WO2023067841A1 - Gis型ゼオライト、吸着材、及び分離方法 - Google Patents
Gis型ゼオライト、吸着材、及び分離方法 Download PDFInfo
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- WO2023067841A1 WO2023067841A1 PCT/JP2022/021932 JP2022021932W WO2023067841A1 WO 2023067841 A1 WO2023067841 A1 WO 2023067841A1 JP 2022021932 W JP2022021932 W JP 2022021932W WO 2023067841 A1 WO2023067841 A1 WO 2023067841A1
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- WIPO (PCT)
- Prior art keywords
- zeolite
- gis
- adsorption
- type zeolite
- potassium
- Prior art date
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- 239000010457 zeolite Substances 0.000 title claims abstract description 253
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 232
- 238000000926 separation method Methods 0.000 title claims description 34
- 239000003463 adsorbent Substances 0.000 title claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims description 136
- 229910052700 potassium Inorganic materials 0.000 claims description 48
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 46
- 229910052782 aluminium Inorganic materials 0.000 claims description 44
- 239000011591 potassium Substances 0.000 claims description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 150000001340 alkali metals Chemical class 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 148
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 117
- 239000000499 gel Substances 0.000 description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 81
- 229910002092 carbon dioxide Inorganic materials 0.000 description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 73
- 239000001569 carbon dioxide Substances 0.000 description 58
- 238000000034 method Methods 0.000 description 41
- 229960003975 potassium Drugs 0.000 description 41
- -1 salt compound Chemical class 0.000 description 41
- 238000003756 stirring Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000003795 chemical substances by application Substances 0.000 description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 31
- 238000003795 desorption Methods 0.000 description 29
- 239000011734 sodium Substances 0.000 description 29
- 239000000377 silicon dioxide Substances 0.000 description 26
- 239000013078 crystal Substances 0.000 description 22
- 238000001027 hydrothermal synthesis Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000002336 sorption--desorption measurement Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 229910001388 sodium aluminate Inorganic materials 0.000 description 16
- 238000000504 luminescence detection Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 14
- 150000001342 alkaline earth metals Chemical class 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 239000011959 amorphous silica alumina Substances 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 235000010724 Wisteria floribunda Nutrition 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 235000011181 potassium carbonates Nutrition 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 229910052701 rubidium Inorganic materials 0.000 description 8
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 7
- 229910052792 caesium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 235000010344 sodium nitrate Nutrition 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005341 cation exchange Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229940091250 magnesium supplement Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- 235000011008 sodium phosphates Nutrition 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000490 cosmetic additive Substances 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 229910052913 potassium silicate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000012690 zeolite precursor Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 2
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
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- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
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- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
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- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- SIWNEELMSUHJGO-UHFFFAOYSA-N 2-(4-bromophenyl)-4,5,6,7-tetrahydro-[1,3]oxazolo[4,5-c]pyridine Chemical compound C1=CC(Br)=CC=C1C(O1)=NC2=C1CCNC2 SIWNEELMSUHJGO-UHFFFAOYSA-N 0.000 description 1
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- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- FKBLOGDSDFJGKB-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;rubidium(1+) Chemical compound [Rb+].[Rb+].[Rb+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FKBLOGDSDFJGKB-UHFFFAOYSA-K 0.000 description 1
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- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- ZRXHLJNBNWVNIM-UHFFFAOYSA-N 3-methyl-1-benzofuran Chemical compound C1=CC=C2C(C)=COC2=C1 ZRXHLJNBNWVNIM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QWNKFHSKFIOVSK-UHFFFAOYSA-N 7-chloro-4-(trifluoromethyl)-1h-indole-2-carboxylic acid Chemical compound C1=CC(Cl)=C2NC(C(=O)O)=CC2=C1C(F)(F)F QWNKFHSKFIOVSK-UHFFFAOYSA-N 0.000 description 1
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- SUWRYHSENBOMCY-UHFFFAOYSA-N B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+] Chemical compound B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+].[Cs+] SUWRYHSENBOMCY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910014130 Na—P Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- CWVZGJORVTZXFW-UHFFFAOYSA-N [benzyl(dimethyl)silyl]methyl carbamate Chemical compound NC(=O)OC[Si](C)(C)CC1=CC=CC=C1 CWVZGJORVTZXFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
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- UNLSXXHOHZUADN-UHFFFAOYSA-N barium cyanide Chemical compound [Ba+2].N#[C-].N#[C-] UNLSXXHOHZUADN-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
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- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
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- 229910052916 barium silicate Inorganic materials 0.000 description 1
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- PAVWOHWZXOQYDB-UHFFFAOYSA-H barium(2+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PAVWOHWZXOQYDB-UHFFFAOYSA-H 0.000 description 1
- UXFOSWFWQAUFFZ-UHFFFAOYSA-L barium(2+);diformate Chemical compound [Ba+2].[O-]C=O.[O-]C=O UXFOSWFWQAUFFZ-UHFFFAOYSA-L 0.000 description 1
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 description 1
- ONPIOWQPHWNPOQ-UHFFFAOYSA-L barium(2+);dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ba+2].[O-]S([O-])(=O)=S ONPIOWQPHWNPOQ-UHFFFAOYSA-L 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- LSWZMKLTBNIIHY-UHFFFAOYSA-N barium(2+);oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Ba+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O LSWZMKLTBNIIHY-UHFFFAOYSA-N 0.000 description 1
- ACOIWNYPCCHUDF-UHFFFAOYSA-N barium(2+);tetraborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] ACOIWNYPCCHUDF-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- BROHICCPQMHYFY-UHFFFAOYSA-N caesium chromate Chemical compound [Cs+].[Cs+].[O-][Cr]([O-])(=O)=O BROHICCPQMHYFY-UHFFFAOYSA-N 0.000 description 1
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- WKDKOOITVYKILI-UHFFFAOYSA-M caesium perchlorate Chemical compound [Cs+].[O-]Cl(=O)(=O)=O WKDKOOITVYKILI-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
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- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
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- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 description 1
- RMISVBXFFXBNAD-UHFFFAOYSA-N calcium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Ca+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O RMISVBXFFXBNAD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
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- XTCPEYCUFMHXBI-UHFFFAOYSA-N cesium;cyanide Chemical compound [Cs+].N#[C-] XTCPEYCUFMHXBI-UHFFFAOYSA-N 0.000 description 1
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- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OKDOLBRCQSOMNV-UHFFFAOYSA-L dicesium dioxido-oxo-sulfanylidene-lambda6-sulfane Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=S OKDOLBRCQSOMNV-UHFFFAOYSA-L 0.000 description 1
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 description 1
- AQWIYQPYXQGBQU-UHFFFAOYSA-N dicesium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Cs+].[Cs+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O AQWIYQPYXQGBQU-UHFFFAOYSA-N 0.000 description 1
- RQASKKKCNLAJJF-UHFFFAOYSA-L dicesium;sulfite Chemical compound [Cs+].[Cs+].[O-]S([O-])=O RQASKKKCNLAJJF-UHFFFAOYSA-L 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- GMKDNCQTOAHUQG-UHFFFAOYSA-L dilithium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=S GMKDNCQTOAHUQG-UHFFFAOYSA-L 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- GLGSRACCZFMWDT-UHFFFAOYSA-N dilithium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Li+].[Li+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GLGSRACCZFMWDT-UHFFFAOYSA-N 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- UCEQBRIYUDETAF-UHFFFAOYSA-L dioxido-oxo-sulfanylidene-lambda6-sulfane rubidium(1+) Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=S UCEQBRIYUDETAF-UHFFFAOYSA-L 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- KKKYJLNWARAYSD-UHFFFAOYSA-N hexacalcium;tetraborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KKKYJLNWARAYSD-UHFFFAOYSA-N 0.000 description 1
- NTFWINCUXYNHSF-UHFFFAOYSA-N hexamagnesium;tetraborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] NTFWINCUXYNHSF-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910002096 lithium permanganate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- FKWSMBAMOQCVPV-UHFFFAOYSA-N magnesium dicyanide Chemical compound [Mg+2].N#[C-].N#[C-] FKWSMBAMOQCVPV-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 description 1
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 description 1
- GIOZLVMCHDGNNZ-UHFFFAOYSA-N magnesium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Mg+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GIOZLVMCHDGNNZ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DUXDETQJUQZYEX-UHFFFAOYSA-L oxalate;rubidium(1+) Chemical compound [Rb+].[Rb+].[O-]C(=O)C([O-])=O DUXDETQJUQZYEX-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940010109 rubidium nitrite Drugs 0.000 description 1
- 229910001489 rubidium perchlorate Inorganic materials 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- SBRXQVGXQDDCIK-UHFFFAOYSA-L rubidium(1+) sulfite Chemical compound [Rb+].[Rb+].[O-]S([O-])=O SBRXQVGXQDDCIK-UHFFFAOYSA-L 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- GZXRGRLACABJNC-UHFFFAOYSA-M rubidium(1+);chlorate Chemical compound [Rb+].[O-]Cl(=O)=O GZXRGRLACABJNC-UHFFFAOYSA-M 0.000 description 1
- LVVHSFSKNVFYAG-UHFFFAOYSA-N rubidium(1+);cyanide Chemical compound [Rb+].N#[C-] LVVHSFSKNVFYAG-UHFFFAOYSA-N 0.000 description 1
- ZIMBPNXOLRMVGV-UHFFFAOYSA-M rubidium(1+);formate Chemical compound [Rb+].[O-]C=O ZIMBPNXOLRMVGV-UHFFFAOYSA-M 0.000 description 1
- VPMVPQJJBGXJAI-UHFFFAOYSA-M rubidium(1+);nitrite Chemical compound [Rb+].[O-]N=O VPMVPQJJBGXJAI-UHFFFAOYSA-M 0.000 description 1
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical compound [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- QVDIYEVPFLCTGI-UHFFFAOYSA-N rubidium(1+);tetraborate Chemical compound [Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[Rb+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] QVDIYEVPFLCTGI-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
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- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- FRTABACCYANHFP-UHFFFAOYSA-L strontium chlorate Chemical compound [Sr+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O FRTABACCYANHFP-UHFFFAOYSA-L 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QZRNTVPRGQDWRA-UHFFFAOYSA-N strontium;boron;oxygen(2-) Chemical compound [B].[O-2].[Sr+2] QZRNTVPRGQDWRA-UHFFFAOYSA-N 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- WTNNIXSCSYFNFP-UHFFFAOYSA-N strontium;dicyanide Chemical compound [Sr+2].N#[C-].N#[C-] WTNNIXSCSYFNFP-UHFFFAOYSA-N 0.000 description 1
- FXWRHZACHXRMCI-UHFFFAOYSA-L strontium;diformate Chemical compound [Sr+2].[O-]C=O.[O-]C=O FXWRHZACHXRMCI-UHFFFAOYSA-L 0.000 description 1
- HOWFTCIROIVKLW-UHFFFAOYSA-L strontium;dinitrite Chemical compound [Sr+2].[O-]N=O.[O-]N=O HOWFTCIROIVKLW-UHFFFAOYSA-L 0.000 description 1
- KGQWMJMXLOXFSX-UHFFFAOYSA-L strontium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Sr+2].[O-]S([O-])(=O)=S KGQWMJMXLOXFSX-UHFFFAOYSA-L 0.000 description 1
- MXRFIUHRIOLIIV-UHFFFAOYSA-L strontium;diperchlorate Chemical compound [Sr+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MXRFIUHRIOLIIV-UHFFFAOYSA-L 0.000 description 1
- JLGUDDVSJCOLTN-UHFFFAOYSA-N strontium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Sr+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JLGUDDVSJCOLTN-UHFFFAOYSA-N 0.000 description 1
- VTBSJEPGLHXIIS-UHFFFAOYSA-L strontium;sulfite Chemical compound [Sr+2].[O-]S([O-])=O VTBSJEPGLHXIIS-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- WDNRWJRRUZRRNB-UHFFFAOYSA-K tricesium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cs+].[Cs+].[Cs+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WDNRWJRRUZRRNB-UHFFFAOYSA-K 0.000 description 1
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- QGAPCDHPGCYAKM-UHFFFAOYSA-H tristrontium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QGAPCDHPGCYAKM-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Images
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
Definitions
- the present invention relates to GIS-type zeolites, adsorbents, and separation methods.
