WO2014055274A1 - Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations - Google Patents
Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations Download PDFInfo
- Publication number
- WO2014055274A1 WO2014055274A1 PCT/US2013/061149 US2013061149W WO2014055274A1 WO 2014055274 A1 WO2014055274 A1 WO 2014055274A1 US 2013061149 W US2013061149 W US 2013061149W WO 2014055274 A1 WO2014055274 A1 WO 2014055274A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mesoporous silica
- ionic liquid
- bis
- polar gas
- mixture
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 14
- -1 (trifluoromethyl)sulfonyl Chemical group 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006557 surface reaction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000011148 porous material Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical compound [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RZYHXKLKJRGJGP-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)N([Si](C)(C)C)C(=O)C(F)(F)F RZYHXKLKJRGJGP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- MZMRZONIDDFOGF-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCCCCCC[N+](C)(C)C MZMRZONIDDFOGF-UHFFFAOYSA-M 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- B01D19/00—Degasification of liquids
- B01D19/0031—Degasification of liquids by filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/38—Liquid-membrane separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
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- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- 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
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3263—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. an heterocyclic or heteroaromatic structure
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3287—Layers in the form of a liquid
Definitions
- the present invention relates to the field of mesoporous silica materials useful for separations. More particularly, it relates to a mesoporous silica having grafted therewith an ionic liquid that is particularly useful for certain separations.
- Mesoporous materials have been known to researchers for many years, and are used for a variety of applications.
- these materials are inorganic, solid materials characterized by a structure which comprises pores, the pores having average diameters in a general range of from 2 to 50 nanometers (nm). These pores may be uniform with constant diameters, or non-uniform with a variety of diameters.
- the porous structure provides for a large internal surface area with adsorptive capacity for molecular species which are capable of entering the pores.
- the pores may penetrate essentially the entire volume of the solid material, and therefore may be essentially two-dimensional or three-dimensional (i.e., channels), depending upon the configuration of the material's structure as a whole.
- Mesoporous materials may be amorphous or crystalline.
- mesoporous materials include synthetic or natural crystalline pure silicates and aluminosilicates. Such may also be referred to as "framework aluminosilicates," where the framework is based on a three-dimensional network of [(Al,Si) 4 ] tetrahedra which are linked to each other, at the corners, by shared oxygen atoms. Substitution of aluminum for silicon generates a charge imbalance, requiring the inclusion of an additional cation.
- Mesoporous silicas have been shown to be able to successfully support ionic liquid catalysts including an acetate counterion, such as is shown in China Publication No. CN 101773852 (14 July 2010). That publication describes functionalizing the surface of the mesoporous silica, followed by reaction with an imidazolium species. The catalyst thus prepared is used for preparing vinyl acetate in an acetylene method.
- the invention is a mesoporous silica composition
- a mesoporous silica having grafted therewith an ionic liquid comprising silylated 3, 3' -(2,2- bis(hydroxymethyl)propane-l,3-diyl)bis(l-methyl-lH-imidazol-3- ium)bis ((trifluoromethyl) sulfonyl) -amide.
- the invention is a process for a separation comprising contacting: (1) a mesoporous silica, the mesoporous silica having grafted therewith an ionic liquid; and (2) a mixture, selected from a first mixture having as constituents a polar gas and a non-polar gas, and a second mixture having as constituents an olefin and a paraffin; under conditions such that, where the first mixture is selected, the polar gas and non-polar gas are substantially separated from one another, and where the second mixture is selected, the olefin and the paraffin are substantially separated from one another.
- the ionic liquid comprises silylated 3,3'-(2,2-bis(hydroxymethyl)propane-l,3-diyl)bis(l-methyl-lH- imidazol- 3 -ium)bis ((trifluoromethyl) sulfonyl) - amide.
- One aspect of the invention is use, as a starting material, of a mesoporous silica, preferably one having a three-dimensional pore system.
- a mesoporous silica preferably one having a three-dimensional pore system.
- Such may be entirely silicate in composition, or may include an amount of tetrahedrally bound alumina, such that the mesoporous silica is technically an aluminosilicate.
- mesoporous silica is technically an aluminosilicate.
