JP6177880B2 - ゼオライト材料及びその製造方法並びにその使用方法 - Google Patents
ゼオライト材料及びその製造方法並びにその使用方法 Download PDFInfo
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- JP6177880B2 JP6177880B2 JP2015507515A JP2015507515A JP6177880B2 JP 6177880 B2 JP6177880 B2 JP 6177880B2 JP 2015507515 A JP2015507515 A JP 2015507515A JP 2015507515 A JP2015507515 A JP 2015507515A JP 6177880 B2 JP6177880 B2 JP 6177880B2
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- zeolitic material
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- 238000000034 method Methods 0.000 title claims description 105
- 239000010457 zeolite Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 239000000463 material Substances 0.000 claims description 273
- 239000000203 mixture Substances 0.000 claims description 126
- 150000001875 compounds Chemical class 0.000 claims description 77
- 150000001768 cations Chemical class 0.000 claims description 51
- -1 2-propen-1-yl Chemical group 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 42
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- 238000005004 MAS NMR spectroscopy Methods 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 16
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- YOJQYJQXIAVABK-UHFFFAOYSA-M prop-2-enyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CC=C YOJQYJQXIAVABK-UHFFFAOYSA-M 0.000 claims description 5
- ALJNOSMHIDMKOA-UHFFFAOYSA-M prop-1-enyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)C=CC ALJNOSMHIDMKOA-UHFFFAOYSA-M 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 238000001116 aluminium-27 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 62
- 239000000523 sample Substances 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 31
- 239000013078 crystal Substances 0.000 description 24
- 239000010936 titanium Substances 0.000 description 24
- 125000003342 alkenyl group Chemical group 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 17
- 238000000926 separation method Methods 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
- BUWDPPUOSGERNF-UHFFFAOYSA-N prop-2-enyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)CC=C BUWDPPUOSGERNF-UHFFFAOYSA-N 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 6
- 229910018557 Si O Inorganic materials 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- VJGWNHDROCRKKK-UHFFFAOYSA-N prop-1-enyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)C=CC VJGWNHDROCRKKK-UHFFFAOYSA-N 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 125000006592 (C2-C3) alkenyl group Chemical group 0.000 description 4