- Zeolites can be used as adsorbents, desiccants, separating agents, catalysts, catalyst carriers, detergent aids, ion exchange agents, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc. Among them, gas separation applications It is useful as
- GIS-type zeolites are called GIS-type zeolites with codes that define the structure of zeolites defined by the IZA (International Zeolite Association).
- a GIS type zeolite is a zeolite having pores composed of eight-membered oxygen rings. Such GIS-type zeolites are described, for example, in Patent Documents 1-4 and Non-Patent Documents 1-7.
- Patent Document 1 it is described that GIS type zeolite is synthesized in order to effectively use slag of coal combustion ash, and in Patent Document 2, a zeolite coating (GIS type zeolite) is formed on the surface of an aluminum plate. It is described that the thermal conductivity is improved by Non-Patent Documents 1, 2 and 3 disclose silica-alumina GIS-type zeolites, and none of the reports shows almost any adsorption of carbon dioxide.
- Non-Patent Document 4 discloses a GIS-type zeolite of silicoaluminophosphate containing phosphoric acid, which adsorbs not only carbon dioxide but also oxygen, nitrogen, and methane.
- Non-Patent Documents 5 and 6 also disclose silica-alumina GIS-type zeolite, but do not mention the adsorption performance of carbon dioxide and the like.
- Patent Documents 3 and 4 disclose GIS-type zeolite with an adjusted crystal structure, which has an adsorption capacity for carbon dioxide, but the amount of carbon dioxide adsorption is not sufficient. There is no mention of desorption hysteresis.
- Non-Patent Document 7 discloses a GIS-type zeolite in which the cations in the zeolite are substituted with Li, Na, K, Rb, and Cs, and has an adsorption capacity for carbon dioxide, but in the carbon dioxide adsorption-desorption isotherm Adsorption/desorption hysteresis is observed.
- JP-A-06-340417 Japanese Patent Publication No. 2012-519148 International publication WO2018/110559 International publication WO2019/202933
- a pressure swing adsorption separation method When separating, recovering, and purifying carbon dioxide using an adsorbent, a pressure swing adsorption separation method, a temperature swing adsorption separation method, or a pressure/temperature swing adsorption separation method is used.
- a pressure swing adsorption separation method As the performance, it is required that the amount of carbon dioxide adsorbed is large, carbon dioxide is selectively adsorbed, the selectivity with respect to the gas to be separated is high, and there is no carbon dioxide adsorption/desorption hysteresis.
- Adsorption/desorption hysteresis represents a phenomenon in which hysteresis occurs between adsorption and desorption in the adsorption/desorption isotherm of carbon dioxide.
- Patent Documents 1 and 2 do not mention the adsorption of carbon dioxide by zeolite, and according to the structural analysis results shown in these, the crystal structure necessary for selectively adsorbing carbon dioxide is clear. It is difficult to say that it is formed. That is, the zeolites described in Patent Documents 1 and 2 are considered to have insufficient carbon dioxide adsorption capacity.
- Non-Patent Documents 1 and 2 do not adsorb carbon dioxide, and carbon dioxide and molecules with larger molecular diameters such as oxygen, nitrogen, methane, etc. cannot be separated by adsorption or gas permeation.
- the reason for this is that the eight-membered ring of the GIS-type zeolite is distorted, has an elliptical shape with a major axis of 4.5 ⁇ and a minor axis of 3.1 ⁇ , and a carbon dioxide molecule with an average molecular diameter of 3.3 ⁇ . It is thought that this is because it cannot easily enter the pores.
- Non-Patent Document 3 discloses a GIS-type zeolite of silicoaluminophosphate, and since the bond distance and bond angle are different from those of silica alumina, the eight-membered ring pores are slightly larger, and carbon dioxide adsorption is observed. However, the adsorption amount cannot be said to be sufficiently high, and the adsorption of oxygen, nitrogen and methane cannot be said to be sufficiently low, resulting in a low selectivity in the separation from carbon dioxide.
- Non-Patent Documents 5 and 6 when the present inventor analyzed zeolites synthesized according to the descriptions of Non-Patent Documents 5 and 6, a suitable structure could not be formed in 29 Si-NMR, and GIS-type zeolite It has been found that the carbon dioxide adsorption performance cannot be exhibited.
- Patent Documents 3 and 4 GIS-type zeolites having a maximum carbon dioxide adsorption amount of 52.4 cc/g and 67.5 cc/g, respectively, are obtained by optimizing the crystal structure of the GIS-type zeolite.
- Non-Patent Document 7 discloses a GIS-type zeolite in which the cations in the zeolite are substituted with Li, Na, K, Rb, and Cs, and the GIS-type zeolite has a maximum carbon dioxide adsorption amount of 82.9 cc / g. was obtained, but adsorption-desorption hysteresis was observed in the adsorption-desorption isotherm of carbon dioxide.
- An object of the present invention is to provide a GIS-type zeolite with a small adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm, an adsorbent containing the same, and a separation method using the same.
- the present inventors have made intensive studies to solve the above problems, and found that the silica-alumina ratio of the GIS-type zeolite is within a predetermined range, and the spectrum obtained by 29 Si-MAS-NMR measurement has a specific The inventors have found that the problem can be solved when the spectral area intensity ratio of is within a predetermined value range, and have completed the present invention.
- the present invention is as follows.
- a GIS type zeolite, The silica-alumina ratio is 3.40 or more,
- the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the 29 Si-MAS-NMR spectrum are a, b, c, and d, respectively, and
- the GIS-type zeolite according to [1] which contains potassium as a cationic species in the zeolite.
- [3] The GIS-type zeolite according to [2], wherein the ratio of potassium atomic concentration to aluminum atomic concentration (K/Al) in the zeolite is 0.05 or more.
- [4] [1] to [3], wherein the ratio (A/T) of the total amount of potassium and lithium substances (A) to the total amount of alkali metal substances (T) in the zeolite is 0.05 or more; GIS-type zeolite according to any one of.
- [5] The GIS-type zeolite according to any one of [1] to [4], which has a carbon atom content of 4% by mass or less.
- [6] The GIS-type zeolite according to any one of [1] to [5], containing silica alumina.
- An adsorbent comprising the GIS-type zeolite according to any one of [1] to [6].
- the separation method according to [8] wherein the gas is separated by a pressure swing adsorption separation method, a temperature swing adsorption separation method, or a pressure/temperature swing adsorption separation method.
- the present invention it is possible to provide a GIS-type zeolite with a small adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm, an adsorbent containing the same, and a separation method using the same.
- FIG. 1 is a 29 Si-MAS-NMR diagram of the GIS-type zeolite obtained in Example 1.
- FIG. 2 is an adsorption isotherm and a desorption isotherm of carbon dioxide of the GIS-type zeolite obtained in Comparative Example 1.
- FIG. 3 is a diagram illustrating an adsorbent according to one embodiment of the invention.
- this embodiment the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail.
- the present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.
- the GIS-type zeolite has a small adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm.
- the GIS-type zeolite has a sufficiently large amount of carbon dioxide to be adsorbed, and can adsorb carbon dioxide with high selectivity when separating gas species such as nitrogen and methane from carbon dioxide.
- the adsorption-desorption hysteresis is small in the adsorption-desorption isotherm of carbon dioxide, the amount of carbon dioxide adsorbed is sufficiently large, and It is possible to provide a GIS-type zeolite that can selectively adsorb only carbon dioxide when separating gas species such as carbon dioxide and nitrogen and methane.
- the bonding mode of Si and Al affects the structural change during adsorption and desorption of the zeolite framework itself.
- the GIS-type zeolite according to the present embodiment has a silica-alumina ratio (which represents the molar ratio between silica and alumina represented by SiO 2 /Al 2 O 3 , hereinafter also referred to as “SAR”) of 3.40 or more.
- SAR silica-alumina ratio
- the SAR is more preferably 4.40 or higher, still more preferably 4.80 or higher.
- the upper limit of the SAR is not particularly limited, but if the SAR is too high, the interaction with the adsorbate becomes small.
- SAR can be calculated from the area intensity of the spectrum obtained by 29 Si-MAS-NMR measurement of zeolite. More specifically, the SAR measurement method is the method shown in Examples.
- the SAR is high in the GIS-type zeolite, it is confirmed that the adsorption-desorption hysteresis in the adsorption-desorption isotherm of carbon dioxide becomes apparent.
- the adsorption/desorption hysteresis in the carbon dioxide adsorption/desorption isotherm can be eliminated by controlling the bonding mode of Si and Al in the zeolite skeleton.
- the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the 29 Si-MAS-NMR spectrum are a, b, and c, respectively.
- the peaks such as Q4 (3Al), Q4 (2Al), Q4 (1Al), and Q4 (0Al) observed in the 29 Si-MAS-NMR spectrum represent the bonding modes of Si and Al in the zeolite framework, and the sum of the area intensities , X and Y represent the sum of the abundances of those bonding modes, and Z represents the abundance ratio. Since the abundance ratio of the bonding modes of Si and Al affects the structural change of the zeolite framework itself during adsorption and desorption, Z, which is the abundance ratio of the bonding modes of Si and Al in the zeolite framework, is set within an appropriate range. Therefore, the adsorption/desorption hysteresis in the adsorption/desorption isotherm can be eliminated.
- 29 Si-MAS-NMR spectrum was obtained by preparing a desiccator filled with water at the bottom, and holding zeolite in a sample tube at the top of the desiccator at room temperature (25 ° C.) for 48 hours. and then measured with a solid-state NMR spectrometer.
- solid-state NMR measurement devices include JEOL's "RESONANCE ECA700” (magnetic field strength: 16.44 T (resonance frequency in 1 H: 700 MHz)).
- the GIS-type zeolite of this embodiment generally exhibits the following five peaks in the 29 Si-MAS-NMR spectrum.
- Q4 (4Al) ) peak of Si bonded to four Al via oxygen
- the peak area intensity of the 29 Si-MAS-NMR spectrum was analyzed using Gaussian and Lorentzian functions using the analysis program dmfit (#202000113 version). , ppm), width (full width at half maximum of spectrum, ppm), and Gaussian/Lorentzian ratio (xG/(1-x)L) by the least squares algorithm.
- the peak area intensity a, b, c, d attributed to Q4 (3Al), Q4 (2Al), Q4 (1Al), Q4 (0Al), and the sum thereof , and Z, which is the ratio thereof, can be obtained.
- the GIS-type zeolite preferably contains silica-alumina from the viewpoint of further improving the selective adsorption capacity of carbon dioxide.
- the GIS-type zeolite of the present embodiment preferably contains silica and alumina as main components (80% by mass or more).
- a main component is a component that accounts for 80% by mass or more.
- the aluminum content in the GIS-type zeolite of the present embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more.
- the upper limit of the aluminum content is not particularly limited as long as the SAR satisfies the above-described predetermined range, and is determined by the silica content and the SAR value.
- the content of silicon in the GIS-type zeolite of the present embodiment is preferably 3% by mass or more, more preferably 5% by mass or more.
- the upper limit of the silicon content is not particularly limited as long as the SAR satisfies the above-described predetermined range, and is determined by the alumina content and the SAR value.
- the phosphorus content in the GIS-type zeolite of the present embodiment is preferably 4% by mass or less.
- the lower limit of the phosphorus content is not particularly limited, and may be 0% by mass or more.
- the Zr content in the GIS-type zeolite of the present embodiment is preferably 8% by mass or less.
- the lower limit of the Zr content is not particularly limited, and may be 0% by mass or more.
- the Ti content in the GIS-type zeolite of the present embodiment is preferably 8% by mass or less.
- the lower limit of the Ti content is not particularly limited, and may be 0% by mass or more.
- the content of phosphorus atoms in the GIS-type zeolite of the present embodiment is more preferably 1.5% by mass or less, and particularly preferably 0% by mass.
- the content of aluminum, silicon, phosphorus, Zr and Ti can be measured by the method described in the examples below.
- the content of aluminum, silicon, phosphorus, Zr and Ti is adjusted to the range described above, for example, by adjusting the composition ratio of the mixed gel used for synthesizing the GIS-type zeolite to the preferred range described later. can do.