- mesoporous silica such shall be collectively termed as "mesoporous silicas," regardless of inclusion of a small proportion of alumina, i.e., a Si:Al molar ratio of greater than 1000.
- Such may also, in alternative embodiments, be doped with even smaller amounts (less than 1 weight percent, wt ) of boron, phosphorus, or other metals.
- suitable materials within this description include, but are not limited to, synthetic mesoporous silicas such as those within the families of Type X, 3 A, 4 A, and 5; MCM-22 through MCM-41, and MCM-48; SBA-1, SB A- 15, and SB A- 16; and combinations thereof.
- the specifically exemplified zeolite grades listed hereinabove all have an average pore diameter generally considered as ranging from 0.3 nm to 0.8 nm and an overall average particle diameter generally considered as ranging from less than 0.5 micrometers ( ⁇ ) to 16 ⁇ , and in particular embodiments, from 2 ⁇ to 16 ⁇ . Such grades are preferred in certain particular embodiments.
- MCM-22 through MCM-41, MCM-48, SBA-15, SBA-1, or SBA-16 in particular, in the present invention, such may advantageously be used as commercially supplied, as to both form and hydration state.
- prior treatment or activation e.g., to remove adsorbed water
- such may be carried out as part of the preparation of the inventive compositions or may have already been carried out as to commercially-obtained starting materials, if and where desired.
- the selected mesoporous silica (or silicas) is (are) used in powder (i.e., particulate) form.
- suitable mesoporous silicas are not commercially available or commercially available materials are otherwise not selected for use in the present invention, such may be prepared from starting materials that include an organic structure-directing template and a silica source.
- suitable structure-directing templates include cetyltrimethylammonium bromide (CTAB, also referred to as hexadecyltrimethylammonium bromide), hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium hydroxide hydrate, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium bis-sulfonate, and combinations thereof.
- CTAB cetyltrimethylammonium bromide
- hexadecyltrimethylammonium chloride hexadecyltrimethylammonium hydroxide hydrate
- a suitable silica source may be selected from, in non-limiting example, tetraethyl orthosilicate (TEOS), fumed silica, silica gel, silicon dioxide, LUDOXTM AM-30 colloidal silica (a suspended silica solution available from Sigma Aldrich), sodium silicate, polysilycic acid, other water soluble silicas and silicates, and combinations thereof.
- TEOS tetraethyl orthosilicate
- fumed silica silica gel
- silicon dioxide silicon dioxide
- LUDOXTM AM-30 colloidal silica a suspended silica solution available from Sigma Aldrich
- sodium silicate polysilycic acid
- other water soluble silicas and silicates and combinations thereof.
- the mesoporous silica may be prepared by contacting the structure- directing template and the silica source, preferably in solution, desirably but optionally in the presence of a promoter and under suitable conditions relating to time, temperature, and/or pressure.
- a promoter may be, in one non-limiting embodiment, sodium nitrate (NaN0 3 ) or another alkali metal nitrate salt such as cesium nitrate (CsN0 3 ), and the molar ratio of the template to the silica source may desirably range in various embodiments from 0.1 to 10, and preferably from 0.1 to 2.0.
- Time may desirably range from 0.5 hours (h) to 200 h, and preferably from 10 h to 150 h; temperature may desirably range from 20 degrees Celsius (°C) to 300°C, and preferably from 50° C to 140°C; and pressure may desirably range from 1 standard atmosphere (atm) (about 101.3 kilopascals, kPa) to 15 atm (about 1519.9 kPa), and preferably from 2 atm (about 202.7 kPa) to 5 atm (about 506.6 kPa). More preferably time may range from 10 h to 120 h; temperature from 50°C to 140°C; and pressure from 2 atm (about 202.7 kPa) to 5 atm (about 506.6 kPa).
- Stirring or other means of maximizing contact during the formation process is desirable.
- further purification steps such as, for example, filtrations and washings and, especially, calcinations, with or without steam, at temperatures ranging from 300°C to 700°C, preferably from 400°C to 600°C, may be used to remove the organic template and/or any impurities and to obtain and/or to activate the desired mesoporous silica.
- activate means to increase the ultimate effectiveness of the prepared mesoporous silica.