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 description 4
- 125000004399 C1-C4 alkenyl group Chemical group 0.000 description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 150000004703 alkoxides Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000012229 microporous material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 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 2
- 239000011149 active material Substances 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
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- 238000006735 epoxidation reaction Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 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 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
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Description
(1)1種以上のYO2用源と、構造規定剤としての1種以上のアルケニルトリアルキルアンモニウムカチオンR1R2R3R4N+含有化合物とを含有する混合物を製造する工程と、
(2)工程(1)で得た混合物を結晶化させ、ゼオライト材料を生成する工程と、を含む。
(4)ゼオライト材料の洗浄、及び/又は、
(5)ゼオライト材料の乾燥、及び/又は、
(6)ゼオライト材料のイオン交換方法での処理。
材料は、少なくとも書き反射を持つX線回折パターンを持つ。
−110.4ppm以下−114.0ppm以上の範囲に含まれる第1ピーク(P1)、及び、
−101.4ppm以下−106.8ppm以上の範囲に含まれる第2ピーク(P2)。
有機テンプレートATPAOHの合成を2工程で行った。ここで、第1工程では、アリルクロライドで、トリプロピルアミンをアルキレート化した。これに関し、 1716gのトリプロピルアミンを、6Lのガラス反応器(HWS)中に配置し、829gメタノールを次いで添加し、混合物を攪拌しながら60℃に加熱した。300gメタノール中984gのアリルクロリドを、1.75時間かけて次いで添加した。反応混合物を、次いで、60〜70℃で24時間攪拌した。
丸底フラスコ内に、500gのテトラエチルオルソシリケート(TEOS)を、15gのテトラエチルオルソチタネート(TEOTi)と一緒に添加した。220gのATPAOH溶液(40質量%N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムモル比が95:5)と、300gの蒸留水を攪拌しながら、Si及びTi源を含むフラスコに添加した。全成分の攪拌後、黄濁溶液を得た。10分の攪拌後、スラリー温度は35℃であり、溶液の色は澄んだ黄色になった。20分の攪拌後、温度は44℃に到達し、溶液は再び濁った。30分攪拌後、スラリー温度は54℃に到達し、再び澄んだ黄色溶液になった。1時間後、シリカ及びチタン源の加水分解が終了し、混合物の温度が54℃で一定であった。TEOS及びTEOTiの加水分解から出たエタノールを、次いで、合成混合物から、95℃、2時間の蒸留により分離した。蒸留プロセスの間、溶液を連続して100U/分回転した。538gのエタノール蒸留物を得た。
520gの20質量%ATPAOH溶液(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が50:50)を用い、エタノールの蒸留前、丸底フラスコ中の最初の混合物の作製に蒸留水を使用せず、実施例1のプロセスを繰り返した。
327gの27質量%ATPAOH溶液(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が50:50)を用い、エタノールの蒸留前、丸底フラスコ中の最初の混合物の作製に193gの蒸留水を添加して、実施例1のプロセスを繰り返した。
137.6mlの蒸留水H2O中20質量%ATPAOH(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が95:5)を、エアロジル200(登録商標)32.38gと600mlフラスコ中で混合し、混合物を15分間攪拌した。分散物を次いで、テフロン(登録商標)インレイを備えた0.25Lオートクレーブ中に移し替え、150℃で120時間加熱した。冷却後、生成された固体を蒸留水で繰り返し洗浄し、120℃で16時間乾燥し、31.2gの白色粉末を得た。その粉末を、次いで、490℃で5時間加熱した。SiO2に対するモル収率は95%であった。