- the carbon atom content is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, relative to the total amount of the GIS-type zeolite.
- the carbon atom content can be measured by CHN elemental analysis. By measuring the content of carbon atoms, it is possible to quantify the organic structure-defining material or a substance that is a modified material.
- an organic structure directing material can be used during synthesis. As described above, the smaller the number, the better.
- the cation species in the GIS-type zeolite preferably contains potassium or lithium, and more preferably contains potassium.
- the total content of potassium and lithium in the zeolite is the ratio (A/T) of the total amount of potassium and lithium (A) to the total amount of alkali metal (T) in the GIS-type zeolite.
- A/T is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more.
- A/T may be 1.00 or less.
- A/T can be measured by thermally dissolving zeolite in an aqueous sodium hydroxide solution or aqua regia, and then performing ICP-luminescence spectroscopic analysis using a solution that has been appropriately diluted. More specifically, A/T can be measured by the method described in Examples below. A/T can be adjusted by changing the ratio of potassium and lithium cationic species in the GIS-type zeolite. It is preferable that the ratio (K/T) of the total amount of potassium (K) to the total amount (T) of each alkali metal in the GIS-type zeolite is 0.05 or more, more preferably. is 0.10 or more, more preferably 0.15 or more. Although the upper limit of K/T is not particularly limited, K/T may be 1.00 or less.
- the above carbon atom content, potassium atom content, SAR, and 29 Si-MAS-NMR spectrum can be measured by the methods described in Examples below. Further, it can be adjusted to the range described above by adjusting the conditions for synthesizing the GIS-type zeolite to the preferable range described later.
- the method for producing a GIS-type zeolite according to the present embodiment includes, for example, a silica source containing silicon, an aluminum source containing aluminum, an alkali source containing at least one selected from an alkali metal (M1) and an alkaline earth metal (M2). , a mixed gel containing a salt compound containing at least one selected from alkali metal (M1) and alkaline earth metal (M2), a phosphorus source containing phosphorus, an organic structure directing agent and water. can.
- a silica source containing silicon an aluminum source containing aluminum
- an alkali source containing at least one selected from an alkali metal (M1) and an alkaline earth metal (M2).
- M1 and an alkaline earth metal M2
- a mixed gel containing a salt compound containing at least one selected from alkali metal (M1) and alkaline earth metal (M2) a phosphorus source containing phosphorus
- organic structure directing agent an organic structure directing agent
- the mixed gel in this embodiment is a mixture containing a silica source, an aluminum source, a salt compound, and water as components, and optionally a phosphorus source, an alkali source, and an organic structure-directing agent.
- the silica source is a component in the mixed gel that serves as a raw material for silicon contained in the zeolite produced from the mixed gel
- the aluminum source is a raw material for aluminum contained in the zeolite produced from the mixed gel.
- the salt compound refers to a component that is a raw material for the alkali metal and/or alkaline earth metal contained in the zeolite produced from the mixed gel
- the alkali source refers to the mixture It refers to a component that adjusts the alkalinity of the gel
- the phosphorus source refers to a component in the mixed gel that serves as a raw material for phosphorus contained in zeolite produced from the mixed gel.
- the silica source is not particularly limited as long as it is generally used, and examples thereof include crystalline silica, amorphous silica, silicic acid, silicates, organic silicic acid compounds, and the like. More specific examples include sodium silicate, potassium silicate, calcium silicate, magnesium silicate, fumed silica, precipitated silica, silica gel, colloidal silica, aluminosilicate, tetraethoxysilane (TEOS), trimethylethoxysilane, and the like. be done. These compounds may be used singly or in combination.
- the aluminosilicate serves as a silica source as well as an aluminum source.
- fumed silica, colloidal silica, or precipitated silica are preferred because they tend to yield zeolite with a high degree of crystallinity.
- the aluminum source is not particularly limited as long as it is commonly used, but specific examples include sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxide, aluminum chloride, and aluminum alkoxide. , metallic aluminum, amorphous aluminosilicate gel, and the like. These compounds may be used singly or in combination.
- sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxide are preferred because they tend to yield zeolite with a high degree of crystallinity. From the same point of view, sodium aluminate and aluminum hydroxide are more preferred, and sodium aluminate is even more preferred.
- Salt compounds are compounds containing alkali metals such as Li, Na, K, Rb, and Cs, and alkaline earth metals such as Ca, Mg, Sr, and Ba, which promote crystallization into a zeolite structure when producing zeolite. be.
- alkali metals and alkaline earth metals contained in the salt compound to be added are preferably Na and K, and more preferably Na, from the viewpoint of facilitating the formation of crystals of the GIS type skeleton.
- the salt compounds may be used singly or in combination.
- salt compounds include, but are not limited to, sodium sulfate, sodium sulfite, sodium thiosulfate, sodium nitrite, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium acetate, formic acid, sodium, sodium citrate, sodium oxalate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, thiosodium, sodium silicate, sodium metasilicate, sodium tetraborate, sodium chlorate, sodium perchlorate, sodium cyanide, sodium metastannate, sodium hexahydroxidostannate(IV), sodium hexacyanideferrate(II), sodium permanganate, sodium chromate, sodium dichromate, Potassium sulfate, potassium sulfite, potassium thiosulfate, potassium nitrite, potassium nitrate, potassium carbonate, potassium hydrogen carbonate, potassium phosphate, potassium acetate, potassium formate, potassium
- the alkalinity source is used for the purpose of adjusting the alkalinity (pH) in the mixed gel in order to promote the crystallization into the zeolite structure when producing the zeolite.
- the alkali to be used may be any compound that exhibits alkalinity, and may be either an inorganic compound or an organic compound, but from the viewpoint of cost, an inorganic compound is preferred, and an alkali metal hydroxide is more preferred.
- Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, preferably sodium hydroxide and potassium hydroxide, more preferably hydroxide. sodium. These compounds may be used singly or in combination.
- the phosphorus source is not particularly limited as long as it is commonly used, but specific examples include phosphoric acid aqueous solution, sodium phosphate, aluminum phosphate, potassium phosphate, lithium phosphate, calcium phosphate, and barium phosphate. etc. These compounds may be used singly or in combination.
- phosphoric acid aqueous solution, sodium phosphate, and aluminum phosphate are preferable because they tend to yield zeolite with a high degree of crystallinity. From the same point of view, an aqueous phosphoric acid solution and sodium phosphate are more preferred, and an aqueous phosphoric acid solution is even more preferred.
- the organic structure-directing agent in producing zeolite by hydrothermally synthesizing a mixed gel is a compound that promotes crystallization into a zeolite structure.
- an organic structure-directing agent can be used as necessary.
- the organic structure-directing agent may be of any type as long as it can form the desired GIS-type zeolite. Further, the organic structure-directing agents may be used singly or in combination.
- organic structure-directing agents include, but are not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkylureas, alkylthioureas, cyanoalkanes, containing nitrogen as a heteroatom.
- Alicyclic heterocyclic compounds can be used, preferably alkylamines, more preferably isopropylamine.
- Some such salts are associated with an anion.
- Representatives of such anions include, but are not limited to, halogen ions such as Cl ⁇ , Br ⁇ , I ⁇ , hydroxide ions, acetate ions, sulfate ions, nitrate ions, carbonate ions and carbonate ions. Contains hydrogen ions. Among these, halogen ions and hydroxide ions are preferred, and halogen ions are more preferred, from the viewpoint of facilitating the formation of crystals of the GIS type skeleton.
- composition ratio of mixed gel addition of a salt compound containing an alkali metal and/or an alkaline earth metal is most important for synthesizing a GIS-type zeolite with an appropriate structure.
- the silica source and aluminum source dissolved in the water solvent react while dissolving and crystallize, but the addition of a salt compound adjusts the Si and Al bonding mode and their abundance ratio in the zeolite skeleton. It is possible to synthesize a GIS having an ideal crystal structure.
- the ratio of cations to aluminum source provided by the addition of the salt compound is of particular importance.
- the cation to aluminum source ratio provided by the salt compound in the mixed gel is expressed as the additive molar ratio of the amount of cations E to Al 2 O 3 , ie E/Al 2 O 3 .
- E represents the molar amount of cations provided by the salt compound .
- E represents the added molar amount of cationic species produced.
- E/Al 2 O 3 can change the aggregation state of Al in the mixed gel, leading to control of the randomness of Al during zeolite crystal formation, resulting in a GIS-type zeolite having an ideal crystal structure. Synthesis becomes possible.
- E/Al 2 O 3 is preferably 0.1 or more and 100.0 or less, more preferably 0.5 or more and 80.0. It is 0 or less, more preferably 0.8 or more and 50.0 or less.
- OH - is OH - derived from inorganic hydroxides such as NaOH and Ca(OH) 2 used as alkali sources and organic hydroxides such as tetraethylammonium hydroxide, and is derived from sodium aluminate and sodium silicate. does not include oxides represented by , or OH - emitted when dissolving the hydrates in water.
- the silica source, aluminum source, and alkali source dissolved in the water solvent are crystallized, and a part of them are eluted into the alkaline solvent, and the equilibrium between crystallization and re-dissolution occurs.
- Adding OH ⁇ derived from inorganic hydroxides such as NaOH and Ca(OH) 2 and organic hydroxides such as tetraethylammonium hydroxide to the mixed gel means that the equilibrium between crystallization and re-dissolution is re-dissolved. It means to move to the side. Redissolution progresses from the amorphous or low crystalline portion.
- the incomplete crystal portion is redissolved and crystallized again, and the formation of the ideal crystal structure can be increased.
- OH - increases too much, excessive dissolution proceeds, crystals cannot be obtained, or other crystal phases such as ANA-type zeolite, which has a more stable structure, are formed.
- dissolved alumina is more reactive than silica, and alumina is more likely to be incorporated into crystals. Therefore, the SAR of the synthesized GIS-type zeolite should be optimized by adjusting the crystallization and re-dissolution rates and optimizing the ratio of silica and alumina incorporated into the crystals by appropriately adjusting OH- . can be done.
- H 2 O/Al 2 O 3 If the ratio of water to alumina (H 2 O/Al 2 O 3 ) is high, the components in the mixed gel are likely to be more uniformly dispersed, but if it is too high, the crystallization rate will be significantly reduced. Therefore, in order to synthesize a GIS-type zeolite with an optimum SAR and an optimum crystal structure, H 2 O /Al 2 O 3 should be optimally controlled.
- H 2 O/Al 2 O 3 and H 2 O/OH ⁇ are preferably 100 ⁇ H 2 O/Al 2 O 3 ⁇ 780 and 50 ⁇ H 2 O/OH ⁇ ⁇ 1000, More preferably 120 ⁇ H 2 O/Al 2 O 3 ⁇ 778 and 60 ⁇ H 2 O/OH ⁇ ⁇ 800, still more preferably 150 ⁇ H 2 O/Al 2 O 3 ⁇ 775 and 70 ⁇ H 2 O /OH ⁇ ⁇ 700.
- the ratio of silica source and aluminum source in the mixed gel is expressed as the molar ratio of the oxides of the respective elements, ie SiO2 / Al2O3 .
- the ratio of the synthesized zeolite and the silica-alumina ratio of the mixed gel do not match.
- the silica-alumina ratio of the synthesized zeolite is determined by other compositions and synthesis conditions.
- the ratio of SiO 2 /Al 2 O 3 in this mixed gel is not particularly limited as long as the ratio is such that zeolite can be formed. 0 or more and 70.0 or less are preferable, 3.5 or more and 65.0 or less are more preferable, and 4.0 or more and 60.0 or less are still more preferable.
- the ratio of the aluminum source to the alkali metal and alkaline earth metal in the mixed gel is expressed as the additive molar ratio of M12O and M2O to Al2O3 , that is, ( M12O +M2O)/ Al2O3 (where M1 represents an alkali metal and M2 represents an alkaline earth metal, which are calculated as oxides).
- M12O +M2O M12O +M2O
- Al2O3 where M1 represents an alkali metal and M2 represents an alkaline earth metal, which are calculated as oxides.