- the selected mesoporous silica has, grafted therewith, an ionic liquid, the graft product being herein termed the mesoporous silica composition.
- the terms "graft” and “grafted” as used herein refer to the presence of a covalent bond between the mesoporous silica and the ionic liquid.
- the ionic liquid serves to modify the properties of the mesoporous silica relating to, for example, efficiency and selectivity in applications such as separations, and in particularly desirable embodiments, in separations of polar gas/non-polar gas and olefin/paraffin mixtures.
- the ionic liquid serves to impart functionalities, to the process or system where the mesoporous silica composition will be used, that are over and above those imparted by or attributed to the mesoporous silica alone.
- the increase in number and/or alteration in type of chemical groups available for catalytic activity during the separation can enhance the transport mechanism that is attributable first to the size- and shape-selectivity of the mesoporous silica alone.
- the selected ionic liquid has an imidazolium cationic functionality.
- the selected ionic liquid is a multiple resonance (i.e., weakly coordinating) salt including an anion such as, in non-limiting example, tetrafluoroborate (BF 4 " ), hexafluorophosphate (PF 6 ⁇ ), dicyanamide (dca ), sulfonate (RSCV , where R is an aliphatic or aromatic hydrocarbon such as methyl, ethyl, propyl, phenyl, tolyl, etc.), triflate (OTf), bis(trifluoro-methanesulfonimide)(Tf 2 ⁇ ), or the like.
- BF 4 " tetrafluoroborate
- PF 6 ⁇ hexafluorophosphate
- dicyanamide dca
- RSCV sulfonate
- R is an aliphatic or aromatic hydrocarbon such as methyl, ethyl, prop
- imidazolium cation-containing ionic liquid silylated 3,3'-(2,2-bis(hydroxymethyl)propane-l,3- diyl)bis(l-methyl-lH-imidazol-3-ium)bis((trifluoromethyl)sulfonyl)-amide), which may be shown as having the empirical formula designated as Formula 1 :
- Rl is H or Si(OR3) 3 ;
- R2 is H or Si(OR3) 3 ;
- R3 is -(CH 2 ) n CH 3 or C 6 H 6 ;
- R4 is H, - (CH 2 ) n CH 3 or C 6 H 6 ;
- R5 is H, -(CH 2 ) n CH 3 or C 6 H 6 ; and
- N is 0-20.
- the structure of this material may alternatively be illustrated by Formula 2 hereinbelow.
- the imidazolium functionality may contribute to thermal stability and that this silylated molecule, as a whole, may enhance the sorption capability and selectivity of the grafted product.
- Additional or alternative functionality, as imparted by an ionic liquid, that may be desirable in other embodiments include, in non-limiting example, methyl, amino or amine.
- the Formula 1 material may contain a hydroxyl functional group (ORl, where Rl is H; or OR2, where R2 is H), the presence of which may facilitate silylation of the compound which, in turn, may facilitate grafting of the ionic liquid onto the surface of the mesoporous silica.
- Silylation can be carried out by a method such as, in non-limiting example, reflux of the selected ionic liquid in the presence of a suitable silane material, for example, trimethylsilylchloride or bis(trimethylsilyl) trifluoroacetamide.
- a suitable silane material for example, trimethylsilylchloride or bis(trimethylsilyl) trifluoroacetamide.
- preparation of the final mesoporous silica-supported ionic liquids having three-dimensional pores of the invention may be by any effective means. See, for example, Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C; Beck, J. S.; Nature, 359, 710, (1992).
- the selected mesoporous silica and selected ionic liquid may be desirably contacted with stirring and refluxed at suitable increased temperature for a period of time. This will help to ensure grafting of the ionic liquid to the mesoporous silica.
- stirring with or without refluxing, may be carried out under conditions wherein the molar ratio of ionic liquid to silica ranges from stoichiometric to greater than stoichiometric, for example, from a 5- to 10-fold excess of the ionic liquid.
- Temperature may conveniently range from 0°C to 240°C, desirably from 20°C to 100°C, more desirably from 50°C to 100°C, and in certain particular embodiments, from 50°C to 60°C, while time may conveniently range from 0.5 h to 40 h, desirably from 0.5 h to 24 h, and most preferably from 10 h to 24 h.