136.9mlの蒸留水H2O中20質量%ATPAOH(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が95:5)を、エアロジル200(登録商標)32.00g及びNaAlO22.02gと600mlフラスコ中で混合し、混合物を15分間攪拌した。分散物を次いで、テフロン(登録商標)インレイを備えた0.25Lオートクレーブ中に移し替え、150℃で120時間加熱した。冷却後、生成された固体を蒸留水で繰り返し洗浄し、120℃で16時間乾燥し、30.2gの黄色がかった粉末を得た。その粉末を、次いで、490℃で5時間加熱した。SiO2に対するモル収率は92%であった。
136.9mlの蒸留水H2O中20質量%ATPAOH(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が95:5)を、エアロジル200(登録商標)32.00g及びAl(OH)30.84gと600mlフラスコ中で混合し、混合物を15分間攪拌した。分散物を次いで、テフロン(登録商標)インレイを備えた0.25Lオートクレーブ中に移し替え、150℃で120時間加熱した。冷却後、生成された固体を蒸留水で繰り返し洗浄し、120℃で16時間乾燥し、30.5gの黄色がかった粉末を得た。その粉末を、次いで、490℃で5時間加熱した。SiO2に対するモル収率は93%であった。
333mlのH2O中40質量%ATPAOH(N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウム:N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムのモル比が95:5)を、757gのテトラエチルオルソシリケートと470gの蒸留水H2Oと、60分間室温で攪拌した。その後、746gのエタノールを、95℃で反応ゲルから蒸留により除去した。冷却後、746gのH2Oと、24.3gのAl2(SO4)3*18H2Oが20mlの蒸留水H2Oに溶解したものを添加した。分散物を0.25Lオートクレーブ中に移し替え、155℃で24時間加熱した。室温まで冷却後、生成された固体を蒸留水で繰り返し洗浄し、120℃で16時間乾燥し、210gの白色粉末を得た。有機残留物を500℃、6時間焼成して除去した。
実施例1、2及び3のTS−1材料に関し、水吸収等温線を測定した。ここで、実施例1、2の試料の吸収/脱離等温線を図1b及び2bにそれぞれ示す。これらの図から分かるように、実施例1の試料に関し、水吸収が2.9質量 %に到達し、実施例2の試料については8.3質量%であった。実施例3の試料についての水吸収等温線の測定吸収が8.7質量%に到達することを示した。
本発明材料の触媒的挙動を試験するため、実施例4、5及び6の本発明ZSM−5材料と、市販のZSM−5材料PZ2−25/H及びPZ2−50/H(それぞれSi:Al原子比(SAR)が17と25)で、イソプロパノール分解反応を行った。試験は、室温(非活性)と200℃以上350℃の範囲で行った。
Claims (40)
- (1)1種以上のYO2源と、構造規定剤としての1種以上のアルケニルトリアルキルアンモニウムカチオンR1R2R3R4N+含有化合物とを含む混合物を製造する工程と、
(2)ゼオライト材料を得るために、工程(1)で得た前記混合物を結晶化する工程と、を含み、
Yは四価元素であり、
R1、R2及びR3は互いに独立してn‐プロピルであり、R4は2‐プロペン‐1‐イル又は1‐プロペン‐1‐イルである
MFI型骨格構造を持つゼオライト材料の製造方法。 - 工程(1)で用いる前記構造規定剤が、N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウムヒドロキシド及び/又はN-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムヒドロキシドを含有する請求項1に記載のゼオライト材料の製造方法。
- 工程(1)で製造する前記混合物は2種以上のR1R2R3R4N+含有化合物を含有し、当該2種以上の化合物のR4が互いに異なり、かつ、2-プロペン-1-イル及び1-プロペン-1-イルである請求項1又は2に記載のゼオライト材料の製造方法。
- 工程(1)で製造される前記混合物が、2種のR1R2R3R4N+含有化合物を含有し、当該化合物のうち、第1化合物(A)のR4が末端鎖−CH=CH2部分を持ち、第2化合物(B)のR4が末端鎖部分‐CH3持つ請求項3に記載のゼオライト材料の製造方法。
- 前記化合物A及びBが、R4中の二重結合の位置に関して構造異性体であり、前記構造異性体は、N-(2-プロペン-1-イル)-トリ-n-プロピルアンモニウムヒドロキシドと、N-(1-プロペン-1-イル)-トリ-n-プロピルアンモニウムヒドロキシドである請求項4に記載のゼオライト材料の製造方法。
- Yは、Si、Sn、Ti、Zr、Ge及びこれらの2種以上の混合物からなる群より選択される請求項1〜5のいずれか1項に記載のゼオライト材料の製造方法。
- 1種以上のYO2源が、ヒュームドシリカ、シリカヒドロゾル、反応性アモルファス固体シリカ、シリカゲル、ケイ酸、水ガラス、メタケイ酸ナトリウム水和物、セスキシリケート、ジシリケート、コロイダルシリカ、焼成シリカ、ケイ酸エステル及びこれら2種以上の混合物からなる群より選択される1種以上の化合物を含有する請求項1〜6のいずれか1項に記載のゼオライト材料の製造方法。
- 工程(1)で製造される前記混合物が、更に、1種以上のX2O3源を含み、Xは三価元素である請求項1〜7のいずれか1項に記載のゼオライト材料の製造方法。
- Xは、Al、B、In、Ga及びこれらの2種以上の混合物から選択される請求項8に記載のゼオライト材料の製造方法。
- 1種以上のX2O3源は、アルミニウム、アルミニウムアルコキシド、アルミナ及び/又は1種以上のアルミネートからなる群より選択される1種以上の化合物を含有する請求項8又は9に記載のゼオライト材料の製造方法。