- (M1 2 O+M2O)/Al 2 O 3 is preferably 1.5 or more, more preferably 1.6 or more, from the viewpoint of facilitating crystal formation of the GIS-type skeleton. More preferably 1.65.
- (M1 2 O+M2O)/Al 2 O 3 is preferably 15.0 or less, more preferably 12.0 or less, from the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS type skeleton, and 10 0.0 or less is more preferable.
- the ratio of the phosphorus source and the aluminum source in the mixed gel is expressed as the molar ratio of the oxides of the respective elements, ie P2O5 / Al2O3 .
- This P 2 O 5 /Al 2 O 3 is not particularly limited as long as it is a ratio at which zeolite can be formed. is preferred, 0.6 or less is more preferred, 0.4 or less is even more preferred, and 0 is particularly preferred.
- the ratio of the aluminum source to the organic structure directing agent in the mixed gel is expressed as the molar ratio of the organic structure directing agent to Al2O3 , i.e., R/ Al2O3 .
- R represents an organic structure directing agent
- It is preferably less than 7.0, more preferably 6.0 or less, from the viewpoint of easier crystal formation of the GIS-type skeleton and/or shorter synthesis time and excellent economic efficiency in producing zeolite. It is preferably 5.0 or less, more preferably 5.0 or less.
- an organic structure-directing agent is used, the organic structure-directing agent remains in the zeolite pores, preventing carbon dioxide from entering the pores and reducing the amount of adsorption.
- R/Al 2 O 3 is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.
- the method for producing a GIS-type zeolite according to the present embodiment includes a silica source containing silicon, an aluminum source containing aluminum, and at least one selected from alkali metals (M1) and alkaline earth metals (M2).
- M1 and M2 alkali metals
- M2 alkaline earth metals
- a phosphorus source a phosphorus source
- the molar ratios ⁇ , ⁇ , ⁇ , ⁇ , and ⁇ represented by (3), (4), (5), and (6) are 0.1 ⁇ 100.0, 3.0 ⁇ 70.0, 1.5 ⁇ 15.0, 0 ⁇ 1.0, 100 ⁇ 780 and 50 ⁇ 1000, preferably 0.5 ⁇ 80.
- the GIS-type zeolite according to this embodiment is obtained by the above-described method for producing a GIS-type zeolite according to this embodiment.
- the GIS-type zeolite of the present embodiment can also be obtained by adding previously produced GIS-type zeolite as seed crystals to the mixed gel.
- the process for preparing the mixed gel is not particularly limited, but for example, a silica source, an aluminum source, a salt compound, water, and, if necessary, a phosphorus source, an alkali source, and an organic structure directing agent are mixed all at once or in multiple stages. and aging the mixture obtained in this mixing step.
- the silica source, aluminum source, salt compound, water, and optionally the phosphorus source, alkali source, and organic structure directing agent can be mixed at once or in multiple steps.
- the order when mixing in multiple stages is not limited, and may be selected as appropriate according to the conditions used. Mixing in multiple stages may be carried out with or without stirring.
- the stirring is not particularly limited as long as it is a generally used stirring method, but specific examples include methods using blade stirring, vibration stirring, rocking stirring, centrifugal stirring, and the like.
- the rotation speed for stirring is not particularly limited as long as it is a generally used stirring speed, but for example, it may be 1 rpm or more and less than 2000 rpm.
- the temperature of the mixing step is not particularly limited as long as it is a commonly used temperature, but for example, -20°C or higher and lower than 80°C can be mentioned.
- the time of the mixing step is not particularly limited and can be appropriately selected depending on the temperature of the mixing step, but it may be, for example, more than 0 minutes and 1000 hours or less.
- the aging process can be carried out either by standing still or by stirring.
- stirring in the aging step there is no particular limitation as long as it is a generally used stirring method, but specific examples include methods using blade stirring, vibration stirring, rocking stirring, centrifugal stirring, and the like. .
- the rotation speed for stirring is not particularly limited as long as it is a generally used stirring speed, but for example, it may be 1 rpm or more and less than 2000 rpm.
- the temperature of the aging step is not particularly limited as long as it is a commonly used temperature, but for example, -20°C or higher and lower than 80°C can be mentioned.
- the time for the aging process is not particularly limited, and can be appropriately selected depending on the temperature of the aging process.
- zeolite is dissolved in the raw materials and the formation and re-dissolution of zeolite precursors during the raw material mixing and aging processes.
- the formation of the zeolite precursor does not proceed excessively.
- the formation of ANA-type zeolite which has a more stable structure, tends to increase, so it is preferable not to ripen excessively.
- the raw materials are sufficiently mixed and the raw material gel is uniform.
- the combined time of the mixing step and the aging step is not particularly limited, and may be appropriately adjusted based on the composition of the raw materials, etc., in order to obtain zeolite with an appropriate structure.
- the time is typically preferably 1 minute or more and less than 24 hours, more preferably 3 minutes or more and less than 23 hours, still more preferably 10 minutes or more and 18 hours or less, even more preferably 12 minutes or more and 15 hours or less. Minutes or more and 6 hours or less are more preferable.
- the method for producing a GIS-type zeolite according to the present embodiment preferably further includes a hydrothermal synthesis step in which the hydrothermal synthesis temperature is 80°C to 200°C, and the hydrothermal synthesis temperature is 100°C to 180°C. is more preferred. That is, preferably, the mixed gel obtained in the preparation step is hydrothermally synthesized by holding the mixed gel at a predetermined temperature for a predetermined time while stirring or standing still.
- the temperature for hydrothermal synthesis is not particularly limited as long as it is a temperature that is commonly used, but it is preferably 80°C or higher from the viewpoint of shortening the synthesis time and improving the economic efficiency of zeolite production. From the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS-type skeleton, the temperature is more preferably 90° C. or higher, and even more preferably 100° C. or higher. From the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS-type skeleton, the temperature is more preferably 200° C. or lower, even more preferably 180° C. or lower, and even more preferably 170° C. or lower. The temperature for hydrothermal synthesis may be constant or may be changed stepwise.
- the time for hydrothermal synthesis is not particularly limited as long as it is a time generally used, and can be appropriately selected depending on the temperature of hydrothermal synthesis.
- the hydrothermal synthesis time is preferably 3 hours or longer, more preferably 10 hours or longer, from the viewpoint of formation of the GIS skeleton. From the viewpoint of obtaining highly crystalline GIS-type zeolite, the time is more preferably 24 hours or longer.
- the hydrothermal synthesis time is preferably 30 days or less, more preferably 20 days or less, and even more preferably 10 days or less, from the viewpoint of excellent economic efficiency when producing zeolite.
- the container in which the mixed gel is placed is not particularly limited as long as it is a commonly used container. In that case, it is preferable to put it in a pressure vessel and perform hydrothermal synthesis.
- the pressure-resistant container is not particularly limited, and various shapes such as a spherical shape, a vertically long shape, and a horizontally long shape can be used.
- the pressure container When stirring the mixed gel in the pressure container, the pressure container is rotated vertically and/or horizontally, preferably vertically.
- the rotation speed is not particularly limited as long as it is within the range generally used, but is preferably 1 to 50 rpm, more preferably 10 to 40 rpm.
- the separation method is not particularly limited as long as it is a general method, and filtration, decantation, spray drying (rotary spray, Nozzle spraying, ultrasonic spraying, etc.), a drying method using a rotary evaporator, a vacuum drying method, a freeze-drying method, a natural drying method, or the like can be used, and the separation can be usually performed by filtration or decantation.
- the separated material can be used as it is, or it can be washed with water or a predetermined solvent. If desired, the separated material can be dried.
- the temperature for drying the separated material is not particularly limited as long as it is a common drying temperature, but it is usually from room temperature to 150°C or less.
- the atmosphere for drying is not particularly limited as long as it is a generally used atmosphere, but an air atmosphere, an inert gas such as nitrogen or argon, or an oxygen-added atmosphere is usually used.
- calcined GIS type zeolite can be used.
- the firing temperature is not particularly limited as long as it is a temperature generally used, but when the organic structure-directing agent is desired to be removed, the remaining ratio can be reduced. is more preferable.
- a temperature of 360° C. or higher is more preferable from the viewpoint of shortening the calcination time and being excellent in economic efficiency when producing zeolite. Since the crystallinity of zeolite tends to be maintained, the temperature is preferably less than 450°C, more preferably 420°C or less, and even more preferably 400°C or less.
- the calcination time is not particularly limited as long as the organic structure-directing agent is sufficiently removed, and can be appropriately selected depending on the calcination temperature. Therefore, the time is preferably 0.5 hours or longer, more preferably 1 hour or longer, and even more preferably 3 hours or longer. Since the crystallinity of zeolite tends to be maintained, the time is preferably 10 days or less, more preferably 7 days or less, and even more preferably 5 days or less.
- the firing atmosphere is not particularly limited as long as it is a generally used atmosphere, but usually an air atmosphere, an inert gas such as nitrogen or argon, or an oxygen-added atmosphere is used.
- Cation exchange includes, but is not limited to, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, ammonium carbonate, or sodium nitrate, Nitrates such as potassium nitrate, lithium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, and ammonium nitrate; Carbonate ions, bicarbonate ions, acetate ions, salts changed to phosphate ions or hydrogen phosphate ions, and acids such as nitric acid and hydrochloric acid can be used.
- carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, ammonium carbonate, or sodium nitrate
- the cation exchange temperature is not particularly limited as long as it is a general cation exchange temperature, but it is usually from room temperature to 100°C or less.
- the separation method is not particularly limited as long as it is a general method, filtration, decantation, spray drying method (rotary atomization, nozzle atomization, ultrasonic atomization, etc.), rotary evaporator can be used, such as drying, vacuum drying, freeze-drying, or air-drying, and usually separation can be carried out by filtration or decantation.
- the separated material can be used as it is, or it can be washed with water or a predetermined solvent. If desired, the separated material can be dried.
- the temperature for drying the separated material is not particularly limited as long as it is a general drying temperature, but it is usually from room temperature to 150°C or less.
- the atmosphere for drying is not particularly limited as long as it is a generally used atmosphere, but an air atmosphere, an inert gas such as nitrogen or argon, or an oxygen-added atmosphere is usually used.
- ammonium-type zeolite can also be converted to proton-type zeolite by calcining the zeolite.
- the zeolite contains potassium atoms as cationic species.
- the potassium content in the zeolite is calculated as the ratio of the potassium atomic concentration to the aluminum atomic concentration (K/Al).
- the ratio (K/Al) of the potassium atomic concentration to the aluminum atomic concentration in the zeolite is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more. .
- K/Al is not particularly limited, but if K/Al exceeds 1.00, excessive K ion species will be present, so the ratio of potassium atomic number concentration to aluminum atomic number concentration in zeolite (K /Al) is preferably 2.00 or less, preferably 1.50 or less, and more preferably 1.00 or less.
- GIS-type zeolite of the present embodiment are not particularly limited. Catalysts for hydrocracking and alkylation, catalyst carriers for supporting metals and metal oxides, adsorbents, desiccants, detergent aids, ion exchange agents, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc. can be used as
- the GIS-type zeolite of the present embodiment can be suitably used as an adsorbent. That is, the adsorbent of this embodiment comprises the GIS-type zeolite of this embodiment. Since the adsorbent of the present embodiment is configured as described above, it can sufficiently adsorb carbon dioxide and has high selectivity for carbon dioxide adsorption relative to the amount of methane adsorbed. Therefore, for example, it can be particularly preferably used for purposes such as selective removal of carbon dioxide from natural gas.
- the configuration of the adsorbent of the present embodiment is not particularly limited as long as it comprises the GIS-type zeolite of the present embodiment, but typical configurations include the example shown in FIG.
- the adsorbent 1 of this embodiment illustrated in FIG. and particles 4 (GIS-type zeolite of the present embodiment).
- the filter 3 for example, a filter made of quartz can be used.
- adsorbent 1 when adsorbent 1 is used to remove carbon dioxide from natural gas, natural gas is introduced from the upper line, impurities are removed by filter 3, and then carbon dioxide is selectively removed by zeolite particles 4. It can be removed by adsorption and the methane-rich gas can be removed from the lower line.
- the object to be used for the adsorbent is not limited to natural gas, and the internal structure of the adsorbent is not limited to the example shown in FIG.