- Alterations of pressure may be used in order to alter reaction time, with such pressures preferably ranging from 1 atm (about 101.3 kPa) to 500 atm (about 50662.5 kPa). In particular, use of higher pressures may conveniently reduce reaction time.
- Other methods may alternatively be employed, provided that the end result is that the ionic liquid ultimately achieves a desired level of grafting to the selected mesoporous silica. In particular but non-limiting embodiments, that level may desirably range from 1 weight percent (wt ) to 100 wt , preferably from 5 wt to 90 wt , and more preferably from 5 wt to 55 wt , based on weight of the silica.
- XRD X-ray diffraction
- NMR solid state nuclear magnetic resonance
- FT-IR Fourier Transform infrared spectroscopy
- TGA thermogravimetric analysis
- a pi-bond phillic salt such as is disclosed in, for example WO 2011037820.
- a salt may include cations such as, in non- limiting embodiments, silver (Ag + ), copper (Cu + ).
- Other pi-bond phillic metals such as palladium (Pd°) or platinum (P°), may alternatively be selected.
- This further modification may be accomplished by subsequent contact of the mesoporous silica composition with, for example, a silver and/or copper salt solution, with the silver and/or copper salt solution being preferably in a concentration in aqueous solution of up to about 20 wt .
- This procedure results in ion exchange of the salt in the ionic liquid and represents a method that is well known to those skilled in the art. See also, for example, WO 2011037820.
- Impregnation using one or more of these salts may serve to enhance the selectivity of the ionic liquid grafted mesoporous silica to pi-bond containing gases, such as olefins, in separations thereof from gases that lack pi-bonds, such as paraffins, while at the same time reducing the loss in selectivity over time which is caused by the transport of the pi-bond phillic salt to the permeate side of a membrane.
- This progressive loss of selectivity is attributable to the relative immobility of the salt-carrying phase, i.e., of the ionic liquid.
- the ionic liquid grafted mesoporous silica materials may be used in a variety of applications.
- separations such as polar gas/non-polar gas separations and olefin/paraffin separations (e.g., C0 2 /alkanes, ethylene/ethane, etc.), can be carried out effectively due to the fact that the mesoporous silica support material is a solid and therefore suitable for use in, for example, fixed beds.
- That level is at least 95 wt , and most desirably at least 99 wt .
- Pressure swing adsorptions can also be effectively accomplished.
- inventive materials may alternatively be fabricated into membranes and used in electronic devices for thermal and/or conductivity management and for a variety of transport-related applications including, but not limited to, gas separations, drug and fragrance release applications, gas detection, heavy metal removal, water purification, and combinations thereof.
- TEOS 10 milliliters (mL) of TEOS is mixed with 50 mL of deionized water and the mixture vigorously (add rpm) stirred for 60 minutes (min) at 308 degrees Kelvin (K, about 35°C). Then, 0.9024 grams (g) of sodium hydroxide (NaOH) is added to the mixture, followed by 0.3835 g of sodium nitrate (NaN0 3 ) as a promoter.
- NaOH sodium hydroxide
- a 100 mL single necked round bottom flask with side arm is equipped with a stir bar and flame dried using a heat gun followed by cooling under vacuum. After releasing the vacuum with argon, the flask is charged with 5 g of 1-methylimidazole (60 mmol), 5 g of 2,2- bis(bromomethyl)- 1,3 -propane diol (20 mmol) and 10 mL of dimethylformamide (DMF) solvent. The contents are flushed with nitrogen for from 30 to 40 min followed by heating the contents to 323 K (about 50°C) for a period ranging from 15 to 16 h. A solid imidazolium bromide salt is found to precipitate slowly from DMF solution as the reaction progresses.
- 1-methylimidazole 60 mmol
- 2,2- bis(bromomethyl)- 1,3 -propane diol 20 mmol
- DMF dimethylformamide
- a 100 mL single necked round bottom flask with side arm is equipped with a stir bar and flame dried using a heat gun followed by cooling under vacuum. After releasing the vacuum with argon, the flask is charged with 2 g (2.4 mmol) of ionic liquid and dried under vacuum to remove any traces of dissolved water. The flask is transferred to a glove box and dissolved in approximately 5 mL of dry acetonitrile followed by addition of 1 g of bis(trimethylsilyl) trifluoroacetamide silylating agent (3.8 mmol). The flask is taken out of the glove box and the contents refluxed at 223 to 228 K (about -50°C to about -45°C) for 5 to 6 h.