- 工程(1)に係る前記混合物のYO2:X2O3モル比が、0.5以上500以下の範囲である請求項8〜10のいずれか1項に記載のゼオライト材料の製造方法。
- 工程(1)で製造される前記混合物が、X2O3源(Xは三価元素である)を含まない請求項1〜7のいずれか1項に記載のゼオライト材料の製造方法。
- 工程(1)に係る前記混合物が、1種以上の溶媒を更に含有する請求項1〜12のいずれか1項に記載のゼオライト材料の製造方法。
- 工程(1)に係る前記混合物のH2O:YO2モル比が、3以上100以下の範囲である請求項13に記載のゼオライト材料の製造方法。
- 工程(1)により製造される前記混合物中、1種以上のアルケニルトリアルキルアンモニウムカチオンR1R2R3R4N+:YO2のモル比が、0.01以上5以下の範囲で
ある請求項1〜14のいずれか1項に記載のゼオライト材料の製造方法。 - 工程(1)に係る前記混合物が、ゼオライト骨格構造中のY原子及び/又はX原子の少なくとも一部の同形置換に適した1種以上の元素の1種以上の源を更に有する請求項1〜15のいずれか1項に記載のゼオライト材料の製造方法。
- 同形置換用の1種以上の前記源が1種以上のチタニア前駆体化合物を含有する請求項16に記載のゼオライト材料の製造方法。
- YO2の、ゼオライト骨格構造中のY原子及び/又はX原子の少なくとも一部の同形置換に適した1種以上の前記元素に対する比が、1以上300以下の範囲である請求項16又は17のゼオライト材料の製造方法。
- 工程(2)での結晶化が、前記混合物を加熱する工程を含む請求項1〜18のいずれか1項に記載のゼオライト材料の製造方法。
- 工程(2)での結晶化が、ソルボサーマル条件下で行われる請求項19に記載のゼオライト材料の製造方法。
- 工程(2)での結晶化が、前記混合物を、5時間以上120時間以下の範囲の期間で加熱する工程を含む請求項19又は20に記載のゼオライト材料の製造方法。
- 工程(2)での前記結晶化が、前記混合物を動かす工程を含む請求項1〜21のいずれか1項に記載のゼオライト材料の製造方法。
- 下記工程:
(3)ゼオライト材料を分離する工程、及び/又は、
(4)ゼオライト材料を洗浄する工程、及び/又は、
(5)ゼオライト材料を乾燥する工程、及び/又は、
(6)ゼオライト材料にイオン交換処置を施す工程、
のうち、1以上の工程を更に含み、
工程(3)及び/又は工程(4)及び/又は工程(5)及び/又は工程(6)は、いかなる順番で行うことも可能である請求項1〜22のいずれか1項に記載のゼオライト材料の製造方法。 - 少なくとも1回の工程(6)で、ゼオライト骨格中に含まれる1種以上のイオン性非骨格元素をイオン交換する請求項23に記載のゼオライト材料の製造方法。
- ゼオライト材料の29Si MAS NMRが、
−110.4ppm以下−114.0ppm以上の範囲の第1ピーク(P1)と、
−101.4ppm以下−106.8ppm以上の範囲の第2ピーク(P2)と、を含む請求項25に記載のゼオライト材料。 - ゼオライト材料の27Al MAS NMRスペクトルが、
50.00ppm以上53.50ppm以下の範囲の第1ピーク(P’1)と、
−0.50ppm以下−2.00ppm以上の範囲の第2ピーク(P’2)と、を有する請求項25又は26に記載のゼオライト材料。 - ゼオライト材料の29Si MAS NMRが、
−110.4ppm以下−114.0ppm以上の範囲の第1ピーク(P’’1)と、
−100.2ppm以下−104.2ppm以上の範囲の第2ピーク(P’’2)と、
を含む請求項28に記載のゼオライト材料。 - 逆畳込29Si MAS NMRスペクトルが、−113.2ppm以下−115.2ppm以上の範囲に、1つの更なるピークを含む請求項28又は29に記載のゼオライト材料。
- MFI型骨格構造中のY原子及び/又はX原子の少なくとも一部が、1種以上の元素により同形置換された請求項28〜30のいずれか1項に記載のゼオライト材料。
- YO2の前記1種以上の元素に対するモル比が、5以上100以下の範囲にある請求項31に記載のゼオライト材料。
- YO2:X2O3モル比が、2以上200以下の範囲にある請求項25〜32のいずれか1項に記載のゼオライト材料。
- ゼオライト材料のMFI型骨格構造が、X2O3を含有しない請求項25〜33のいずれか1項に記載のゼオライト材料。
- Yが、Si、Sn、Ti、Zr、Ge及びこれら2種以上の混合物からなる群より選択される請求項25〜34のいずれか1項に記載のゼオライト材料。
- Xが、Al、B、In、Ga及びこれら2種以上の混合物からなる群より選択される請求項25〜33、35のいずれか1項に記載のゼオライト材料。
- ゼオライト材料が、イオン性非骨格元素として、1種以上のカチオン及び/またはカチオン元素を含有する請求項25〜36のいずれか1項に記載のゼオライト材料。
- DIN 66135によるゼオライト材料のBET表面積が、50m2/g以上700m2/g以下の範囲である請求項25〜37のいずれか1項に記載のゼオライト。
- アルケニルトリアルキルアンモニウムカチオンR1R2R3R4N+含有化合物を、MFI型骨格構造を持つゼオライト材料の合成の構造規定剤として使用する方法であって、
R1、R2及びR3は互いに独立して、n−プロピルであり、
R4は、2‐プロペン‐1‐イル又は1‐プロペン‐1‐イルである使用方法。 - 分子ふるいとして、吸収剤として、イオン交換用に、触媒及び/又は触媒担体として使用する請求項25〜38のいずれか1項に記載のゼオライト材料を使用する使用方法。
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