- the separation method of the present embodiment uses an adsorbent containing the GIS-type zeolite of the present embodiment, and contains two or more gases selected from the group consisting of H 2 , N 2 , O 2 , CO, and hydrocarbons.
- One or more selected from the group consisting of CO2 , H2O , He, Ne, Cl2 , NH3 , and HCl is separated from the mixture.
- at least one selected from the group consisting of CO 2 and H 2 O is separated from one or more gases selected from the group consisting of N 2 , O 2 , CO, and hydrocarbons. is preferred.
- hydrocarbons include, but are not limited to, methane, ethane, ethylene, propane, propylene, 1-butene, 2-butene, 2-methylpropene, dimethyl ether, and acetylene.
- the GIS-type zeolite of the present embodiment has a large CO 2 adsorption capacity, and physical adsorption without chemical bonds is observed.
- the separation method using the GIS-type zeolite of the present embodiment is not particularly limited, but a method that requires low energy during regeneration of the adsorbent and is excellent in economic efficiency is preferable. Specific examples of such a method are not particularly limited, but it is preferable to use any one of a pressure swing adsorption separation method, a temperature swing adsorption separation method, or a pressure/temperature swing adsorption separation method.
- the pressure swing adsorption separation method is a method in which the pressure at the time of desorption is lowered from the pressure at the time of gas adsorption, and the difference between the adsorption amount at high pressure and the adsorption amount at low pressure is used. It is a method for gas separation.
- the temperature swing type adsorption separation method TSA: Thermal Swing Adsorption
- TSA Thermal Swing Adsorption
- PTSA Pressure and Thermal Swing Adsorption
- ICP-AES ICP-luminescence spectrometry
- the concentration of various elements such as silicon, aluminum, phosphorus, potassium and lithium in zeolite was measured by The content of potassium and lithium in the zeolite was calculated as the ratio (A/T) of the sum of the amounts of potassium and lithium (A) to the sum of the amounts of alkali metals (T) in the zeolite. . K/T was also calculated in the same manner. Also, the potassium content in the zeolite was calculated as the ratio of the potassium atomic concentration to the aluminum atomic concentration (K/Al).
- X-ray diffraction was performed in the following procedure. (1) The dried materials obtained in each of the examples and comparative examples were used as samples and pulverized in an agate mortar. Further, 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was added, and the mixture was mixed in an agate mortar until uniform, which was used as a sample for structural analysis.
- the 29 Si-MAS-NMR measurement of zeolite was carried out by the following method. Also, the SAR of zeolite can be obtained by measuring 29 Si-MAS-NMR. First, to adjust the humidity of the zeolite, the bottom of the desiccator was filled with water, and the zeolite placed in the sample tube was held on top of the desiccator for 48 hours. After the humidity conditioning treatment, 29 Si-MAS-NMR was measured under the following conditions.
- the peak position may vary depending on the cationic species present in the zeolite skeleton, the peak position generally exists within the following range.
- Example 1 61.93 g of water, 0.403 g of sodium hydroxide (NaOH, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.39 g of sodium nitrate (NaNO3, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), sodium aluminate (NaAlO 2 , Fuji Film Wako Pure Chemical Co., Ltd.) 1.64 g and colloidal silica 10.82 g (Ludox AS-40, solid content concentration 40%, Grace) were mixed and stirred for 30 minutes to prepare a mixed gel.
- NaOH sodium hydroxide
- NaNO3 sodium nitrate
- NaNO3 sodium nitrate
- NaAlO 2 sodium aluminate
- Fuji Film Wako Pure Chemical Co., Ltd. 1.64 g
- colloidal silica 10.82 g Lidox AS-40, solid content concentration 40%, Grace
- the mixed gel was placed in a 200 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 135 ° C., Hydrothermal synthesis was carried out for 4 days.
- a powdery zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- Carbon atom concentration was measured by CHN analysis, but no carbon atoms were detected.
- Example 2 61.65 g of water, 0.60 g of 48% by mass sodium hydroxide aqueous solution (NaOH, solid content concentration 48% by mass, manufactured by Tokuyama Soda), 2.27 g of sodium carbonate (Na 2 CO 3 , manufactured by Tokuyama Soda), 1.64 g of sodium aluminate (NaAlO 2 , manufactured by Hokuriku Kasei Kogyo) and 10.82 g of colloidal silica (Ludox AS-40, solid content concentration 40%, manufactured by Grace) are mixed and mixed by stirring for 30 minutes. A gel was prepared.
- the mixed gel was charged in a 200 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 130 ° C., Hydrothermal synthesis was carried out for 5 days.
- a powdery zeolite was obtained. 1 g of the obtained zeolite was added to 500 mL of a 0.05 N potassium carbonate aqueous solution prepared using potassium carbonate (K 2 CO 3 , manufactured by Nippon Soda Co., Ltd.) and stirred at room temperature for 3 hours at 500 rpm. The product was filtered and dried at 120° C. to obtain a powdery zeolite with some of the cations exchanged for potassium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- Example 3 141.41 g of water, 2.62 g of aqueous sodium hydroxide solution (NaOH, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 8.53 g of sodium nitrate (NaNO 3 , manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO 2 ) , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 17.41 g of amorphous silica (Perkasil SM500, manufactured by Grace) were mixed and stirred for 1 hour to prepare a mixed gel.
- NaOH aqueous sodium hydroxide solution
- NaNO 3 sodium nitrate
- NaAlO 2 sodium aluminate
- Fuji Film Wako Pure Chemical Industries, Ltd. 17.41 g of amorphous silica
- the mixed gel was placed in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 130 ° C., Hydrothermal synthesis was carried out for 4 days.
- a powdery zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- Example 4 141.41 g of water, 2.62 g of aqueous sodium hydroxide solution (NaOH, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO 3 , manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO 2 ) , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 35.33 g of aluminosilicate (SIPERNAT 820A, manufactured by Evonik) were mixed and stirred for 1 hour to prepare a mixed gel.
- NaOH aqueous sodium hydroxide solution
- NaNO 3 sodium nitrate
- NaAlO 2 sodium aluminate
- SIPERNAT 820A manufactured by Evonik
- the mixed gel was placed in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 130 ° C., Hydrothermal synthesis was carried out for 5 days.
- a powdery zeolite was obtained. 1 g of the obtained zeolite was added to 500 mL of a 0.005N potassium carbonate aqueous solution prepared using potassium carbonate (K 2 CO 3 , manufactured by Nippon Soda Co., Ltd.) and stirred at room temperature for 3 hours at 500 rpm. The product was filtered and dried at 120° C. to obtain a powdery zeolite with some of the cations exchanged for potassium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- Example 5 21.05 g of water, 0.53 g of sodium hydroxide aqueous solution (NaOH, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 1.37 g of sodium nitrate (NaNO 3 , manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO 2 ) , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 15.5 g of Water Glass No. 3 (manufactured by Kishida Chemical Co., Ltd.) were mixed and stirred for 1 hour to prepare a mixed gel.
- NaOH sodium hydroxide aqueous solution
- NaNO 3 sodium nitrate
- NaAlO 2 sodium aluminate
- the mixed gel was placed in a 100 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 130 ° C., Hydrothermal synthesis was carried out for 5 days.
- a powdery zeolite was obtained. 1 g of the obtained zeolite was added to 500 mL of a 0.003 N potassium carbonate aqueous solution prepared using potassium carbonate (K 2 CO 3 , manufactured by Nippon Soda Co., Ltd.) and stirred at room temperature for 3 hours at 500 rpm. The product was filtered and dried at 120° C. to obtain a powdery zeolite with some of the cations exchanged for potassium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- the mixed gel was placed in a 200 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm, 135 ° C., Hydrothermal synthesis was carried out for 4 days.
- a powdery zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- the mixed gel was charged in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 60 rpm, 150 ° C., Hydrothermal synthesis was carried out for 3 days.
- a powdery zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- the mixed gel is charged into a 1000 mL stainless steel autoclave containing a fluororesin inner cylinder, hydrothermally synthesized at 130 ° C. for 5 days without stirring, the product is filtered and dried at 120 ° C., and powdered zeolite is obtained. rice field. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- Non-Patent Document 1 Based on the contents of Non-Patent Document 1, 132.86 g of water, 15.66 g of sodium hydroxide, 7.2 g of sodium aluminate (manufactured by Alpha Acer) and colloidal silica (Ludox AS-40, solid content concentration 40% by mass) ) and stirred at room temperature for 24 hours to prepare a mixed gel.
- the mixed gel is charged into a 200 mL stainless steel autoclave containing a fluororesin inner cylinder, hydrothermally synthesized at 100 ° C. for 7 days without stirring, the product is filtered and dried at 120 ° C., and powdered zeolite is obtained. rice field. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.
- the mixed gel was hydrothermally synthesized at 100° C. for 24 hours while being stirred at 1000 rpm, and the product was filtered and dried at 120° C. to obtain powdered GIS-type zeolite.
- the mixed gel was heated at 100° C. for 24 hours in an autoclave, and the product was filtered and dried at 120° C. to obtain powdered GIS type zeolite.
- the mixed gel was placed in a stainless steel micro bomb and heated at 200° C. for 7 days to synthesize zeolite.
- 1.134 g of aluminum powder Al, manufactured by Wako Pure Chemical Industries
- Al manufactured by Wako Pure Chemical Industries
- the mixed gel was hydrothermally synthesized at 100°C for 13 days, and the product was filtered and dried at 120°C to obtain powdered zeolite.
- the mixed gel is charged into a 1000 mL stainless steel autoclave containing a fluororesin inner cylinder, hydrothermally synthesized at 110 ° C. for 2 days without stirring, the product is filtered and dried at 120 ° C., and powdered zeolite is obtained. rice field.
- zeolite 1 g was added to 500 mL of a 0.1 N potassium nitrate aqueous solution and stirred at 60°C for 3 hours at 400 rpm. After filtering the product and drying at 120° C., a powdery zeolite with some of the cations exchanged for potassium was obtained.
- ⁇ to ⁇ in Table 1 represent the following molar ratios.
- ⁇ E/Al 2 O 3
- E represents the added molar amount of cationic species generated by the addition of the salt compound.
- ⁇ SiO2 / Al2O3
- ⁇ (M1 2 O+M2O)/Al 2 O 3 (wherein M1 represents an alkali metal and M2 represents an alkaline earth metal)
- ⁇ P2O5 / Al2O3
- ⁇ H 2 O/Al 2 O 3
- ⁇ H 2 O/OH ⁇
- ⁇ R/Al 2 O 3 (R represents an organic structure directing agent.)
- the GIS-type zeolite according to the present invention can be used for separating agents and membranes for various gases and liquids, electrolyte membranes for fuel cells, etc., fillers for various resin moldings, membrane reactors, catalysts for hydrocracking, alkylation, etc., metals, It has potential industrial applications as catalyst carriers for supporting metal oxides, adsorbents, desiccants, detergent aids, ion exchange agents, wastewater treatment agents, fertilizers, food additives, cosmetic additives, and the like.
