478482A1 (en) * | 1980-03-21 | 1981-09-25 | Lidorenko Nikolai | Supported gas-permeable membranes - for use in blood oxygenator(s) |
FR2482468A1 (en) * | 1980-05-19 | 1981-11-20 | Bend Res Inc | Reverse osmosis composite membrane is hollow fibre - whose inner surface is coated with interfacial salt rejecting membrane |
JPS5794304A (en) * | 1980-12-03 | 1982-06-11 | Sumitomo Chem Co Ltd | Gas separating membrane made of polysulfone hollow fiber and its manufacture |
JPS57104007A (en) * | 1980-12-19 | 1982-06-28 | Matsushita Electric Ind Co Ltd | Oxygen-enriched gas supplying equipment for combustion |
US4367135A (en) * | 1981-03-12 | 1983-01-04 | Monsanto Company | Processes |
US4362613A (en) * | 1981-03-13 | 1982-12-07 | Monsanto Company | Hydrocracking processes having an enhanced efficiency of hydrogen utilization |
JPS588514A (en) * | 1981-07-08 | 1983-01-18 | Ube Ind Ltd | Preparation of composite separation film |
JPS58132111A (en) * | 1982-01-29 | 1983-08-06 | Asahi Chem Ind Co Ltd | Polysulfone hollow fiber |
US4428776A (en) * | 1982-06-23 | 1984-01-31 | The Standard Oil Company | Cellulosic semipermeable membranes containing silicon compounds |
JPS59160506A (en) * | 1983-02-28 | 1984-09-11 | Kuraray Co Ltd | Composite hollow yarn separating membrane and its production |
JPS59169509A (en) * | 1983-03-14 | 1984-09-25 | Toray Ind Inc | Hollow yarn membrane for separating gas and preparation thereof |
US4530703A (en) * | 1983-06-30 | 1985-07-23 | Monsanto Company | Cross-linked polyarylene oxide membranes |
EP0141793A1 (en) * | 1983-06-30 | 1985-05-15 | Monsanto Company | Asymmetric gas separation membranes having increased selectivy, and process for their production |
EP0131559B1 (en) * | 1983-06-30 | 1987-12-02 | Monsanto Company | Amorphous aryl substituted polyarylene oxide membranes |
DE3582394D1 (en) * | 1984-04-11 | 1991-05-08 | Syrinx Res Pty Ltd | HIGH FLUX MEMBRANE. |
JPS61408A (en) * | 1984-06-11 | 1986-01-06 | Toyobo Co Ltd | Hollow yarn composite membrane |
DE3567809D1 (en) * | 1985-02-14 | 1989-03-02 | Uop Inc | Thin-film semipermeable membranes, a method for their preparation and hydrogen-sensing and-separating devices including them |
DE3525235C1 (en) * | 1985-07-15 | 1986-11-27 | Gkss - Forschungszentrum Geesthacht Gmbh, 2054 Geesthacht | Process for producing and increasing the selectivity of an integral asymmetrical membrane |
JPH0822373B2 (en) * | 1986-02-10 | 1996-03-06 | 旭化成工業株式会社 | Method for forming polysulfone-based composite membrane |
EP0242069A3 (en) * | 1986-04-14 | 1988-08-03 | Dow Corning Corporation | Semipermeable composite membranes produced from silicone water based emulsions applied to porous substrates |
US4894068A (en) * | 1988-12-27 | 1990-01-16 | Permea, Inc. | Process for capturing nitrogen from air using gas separation membranes |
DE4242806A1 (en) * | 1992-12-17 | 1994-06-23 | Siemens Ag | Sensor hose |
US5286280A (en) * | 1992-12-31 | 1994-02-15 | Hoechst Celanese Corporation | Composite gas separation membrane having a gutter layer comprising a crosslinked polar phenyl-containing - organopolysiloxane, and method for making the same - |
US5514413A (en) * | 1994-03-31 | 1996-05-07 | Air Products And Chemicals, Inc. | Process for producing composite membranes |
US5443728A (en) * | 1994-04-28 | 1995-08-22 | Praxair Technology, Inc. | Method of preparing membranes from blends of polyetherimide and polyimide polymers |
US6315968B1 (en) * | 1995-01-18 | 2001-11-13 | Air Products And Chemicals, Inc. | Process for separating acid gases from gaseous mixtures utilizing composite membranes formed from salt-polymer blends |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL236452A (en) * | 1958-02-24 | 1900-01-01 | ||
US3350844A (en) * | 1964-09-21 | 1967-11-07 | Gen Electric | Process for the separation or enrichment of gases |
AU412451B1 (en) * | 1966-02-21 | 1971-04-21 | E. I. Dupont De Nemours And Company | Process and apparatus for separation of fluid mixtures |
FR1566272A (en) * | 1968-01-19 | 1969-05-09 | ||
NL158087B (en) * | 1968-01-30 | 1978-10-16 | Universal Oil Prod Co | PROCESS FOR SEPARATING GASES USING A MEMBRANE FROM A CELLULOSE ESTER. |
FR2082095A5 (en) * | 1970-03-03 | 1971-12-10 | Rhone Poulenc Sa | |
US3926798A (en) * | 1974-10-17 | 1975-12-16 | Us Interior | Reverse osmosis membrane |
JPS5255719A (en) * | 1975-10-31 | 1977-05-07 | Daicel Chem Ind Ltd | Hollow fibers having selective gas permeability and production thereof |
US3980456A (en) * | 1975-03-31 | 1976-09-14 | General Electric Company | Method for sealing breaches in multi-layer ultrathin membrane composites |
-
1977
- 1977-11-10 FR FR7734031A patent/FR2410501A1/en active Granted
- 1977-11-11 NL NLAANVRAGE7712432,A patent/NL175387C/en not_active IP Right Cessation
- 1977-11-11 ES ES464048A patent/ES464048A1/en not_active Expired