- silylated ionic liquid is characterized by LC-Mass spectroscopy analysis (Thermo Make Focus GC DSQ II MS), and ] H- NMR (300 MHz Varian, using dimethyl sulfoxide-d6 (DMSO-d6) as a solvent). Product is termed silylated ionic liquid.
- the silylated ionic liquid described hereinabove is grafted onto the surfaces of MCM- 48 by refluxing 0.25 g of calcined MCM-48 with 15 mL of chloroform (dry, 99.8% purity, from Aldrich) and 0.72 g of the silylated ionic liquid. The mixture is stirred and refluxed at 334 K (about 61°C) for 24 h. The ionic liquid functionalized MCM-48 is then washed repeatedly with chloroform (ethanol may alternatively be used) and dried at 353 K (about 80°C) for 8 h.
- the ionic liquid grafted silica is characterized by using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area measurements, scanning electron microscopy (SEM), Fourier Transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA) in nitrogen.
- XRD patterns of all samples are recorded on a PANanalytical, X'pert PRO X-ray diffractometer using copper (Cu) radiation source.
- N 2 isotherms are carried out by using Micromeritics ASAP 2010. The morphology and crystallite particle sizes are determined using the Leica 440 SEM.
- FTIR spectra are collected using ThermoFisher (ICC) (DRIFTS-cup experiments).
- Table 1 lists various loadings of silylated ionic liquids onto mesoporous supports, and Table 2 gives the change in surface areas and pore volumes of the mesoporous supports after grafting of the silylated ionic liquids.
- Table 2 Comparison of surface areas and pore volumes with and without grafting of silylated ionic liquids onto mesoporous silica supports.
- BJH B arret- Joyner-Halenda method, which calculates mesopore distribution from nitrogen adsorption data
- Sample 7 is a comparative and does not include an ionic liquid graft.
- Sorption measurement of carbon dioxide on the ionic liquid grafted mesoporous composition of Example 1 is carried out using BET measurements taken from a pressure of from 19 to 760 millimeters of mercury (mm Hg, torr) at 297 K (about 24°C). It shows carbon dioxide sorption capacity of 25 mL/g at 297 K (about 24°C) and 760 mm Hg.
- the observed BET surface area using carbon dioxide is 45 m 2 /g with pore size of 40 angstroms (A).
- the carbon dioxide isotherm shows weak to medium interaction of carbon dioxide with the grafted mesoporous silica composition, which is beneficial in the case of use of the inventive materials in membrane separation processes.
- a 50/50 wt mixture of ethylene and ethane is process over a fixed bed packed with the mesoporous silica composition of Example 1 in order to separate the olefin (ethylene) from the paraffin (ethane).
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Abstract
Description
Claims
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EP13771037.2A EP2903720A1 (en) | 2012-10-01 | 2013-09-23 | Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations |
US14/426,867 US9370735B2 (en) | 2012-10-01 | 2013-09-23 | Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations |
BR112015007154A BR112015007154A2 (en) | 2012-10-01 | 2013-09-23 | process for a separation |
JP2015534577A JP5867889B2 (en) | 2012-10-01 | 2013-09-23 | Ionic liquid grafted mesoporous silica composition for polar gas / nonpolar gas and olefin / paraffin separation |
CN201380051022.4A CN105120983B (en) | 2012-10-01 | 2013-09-23 | The ionic liquid grafting meso-porous titanium dioxide silicon composition separated with olefin/paraffin for polar gas/non-polar gas |
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CN104190382A (en) * | 2014-08-11 | 2014-12-10 | 湖北师范学院 | Preparation method and application of PVA supported ionic liquid adsorbing material |
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CN113277519B (en) * | 2021-06-22 | 2022-09-16 | 清华大学 | Silicon dioxide mesoporous material using waste glass as raw material and preparation method and application thereof |
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US9370735B2 (en) | 2016-06-21 |
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BR112015007154A2 (en) | 2017-07-04 |
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