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Abstract
Description
[1]
GIS型ゼオライトであって、
シリカアルミナ比が3.40以上であり、
29Si-MAS-NMRスペクトルで観測されるQ4(3Al)、Q4(2Al)、Q4(1Al)、Q4(0Al)に帰属されるピーク面積強度をそれぞれ、a、b、c、dとし、(a+d)/(b+c)≧0.192を満たす、GIS型ゼオライト。
[2]
ゼオライト中のカチオン種としてカリウムを含む、[1]に記載のGIS型ゼオライト。
[3]
ゼオライト中のアルミ原子数濃度に対するカリウム原子数濃度の割合(K/Al)は、0.05以上である、[2]に記載のGIS型ゼオライト。
[4]
ゼオライト中のアルカリ金属の物質量の合計値(T)に対するカリウム及びリチウムの物質量の合計値(A)の割合(A/T)が、0.05以上である、[1]~[3]のいずれか一項に記載のGIS型ゼオライト。
[5]
炭素原子の含有量が4質量%以下である、[1]~[4]のいずれかに記載のGIS型ゼオライト。
[6]
シリカアルミナを含む、[1]~[5]のいずれかに記載のGIS型ゼオライト。
[7]
[1]~[6]のいずれかに記載のGIS型ゼオライトを含む、吸着材。
[8]
[7]に記載の吸着材を用い、H2、N2、O2、Ar、CO、及び炭化水素からなる群より選択される2種以上の気体を含む混合物から、CO2、H2O、He、Ne、Cl2、NH3、及びHClからなる群より選択される1種以上を分離する、分離方法。
[9]
圧力スイング式吸着分離法、温度スイング式吸着分離法、又は圧力・温度スイング式吸着分離法により前記気体の分離を行う、[8]に記載の分離方法。
(1)Q4(0Al):酸素を介してAlと全く結合していないSiのピーク
(2)Q4(1Al):酸素を介して1個のAlと結合しているSiのピーク
(3)Q4(2Al):酸素を介して2個のAlと結合しているSiのピーク
(4)Q4(3Al):酸素を介して3個のAlと結合しているSiのピーク
(5)Q4(4Al):酸素を介して4個のAlと結合しているSiのピーク
(1)Q4(0Al):-105ppmから-112ppm
(2)Q4(1Al):-100ppmから-105ppm
(3)Q4(2Al):-95ppmから-100ppm
(4)Q4(3Al):-87ppmから-95ppm
(5)Q4(4Al):-80ppmから-87ppm
なお、本実施形態のGIS型ゼオライトは、シリカ及びアルミナが主成分(80質量%以上)であることが好ましい。主成分とは、80質量%以上を占める成分である。
本実施形態のGIS型ゼオライトにおけるアルミニウムの含有量は、好ましくは1質量%以上であり、より好ましくは3質量%以上であり、さらに好ましくは5質量%以上である。アルミニウムの含有量の上限としては、SARが上述した所定の範囲を満たす限り特に限定されず、シリカ含有量及びSARの値により定められる。
本実施形態のGIS型ゼオライトにおけるシリコンの含有量は、好ましくは3質量%以上であり、より好ましくは5質量%以上である。シリコンの含有量の上限としては、SARが上述した所定の範囲を満たす限り特に限定されず、アルミナ含有量及びSARの値により定められる。
本実施形態のGIS型ゼオライトにおけるリンの含有量は、好ましくは4質量%以下である。リンの含有量の下限としては、特に限定されず、0質量%以上であってもよい。
本実施形態のGIS型ゼオライトにおけるZrの含有量は、好ましくは8質量%以下である。Zrの含有量の下限としては、特に限定されず、0質量%以上であってもよい。
本実施形態のGIS型ゼオライトにおけるTiの含有量は、好ましくは8質量%以下である。Tiの含有量の下限としては、特に限定されず、0質量%以上であってもよい。
二酸化炭素の選択的吸着能をより向上させる観点から、本実施形態のGIS型ゼオライトにおけるリン原子の含有量が1.5質量%以下であることがより好ましく、とりわけ好ましくは0質量%である。
また、上記アルミニウム、シリコン、リン、Zr及びTiの含有量については、後述する実施例に記載の方法により測定することができる。また、上記アルミニウム、シリコン、リン、Zr及びTiの含有量については、例えば、GIS型ゼオライトの合成に用いる混合ゲルの組成比等を後述する好ましい範囲に調整すること等により、上述した範囲に調整することができる。
GIS型ゼオライト中のアルカリ金属の各々の物質量の合計値(T)に対するカリウムの物質量の合計値(K)の割合(K/T)が、0.05以上であることが好ましく、より好ましくは0.10以上であり、さらに好ましくは0.15以上である。K/Tの上限は特に制限されないが、K/Tは1.00以下であってもよい。
本実施形態に係るGIS型ゼオライトの製造方法は、例えば、珪素を含むシリカ源、アルミニウムを含むアルミ源、アルカリ金属(M1)及びアルカリ土類金属(M2)から選ばれる少なくとも1種を含むアルカリ源、アルカリ金属(M1)及びアルカリ土類金属(M2)から選ばれる少なくとも1種を含む塩化合物、リンを含むリン源、有機構造規定剤及び水を含有する混合ゲルの調製工程を含むものとすることができる。以下、混合ゲル及びこれに含まれる各成分について説明する。
本実施形態における混合ゲルとは、シリカ源、アルミ源、塩化合物、及び水を成分として含み、必要に応じてリン源、アルカリ源、有機構造規定剤を含む混合物のことである。
シリカ源としては、一般的に使用されるものであれば特に限定されず、結晶性シリカ、非晶性シリカ、ケイ酸、ケイ酸塩、有機ケイ酸化合物等が挙げられる。より具体例には、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸カルシウム、ケイ酸マグネシウム、ヒュームドシリカ、沈降シリカ、シリカゲル、コロイダルシリカ、アルミノシリケート、テトラエトキシシラン(TEOS)、トリメチルエトキシシラン等が挙げられる。これらの化合物は、単独で使用しても、複数を組み合わせて使用してもよい。ここで、アルミノシリケートは、シリカ源であるとともにアルミ源となる。
アルミ源としては、一般的に使用されるものであれば特に限定されないが、具体例としては、アルミン酸ナトリウム、硫酸アルミニウム、硝酸アルミニウム、酢酸アルミニウム、水酸化アルミニウム、酸化アルミニウム、塩化アルミニウム、アルミニウムアルコキシド、金属アルミニウム、無定形アルミノシリケートゲル等が挙げられる。これらの化合物は、単独で使用しても、複数を組み合わせて使用してもよい。
塩化合物は、ゼオライトを製造する場合に、ゼオライト構造への結晶化を促進させるLi、Na、K、Rb、Csといったアルカリ金属や、Ca、Mg、Sr、Baといったアルカリ土類金属を含む化合物である。添加する塩化合物に含まれるアルカリ金属、及びアルカリ土類金属としては、GIS型骨格の結晶形成がより容易となる観点から、Na、Kであることが好ましく、Naであることがより好ましい。また、塩化合物は単独でも、複数を組み合わせて使用してもよい。
硫酸カリウム、亜硫酸カリウム、チオ硫酸カリウム、亜硝酸カリウム、硝酸カリウム、炭酸カリウム、炭酸水素カリウム、リン酸カリウム、酢酸カリウム、ギ酸カリウム、クエン酸カリウム、シュウ酸カリウム、フッ化カリウム、塩化カリウム、臭化カリウム、ヨウ化カリウム、チオカリウム、ケイ酸カリウム、メタケイ酸カリウム、四ホウ酸カリウム、塩素酸カリウム、過塩素酸カリウム、シアン化カリウム、メタスズ酸カリウム、ヘキサヒドロキシドスズ(IV)酸カリウム、ヘキサシアニド鉄(II)酸カリウム、過マンガン酸カリウム、クロム酸カリウム、ニクロム酸カリウム、
硫酸リチウム、亜硫酸リチウム、チオ硫酸リチウム、亜硝酸リチウム、硝酸リチウム、炭酸リチウム、炭酸水素リチウム、リン酸リチウム、酢酸リチウム、ギ酸リチウム、クエン酸リチウム、シュウ酸リチウム、フッ化リチウム、塩化リチウム、臭化リチウム、ヨウ化リチウム、チオリチウム、ケイ酸リチウム、メタケイ酸リチウム、四ホウ酸リチウム、塩素酸リチウム、過塩素酸リチウム、シアン化リチウム、メタスズ酸リチウム、ヘキサヒドロキシドスズ(IV)酸リチウム、ヘキサシアニド鉄(II)酸リチウム、過マンガン酸リチウム、クロム酸リチウム、ニクロム酸リチウム、
硫酸ルビジウム、亜硫酸ルビジウム、チオ硫酸ルビジウム、亜硝酸ルビジウム、硝酸ルビジウム、炭酸ルビジウム、炭酸水素ルビジウム、リン酸ルビジウム、酢酸ルビジウム、ギ酸ルビジウム、クエン酸ルビジウム、シュウ酸ルビジウム、フッ化ルビジウム、塩化ルビジウム、臭化ルビジウム、ヨウ化ルビジウム、チオルビジウム、ケイ酸ルビジウム、メタケイ酸ルビジウム、四ホウ酸ルビジウム、塩素酸ルビジウム、過塩素酸ルビジウム、シアン化ルビジウム、メタスズ酸ルビジウム、ヘキサヒドロキシドスズ(IV)酸ルビジウム、ヘキサシアニド鉄(II)酸ルビジウム、過マンガン酸ルビジウム、クロム酸ルビジウム、ニクロム酸ルビジウム、
硫酸セシウム、亜硫酸セシウム、チオ硫酸セシウム、亜硝酸セシウム、硝酸セシウム、炭酸セシウム、炭酸水素セシウム、リン酸セシウム、酢酸セシウム、ギ酸セシウム、クエン酸セシウム、シュウ酸セシウム、フッ化セシウム、塩化セシウム、臭化セシウム、ヨウ化セシウム、チオセシウム、ケイ酸セシウム、メタケイ酸セシウム、四ホウ酸セシウム、塩素酸セシウム、過塩素酸セシウム、シアン化セシウム、メタスズ酸セシウム、ヘキサヒドロキシドスズ(IV)酸セシウム、ヘキサシアニド鉄(II)酸セシウム、過マンガン酸セシウム、クロム酸セシウム、ニクロム酸セシウム、
硫酸マグネシウム、亜硫酸マグネシウム、チオ硫酸マグネシウム、亜硝酸マグネシウム、硝酸マグネシウム、炭酸マグネシウム、炭酸水素マグネシウム、リン酸マグネシウム、酢酸マグネシウム、ギ酸マグネシウム、クエン酸マグネシウム、シュウ酸マグネシウム、フッ化マグネシウム、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、チオマグネシウム、ケイ酸マグネシウム、メタケイ酸マグネシウム、四ホウ酸マグネシウム、塩素酸マグネシウム、過塩素酸マグネシウム、シアン化マグネシウム、メタスズ酸マグネシウム、ヘキサヒドロキシドスズ(IV)酸マグネシウム、ヘキサシアニド鉄(II)酸マグネシウム、過マンガン酸マグネシウム、クロム酸マグネシウム、ニクロム酸マグネシウム、
硫酸カルシウム、亜硫酸カルシウム、チオ硫酸カルシウム、亜硝酸カルシウム、硝酸カルシウム、炭酸カルシウム、炭酸水素カルシウム、リン酸カルシウム、酢酸カルシウム、ギ酸カルシウム、クエン酸カルシウム、シュウ酸カルシウム、フッ化カルシウム、塩化カルシウム、臭化カルシウム、ヨウ化カルシウム、チオカルシウム、ケイ酸カルシウム、メタケイ酸カルシウム、四ホウ酸カルシウム、塩素酸カルシウム、過塩素酸カルシウム、シアン化カルシウム、メタスズ酸カルシウム、ヘキサヒドロキシドスズ(IV)酸カルシウム、ヘキサシアニド鉄(II)酸カルシウム、過マンガン酸カルシウム、クロム酸カルシウム、ニクロム酸カルシウム、
硫酸ストロンチウム、亜硫酸ストロンチウム、チオ硫酸ストロンチウム、亜硝酸ストロンチウム、硝酸ストロンチウム、炭酸ストロンチウム、炭酸水素ストロンチウム、リン酸ストロンチウム、酢酸ストロンチウム、ギ酸ストロンチウム、クエン酸ストロンチウム、シュウ酸ストロンチウム、フッ化ストロンチウム、塩化ストロンチウム、臭化ストロンチウム、ヨウ化ストロンチウム、チオストロンチウム、ケイ酸ストロンチウム、メタケイ酸ストロンチウム、四ホウ酸ストロンチウム、塩素酸ストロンチウム、過塩素酸ストロンチウム、シアン化ストロンチウム、メタスズ酸ストロンチウム、ヘキサヒドロキシドスズ(IV)酸ストロンチウム、ヘキサシアニド鉄(II)酸ストロンチウム、過マンガン酸ストロンチウム、クロム酸ストロンチウム、ニクロム酸ストロンチウム、
硫酸バリウム、亜硫酸バリウム、チオ硫酸バリウム、亜硝酸バリウム、硝酸バリウム、炭酸バリウム、炭酸水素バリウム、リン酸バリウム、酢酸バリウム、ギ酸バリウム、クエン酸バリウム、シュウ酸バリウム、フッ化バリウム、塩化バリウム、臭化バリウム、ヨウ化バリウム、チオバリウム、ケイ酸バリウム、メタケイ酸バリウム、四ホウ酸バリウム、塩素酸バリウム、過塩素酸バリウム、シアン化バリウム、メタスズ酸バリウム、ヘキサヒドロキシドスズ(IV)酸バリウム、ヘキサシアニド鉄(II)酸バリウム、過マンガン酸バリウム、クロム酸バリウム、ニクロム酸バリウム、等が挙げられる。
アルカリ源は、ゼオライトを製造する場合に、ゼオライト構造への結晶化を促進するために、混合ゲル中のアルカリ性(pH)を調整する目的で用いられる。用いるアルカリはアルカリ性を示す化合物であればよく、無機化合物、有機化合物どちらでもよいが、コストの面から無機化合物である方が好ましく、より好ましくはアルカリ金属水酸化物が挙げられる。アルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等が挙げられ、好ましくは水酸化ナトリウム、水酸化カリウムが挙げられ、より好ましくは水酸化ナトリウムが挙げられる。これらの化合物は、単独で使用しても、複数を組み合わせて使用してもよい。
混合ゲルを水熱合成することによってゼオライトを製造する場合の有機構造規定剤は、ゼオライト構造への結晶化を促進する作用をする化合物である。ゼオライトの結晶化においては、必要に応じて有機構造規定剤を用いることができる。
本実施形態において、アルカリ金属、及び/又はアルカリ土類金属を含む塩化合物を添加することが、適切な構造を持ったGIS型ゼオライトを合成するために最も重要である。ゼオライトの生成は、水溶媒に溶解したシリカ源、アルミ源が溶解しながら反応し、結晶化していくが、塩化合物の添加によってゼオライト骨格中におけるSi及びAlの結合様式やその存在比を調整することが可能で、理想的な結晶構造を有するGISを合成することが可能となる。
α=E/Al2O3 (1)
β=SiO2/Al2O3 (2)
γ=(M12O+M2O)/Al2O3 (3)
δ=P2O5/Al2O3 (4)
ε=H2O/Al2O3 (5)