- 1977-11-11 BR BR7707583A patent/BR7707583A/en unknown
- 1977-11-14 RO RO7792112A patent/RO76391A/en unknown
- 1977-11-14 FI FI773439A patent/FI61636C/en not_active IP Right Cessation
- 1977-11-14 MX MX171323A patent/MX148173A/en unknown
- 1977-11-14 DD DD7700202073A patent/DD133298A5/en unknown
- 1977-11-14 AR AR269964A patent/AR224102A1/en active
- 1977-11-14 MX MX193977A patent/MX172537B/en unknown
- 1977-11-14 JP JP52137219A patent/JPS5951321B2/en not_active Expired
- 1977-11-14 BE BE182612A patent/BE860811A/en not_active IP Right Cessation
- 1977-11-14 AT AT0812477A patent/AT374375B/en not_active IP Right Cessation
- 1977-11-14 PT PT67269A patent/PT67269B/en unknown
- 1977-11-14 GB GB47269/77A patent/GB1590813A/en not_active Expired
- 1977-11-14 DE DE2750874A patent/DE2750874C2/en not_active Expired
- 1977-11-14 SE SE7712818A patent/SE440744B/en not_active IP Right Cessation
- 1977-11-14 IT IT29640/77A patent/IT1089058B/en active
- 1977-11-14 NO NO773882A patent/NO149019C/en unknown
- 1977-11-14 CA CA290,702A patent/CA1107203A/en not_active Expired
- 1977-11-14 DK DK503277A patent/DK148735C/en not_active IP Right Cessation
- 1977-11-14 CS CS777473A patent/CS257751B2/en unknown
- 1977-11-14 PL PL1977202124A patent/PL125022B1/en unknown
- 1977-11-14 IL IL53379A patent/IL53379A/en unknown
- 1977-11-14 AU AU30607/77A patent/AU504016B2/en not_active Expired
- 1977-11-15 PH PH20438A patent/PH14682A/en unknown
- 1977-11-15 YU YU2722/77A patent/YU41572B/en unknown
- 1977-11-15 EG EG639/77A patent/EG13082A/en active
- 1977-11-16 TR TR19886A patent/TR19886A/en unknown
-
1978
- 1978-01-30 ES ES466474A patent/ES466474A1/en not_active Expired
- 1978-12-01 ES ES475666A patent/ES475666A1/en not_active Expired
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2151597A (en) * | 1983-12-16 | 1985-07-24 | Petrocarbon Dev Ltd | Recovery of carbon dioxide from gas mixtures |
US4639257A (en) * | 1983-12-16 | 1987-01-27 | Costain Petrocarbon Limited | Recovery of carbon dioxide from gas mixture |
GB2154600A (en) * | 1984-02-23 | 1985-09-11 | British Gas Corp | Producing and purifying methane |
US6085549A (en) * | 1998-04-08 | 2000-07-11 | Messer Griesheim Industries, Inc. | Membrane process for producing carbon dioxide |
US6128919A (en) * | 1998-04-08 | 2000-10-10 | Messer Griesheim Industries, Inc. | Process for separating natural gas and carbon dioxide |
AU2007240194B2 (en) * | 2006-12-07 | 2013-09-26 | Bha Altair, Llc | Method and system for using low btu fuel gas in a gas turbine |
GB2445078A (en) * | 2006-12-19 | 2008-06-25 | Gen Electric | Inert gas sequestrationn unit allowing the efficient use of a low heating value fuel |
GB2445078B (en) * | 2006-12-19 | 2011-08-31 | Gen Electric | Method and system for using low btu fuel gas in a gas turbine |
ITUB20159436A1 (en) * | 2015-12-28 | 2017-06-28 | Medica S P A | USE OF A MEMBRANE FOR BIOGAS PURIFICATION |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4230463A (en) | Multicomponent membranes for gas separations | |
GB1590813A (en) | Multicomponent membranes | |
KR940006394B1 (en) | Composite membrane and their manufacture and use | |
Chung et al. | Formation of ultrathin high-performance polyethersulfone hollow-fiber membranes | |
US5181940A (en) | Hollow fiber membranes | |
US4157960A (en) | Method for enhancing membrane separation | |
KR900008712B1 (en) | Asymmetric gas seperation membranes having graded density skins | |
US4654055A (en) | Asymmetric gas separation membranes | |
US4728345A (en) | Multicomponent gas separation membranes having polyphosphazene coatings | |
US4214020A (en) | Processes for coating bundles of hollow fiber membranes | |
US4486202A (en) | Asymmetric gas separation membranes | |
US4530703A (en) | Cross-linked polyarylene oxide membranes | |
EP0649676A1 (en) | Fluoropolymer posttreatment of gas separation membranes | |
JPS63116723A (en) | Method of forming hollow fiber irregular gas separating film | |
CA1141510A (en) | Methods for preparing anisotropic membranes and membranes prepared therefrom | |
JPH02501991A (en) | Improved composite membranes, their manufacture and use | |
US5091216A (en) | Reactive post treatment for gas separation membranes | |
EP0354937B1 (en) | Composite membranes of poly(methyl methacrylate) blends | |
JP2688882B2 (en) | Method for producing composite membrane for gas separation | |
JPS5825371B2 (en) | Anisotropic membrane and its manufacturing method | |
KR820000171B1 (en) | Method for gas separation by multicomponent membranes | |
EP0336999B1 (en) | Reactive posttreatment for gas separation membranes | |
Brown | Hollow fibre membranes for gas separation | |
KR950004142B1 (en) | Impoved composite membranes, their manufacture and their use | |
JPS5951841B2 (en) | Multicomponent membrane for gas separation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951114 |