ζ=H2O/OH- (6)
η=R/Al2O3 (7)
混合ゲルの調製工程は、特に限定されないが、例えば、シリカ源、アルミ源、塩化合物、水、及び必要に応じてリン源、アルカリ源、有機構造規定剤を一時にあるいは多段階で混合する混合工程と、この混合工程で得られた混合物の熟成工程とを含んでもよい。
本実施形態に係るGIS型ゼオライトの製造方法において、水熱合成温度が80℃~200℃である水熱合成工程をさらに含むことが好ましく、当該水熱合成温度は100℃~180℃であることがより好ましい。すなわち、好ましくは、調製工程により得た混合ゲルを所定の温度で、所定の時間、撹拌又は静置状態で保持することにより水熱合成する。
水熱合成工程後、生成物である固体と水を含む液体とを分離するが、その分離方法は一般的な方法であれば特に限定されず、濾過、デカンテーション、噴霧乾燥法(回転噴霧、ノズル噴霧及び超音波噴霧など)、回転蒸発器を用いた乾燥法、真空乾燥法、凍結乾燥法、又は自然乾燥法等を用いることができ、通常は濾過又はデカンテーションにより分離することができる。
必要に応じて、GIS型ゼオライトを焼成して用いることができる。焼成する温度は、一般的に用いられる温度であれば特に限定されないが、有機構造規定剤を除去したい場合、その残っている割合を少なくできることから、300℃以上であることが好ましく、350℃以上であることがより好ましい。焼成の時間が短くなり、ゼオライトを製造する際の経済性に優れる点から、360℃以上であることがさらに好ましい。ゼオライトの結晶性が保持される傾向にあることから、450℃未満であることが好ましく、420℃以下であることがより好ましく、400℃以下であることがさらに好ましい。
必要に応じて、GIS型ゼオライトを、所望のカチオン型へカチオン交換を行うことができる。カチオン交換は、以下に限定されないが、例えば、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸ルビジウム、炭酸セシウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、炭酸アンモニウムなどの炭酸塩、あるいは硝酸ナトリウム、硝酸カリウム、硝酸リチウム、硝酸ルビジウム、硝酸セシウム、硝酸マグネシウム、硝酸カルシウム、硝酸ストロンチウム、硝酸バリウム、硝酸アンモニウムなどの硝酸塩、あるいは前記炭酸塩、硝酸塩に含まれる炭酸イオン、硝酸イオンをハロゲン化物イオン、硫酸イオン、炭酸イオン、炭酸水素イオン、酢酸イオン、リン酸イオン又はリン酸水素イオンに変更した塩、硝酸や塩酸などの酸を用いることができる。
本実施形態の分離方法は、本実施形態のGIS型ゼオライトを含む吸着材を用い、H2、N2、O2、CO、及び炭化水素からなる群より選択される2種以上の気体を含む混合物から、CO2、H2O、He、Ne、Cl2、NH3、及びHClからなる群より選択される1種以上を分離する。本実施形態においては、N2、O2、CO、及び炭化水素からなる群より選択される1種以上の気体から、CO2、H2Oからなる群より選択される1種以上を分離することが好ましい。なお、炭化水素としては、特に限定されないが、メタン、エタン、エチレン、プロパン、プロピレン、1-ブテン、2-ブテン、2-メチルプロペン、ジメチルエーテル、アセチレン等が挙げられる。
ゼオライトを水酸化ナトリウム水溶液あるいは王水で熱溶解し、適宜希釈した液を用いてICP-発光分光分析(以下、「ICP-AES」ともいう、株式会社日立ハイテクサイエンス製SPS3520UV-DD:装置名)によってゼオライト中のシリコン、アルミニウム、リン、カリウム及びリチウムなどの各種元素濃度を測定した。ゼオライト中のカリウム及びリチウムの含有量は、ゼオライト中のアルカリ金属の各々の物質量の合計値(T)に対するカリウム及びリチウムの物質量の合計値(A)の割合(A/T)として算出した。K/Tも同様にして算出した。また、ゼオライト中のカリウムの含有量は、アルミ原子数濃度に対するカリウム原子数濃度の割合(K/Al)として算出した。
当該GIS型ゼオライトの粉体試料約2mgを計量し、CHN元素分析(ヤナコ分析工業株式会社社製MT-6:装置名)によってゼオライト中の炭素原子の含有量を測定した。CO2を吸着した後のゼオライト試料は、ゼオライトに含有する炭素原子のみを検出するため、ゼオライト粉末試料を密閉容器に入れ、200℃で加熱しながら真空ポンプで3時間以上真空引きした後、大気中に取り出し、24時間以上大気下で静置してから計量、元素分析を行った。
X線回折は以下の手順で行った。
(1)各実施例及び比較例で得られた乾燥物を試料として、メノウ乳鉢で粉砕した。さらに結晶性シリコン(株式会社レアメタリック製)を10質量%加え、メノウ乳鉢で均一になるまで混合したものを構造解析の試料とした。
X線回折装置(XRD):リガク社製粉末X線回折装置「RINT2500型」(商品名)
X線源:Cu管球(40kV、200mA)
測定温度:25℃
測定範囲:5~60°(0.02°/step)
測定速度:0.2°/分
スリット幅(散乱、発散、受光):1°、1°、0.15mm
ゼオライトの29Si-MAS-NMRの測定は、以下の方法で行った。また、ゼオライトのSARは29Si-MAS-NMRを測定することで求めることができる。
まず、ゼオライトの調湿として、デシケーターの底に水を張っておき、その上部に試料管に入れたゼオライトを48時間保持した。調湿処理を行った後、下記条件で29Si-MAS-NMRの測定を行った。
装置:JEOL RESONANCE ECA700
磁場強度:16.44 T(1H共鳴周波数700MHz)
測定核:29Si
共鳴周波数:139.08MHz
NMR管:4mmφ(ジルコニア製ローター)
測定方法:DD/MAS(dipolar decoupling magic anglespinning)
パルス幅:45°
待ち時間:50sec
積算回数:800回 (測定時間;約22時間)
MAS:10,000Hz
化学シフト基準:シリコーンゴム(-22.34ppm)外部基準
GIS型ゼオライトを含む成形体では、29Si-MAS-NMRスペクトルにおいて、次の5つのピークを示す。
(1)Q4(0Al):酸素を介してAlと全く結合していないSiのピーク
(2)Q4(1Al):酸素を介して1個のAlと結合しているSiのピーク
(3)Q4(2Al):酸素を介して2個のAlと結合しているSiのピーク
(4)Q4(3Al):酸素を介して3個のAlと結合しているSiのピーク
(5)Q4(4Al):酸素を介して4個のAlと結合しているSiのピーク
また、29Si-MAS-NMRスペクトルにおいて、それらのピーク位置は、一般的には-112ppmから-80ppmに存在し、高磁場側からQ4(0Al)、Q4(1Al)、Q4(2Al)、Q4(3Al)、Q4(4Al)に帰属できる。ゼオライト骨格中に存在するカチオン種によってピーク位置は変化し得るが、一般的には以下の範囲にピーク位置が存在する。
(1)Q4(0Al):-105ppmから-112ppm
(2)Q4(1Al):-100ppmから-105ppm
(3)Q4(2Al):-95ppmから-100ppm
(4)Q4(3Al):-87ppmから-95ppm
(5)Q4(4Al):-80ppmから-87ppm
29Si-MAS-NMRスペクトルのピーク面積強度については、解析プログラムdmfit(♯202000113バージョン)を用いて、ガウス及びローレンツ関数により解析を行い、振幅(スペクトルの最大値の高さ)、位置(スペクトル位置、ppm)、幅(スペクトルの半値全幅、ppm)、ガウス/ローレンツ比(xG/(1-x)L)の4つのパラメーターを最小二乗法のアルゴリズムで最適化計算することで得られる。こうして求められたQ4(0Al)、Q4(1Al)、Q4(2Al)、Q4(3Al)、Q4(4Al)それぞれのピーク面積をA_Q4(0Al)、A_Q4(1Al)、A_Q4(2Al)、A_Q4(3Al)、A_Q4(4Al)とし、A_Q4(0Al)、A_Q4(1Al)、A_Q4(2Al)、A_Q4(3Al)、A_Q4(4Al)の合計値をA_totalするとSARとしては以下で求めることが可能である。
SAR=100/〔A_Q4(1Al)/4+2×A_Q4(2Al)/4
+3×A_Q4(3Al)/4+4×A_Q4(4Al)/4〕×2
ガス吸脱着等温線測定は以下の手順で行った。
(1)各実施例及び比較例で得られた乾燥物を試料とし、12mmセル(Micro Meritics社製)に0.2g入れた。
ガス吸着等温線測定は以下の手順で行った。
(1)各実施例及び比較例で得られた乾燥物を試料とし、12mmセル(Micro Meritics社製)に0.2g入れた。
水61.93gと水酸化ナトリウム(NaOH、富士フイルム和光純薬社製)0.403gと、硝酸ナトリウム(NaNO3、富士フイルム和光純薬社製)3.39gと、アルミン酸ナトリウム(NaAlO2、富士フイルム和光純薬社製)1.64gとコロイダルシリカ(Ludox AS-40、固形分濃度40質量%、Grace社製)10.82gを混合し、30分間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=4.53、β=SiO2/Al2O3=8.17、γ=Na2O/Al2O3=3.99、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=431.0、ζ=H2O/OH-=376.7、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った200mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、135℃、4日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
水61.65gと48質量%水酸化ナトリウム水溶液(NaOH、固形分濃度48質量%、トクヤマソーダ社製)0.60gと、炭酸ナトリウム(Na2CO3、トクヤマソーダ社製)2.27gと、アルミン酸ナトリウム(NaAlO2、北陸化成工業所製)1.64gとコロイダルシリカ(Ludox AS-40、固形分濃度40質量%、Grace社製)10.82gを混合し、30分間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=4.86、β=SiO2/Al2O3=8.17、γ=Na2O/Al2O3=3.99、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=431.2、ζ=H2O/OH-=527.8、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った200mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、130℃、5日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。得られたゼオライト1gを、炭酸カリウム(K2CO3、日本曹達社製)を用いて調整した0.05Nの炭酸カリウム水溶液500mLに入れ、室温で3時間、500rpmで攪拌した。生成物をろ過して120℃で乾燥し、カチオンの一部がカリウムに交換された粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
水141.41gと水酸化ナトリウム水溶液(NaOH、富士フイルム和光純薬社製)2.62gと、硝酸ナトリウム(NaNO3、富士フイルム和光純薬社製)8.53gと、アルミン酸ナトリウム(NaAlO2、富士フイルム和光純薬社製)3.85gと非晶質シリカ(Perkasil SM500、Grace社製)17.41gを混合し、1時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=4.85、β=SiO2/Al2O3=14.00、γ=Na2O/Al2O3=5.16、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=379.3、ζ=H2O/OH-=120.0、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った300mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、130℃、4日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
水141.41gと水酸化ナトリウム水溶液(NaOH、富士フイルム和光純薬社製)2.62gと、硝酸ナトリウム(NaNO3、富士フイルム和光純薬社製)2.43gと、アルミン酸ナトリウム(NaAlO2、富士フイルム和光純薬社製)0.55gとアルミノシリケート(SIPERNAT 820A、Evonik社製)35.33gを混合し、1時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.88、β=SiO2/Al2O3=14.00、γ=Na2O/Al2O3=2.62、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=242.4、ζ=H2O/OH-=120.0、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った300mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、130℃、5日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。得られたゼオライト1gを、炭酸カリウム(K2CO3、日本曹達社製)を用いて調整した0.005Nの炭酸カリウム水溶液500mLに入れ、室温で3時間、500rpmで攪拌した。生成物をろ過して120℃で乾燥し、カチオンの一部がカリウムに交換された粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
水21.05gと水酸化ナトリウム水溶液(NaOH、富士フイルム和光純薬社製)0.53gと、硝酸ナトリウム(NaNO3、富士フイルム和光純薬社製)1.37gと、アルミン酸ナトリウム(NaAlO2、富士フイルム和光純薬社製)1.13gと水ガラス3号(キシダ化学社製)15.5gを混合し、1時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=2.66、β=SiO2/Al2O3=12.39、γ=Na2O/Al2O3=6.10、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=197.9、ζ=H2O/OH-=90.2、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った100mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、130℃、5日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。得られたゼオライト1gを、炭酸カリウム(K2CO3、日本曹達社製)を用いて調整した0.003Nの炭酸カリウム水溶液500mLに入れ、室温で3時間、500rpmで攪拌した。生成物をろ過して120℃で乾燥し、カチオンの一部がカリウムに交換された粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
水56.70gと水酸化ナトリウム(NaOH、富士フイルム和光純薬社製)0.335gと、アルミン酸ナトリウム(NaAlO2、富士フイルム和光純薬社製)1.13gと、水ガラス3号(キシダ化学社製)12.42gを混合し、30分間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=8.17、γ=Na2O/Al2O3=9.23、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=431.0、ζ=H2O/OH-=377.0、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った200mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度30rpm、135℃、4日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
非特許文献7の内容に基づき、水143.10gと50質量%水酸化ナトリウム水溶液(NaOH、固形分濃度50質量%、Aldrich社製)40.00gと、アルミニウムパウダー(Al、富士フイルム和光純薬社製)2.70gと、コロイダルシリカ(Ludox HS-40、固形分濃度40質量%、Aldrich社製)75.10gを混合し、24時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=10.0、γ=Na2O/Al2O3=2.50、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=220.0、ζ=H2O/OH-=44.0、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った300mLのステンレス製マイクロボンベ(HIRO COMPANY製)に仕込み、マイクロボンベ上下方向に回転可能な撹拌型恒温槽(HIRO COMPANY製)によって、撹拌速度60rpm、150℃、3日間水熱合成した。生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。XRDスペクトルより、得られたゼオライトがGIS型ゼオライトであることを確認した。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
特許文献3の内容に基づき、水207.30gと水酸化ナトリウム8.78gと、アルミン酸ナトリウム16.4gと水ガラス3号248.3gを混合し、15分間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=12.39、γ=Na2O/Al2O3=6.10、δ=P2O5/Al2O3=0.0、ε=H2O/Al2O3=197.86、ζ=H2O/OH-=90.17、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った1000mLのステンレス製オートクレーブに仕込み、撹拌なしで130℃、5日間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
非特許文献1の内容に基づき、水132.86gと水酸化ナトリウム15.66gと、アルミン酸ナトリウム(アルファ・エイサー社製)7.2gとコロイダルシリカ(Ludox AS-40、固形分濃度40質量%)25.56gを混合し、室温で24時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=7.96、γ=Na2O/Al2O3=10.75、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=371.79、ζ=H2O/OH-=19.08、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った200mLのステンレス製オートクレーブに仕込み、撹拌なしで100℃、7日間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。さらに、他のゼオライトや非晶質シリカアルミナなどに由来するピークが見られなかったことから、高純度のGIS型ゼオライトであると評価した。
非特許文献3の内容に基づき、水102.57gと水酸化ナトリウム(純正化学社製)2.45gと、アルミン酸ナトリウム(昭和化学社製)1.15gと水ガラス(富士フィルム和光純薬社製)24.07gを混合し、N2雰囲気下で1800rpm、24時間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=20.0、γ=Na2O/Al2O3=14.00、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=840.00、ζ=H2O/OH-=103.05、η=R/Al2O3=0.00であった。混合ゲルを1000rpmで撹拌しながら100℃で24時間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のGIS型ゼオライトを得た。
特許文献1の内容に基づき、二酸化ケイ素(SiO2、富士フイルム和光純薬工業製)21.54gと酸化アルミニウム(Al2O3、富士フイルム和光純薬工業製)5.97gと酸化鉄(Fe2O3、富士フイルム和光純薬工業製)1.17gと酸化チタン(TiO2、富士フイルム和光純薬工業製)0.27gと酸化カルシウム(CaO、富士フイルム和光純薬工業製)0.21gと酸化マグネシウム(MgO、富士フイルム和光純薬工業製)0.06gと水酸化ナトリウム0.03gと水酸化カリウム0.21gと酸化リン(P2O5、富士フイルム和光純薬工業製)0.05gと炭素粉末(Strem Chemicals製)0.53gとを自動乳鉢で混錬したものに炭酸ナトリウム(Na2CO3、富士フイルム和光純薬工業製)17.6gを加えて混合し、電気炉内で1000℃で1時間溶融した。その後、その溶融物を冷却粉砕し、水をH2O/Na2Oモル比で50となるように149.78g加えて混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=5.67、β=SiO2/Al2O3=6.12、γ=Na2O/Al2O3=2.84、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=142.00、ζ=H2O/OH-=1848.89、η=R/Al2O3=0.00であった。混合ゲルを、オートクレーブ内で100℃で24時間加熱し、生成物をろ過して120℃で乾燥した後、粉末状のGIS型ゼオライトを得た。
非特許文献6の内容に基づき、アルミン酸ナトリウム0.55gとメタケイ酸ナトリウム(Na2SiO3、富士フイルム和光純薬社製)0.35gとフュームドシリカ(Aerosil 300、日本アエロジル社製)1.43gを0.1mol/Lの水酸化ナトリウム水溶液10ccと混合し、混合ゲルを得た。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=8.0、γ=Na2O/Al2O3=1.00、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=166.00、ζ=H2O/OH-=550.00、η=R/Al2O3=0.00であった。混合ゲルをステンレス製のマイクロボンベに入れ、200℃7日間加熱してゼオライトを合成した。
特許文献2の内容に基づき、メタケイ酸ナトリウム五水和物(Na2O3Si/5H2O、アルドリッチ製)18gと水210.0gを混合した液にトリエタノールアミン(C6H25NO3、Carl Roth GmbH社製)127.1gを加え、600rpmで30分間撹拌した。この液に、水酸化ナトリウム2.34gと水148.0gとを混合した液を添加し、室温、600rpmで30分間撹拌してAlを含まない混合液を得た。混合液の組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=∞、γ=Na2O/Al2O3=∞、δ=P2O5/Al2O3=∞、ε=H2O/Al2O3=∞、ζ=H2O/OH-=∞、η=R/Al2O3=∞であった。フッ素樹脂内筒の入った1000mLのステンレス製オートクレーブにアルミニウム粉末(Al、和光純薬製)1.134gを仕込み、混合液を入れ、熟成時間無しで、撹拌なしで95℃、5日間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。
非特許文献5の内容に基づき、水189.90gとアルミニウムイソプロポキシド8.17gとテトラエチルオルトシリケイト(アルドリッチ製)17.37gと有機構造規定剤として水酸化テトラメチルアンモニウム・5水和物(アルドリッチ製)176.85gを混合し、30分間撹拌した。この液を0℃で1時間保持した後、旋回シェーカーで20時間撹拌し、120℃で33分間加熱した後、0℃で15分間冷却することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=4.78、γ=Na2O/Al2O3=0.0、δ=P2O5/Al2O3=0.0、ε=H2O/Al2O3=253、ζ=H2O/OH-=51.66、η=R/Al2O3=4.78であった。混合ゲルを100℃で13日間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。
特許文献4の内容に基づき、水259.10gと水酸化ナトリウム0.98gと、アルミン酸ナトリウム20.50gと水ガラス3号310.4gを混合し、45分間撹拌することで混合ゲルを調製した。混合ゲルの組成は、α=E/Al2O3=0.00、β=SiO2/Al2O3=12.00、γ=Na2O/Al2O3=3.00、δ=P2O5/Al2O3=0.00、ε=H2O/Al2O3=200.00、ζ=H2O/OH-=1009.8、η=R/Al2O3=0.00であった。混合ゲルをフッ素樹脂内筒の入った1000mLのステンレス製オートクレーブに仕込み、撹拌なしで110℃、2日間水熱合成し、生成物をろ過して120℃で乾燥した後、粉末状のゼオライトを得た。
α=E/Al2O3、(Eは塩化合物の添加により生じたカチオン種の加算モル量を表す。)
β=SiO2/Al2O3、
γ=(M12O+M2O)/Al2O3(ここで、M1はアルカリ金属を示し、M2はアルカリ土類金属を示す。)、
δ=P2O5/Al2O3、
ε=H2O/Al2O3、
ζ=H2O/OH-、
η=R/Al2O3 (Rは有機構造規定剤を表す。)
2 容器
3 フィルター
4 ゼオライト粒子
Claims (9)
- GIS型ゼオライトであって、
シリカアルミナ比が3.40以上であり、
29Si-MAS-NMRスペクトルで観測されるQ4(3Al)、Q4(2Al)、Q4(1Al)、Q4(0Al)に帰属されるピーク面積強度をそれぞれ、a、b、c、dとし、(a+d)/(b+c)≧0.192を満たす、GIS型ゼオライト。 - ゼオライト中のカチオン種としてカリウムを含む、請求項1に記載のGIS型ゼオライト。
- ゼオライト中のアルミ原子数濃度に対するカリウム原子数濃度の割合(K/Al)は、0.05以上である、請求項2に記載のGIS型ゼオライト。
- ゼオライト中のアルカリ金属の物質量の合計値(T)に対するカリウム及びリチウムの物質量の合計値(A)の割合(A/T)が、0.05以上である、請求項1に記載のGIS型ゼオライト。
- 炭素原子の含有量が4質量%以下である、請求項1に記載のGIS型ゼオライト。
- シリカアルミナを含む、請求項1に記載のGIS型ゼオライト。
- 請求項1~6のいずれかに記載のGIS型ゼオライトを含む、吸着材。
- 請求項7に記載の吸着材を用い、H2、N2、O2、Ar、CO、及び炭化水素からなる群より選択される2種以上の気体を含む混合物から、CO2、H2O、He、Ne、Cl2、NH3、及びHClからなる群より選択される1種以上を分離する、分離方法。
- 圧力スイング式吸着分離法、温度スイング式吸着分離法、又は圧力・温度スイング式吸着分離法により前記気体の分離を行う、請求項8に記載の分離方法。
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