WO2015060189A1 - 高級シランの製造触媒および高級シランの製造方法 - Google Patents
高級シランの製造触媒および高級シランの製造方法 Download PDFInfo
- Publication number
- WO2015060189A1 WO2015060189A1 PCT/JP2014/077538 JP2014077538W WO2015060189A1 WO 2015060189 A1 WO2015060189 A1 WO 2015060189A1 JP 2014077538 W JP2014077538 W JP 2014077538W WO 2015060189 A1 WO2015060189 A1 WO 2015060189A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silane
- catalyst
- producing
- reaction
- higher silane
- Prior art date
Links
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 326
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 193
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 84
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 61
- 239000010703 silicon Substances 0.000 claims abstract description 59
- 239000011148 porous material Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 19
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 16
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical group [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 108
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 97
- 239000007789 gas Substances 0.000 claims description 82
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 150000004756 silanes Chemical class 0.000 claims description 14
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 11
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 194
- 239000007787 solid Substances 0.000 abstract description 45
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 description 62
- 229910021536 Zeolite Inorganic materials 0.000 description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 56
- 239000007795 chemical reaction product Substances 0.000 description 39
- 238000001556 precipitation Methods 0.000 description 37
- 239000011734 sodium Substances 0.000 description 28
- 238000001514 detection method Methods 0.000 description 22
- -1 4 Chemical class 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 14
- 230000004913 activation Effects 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229910052680 mordenite Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000694 effects Effects 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
- 150000002739 metals Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 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 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical group [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a catalyst for producing higher silane and a method for producing higher silane.
- silanes such as monosilane (SiH 4 ) and disilane (Si 2 H 6 ) are recently important as raw materials for producing silicon-based thin films for semiconductor production.
- SiH 4 monosilane
- disilane Si 2 H 6
- Conventionally known methods for producing higher silanes such as disilane include several methods as exemplified below.
- Patent Document 1 Method for producing silicon by hydrogen reduction using hydrogen sulfide or metal sulfide as a catalyst
- Patent Document 2 Method for producing silicon chloride compound by reduction
- Patent Document 3 Silicon-hydrogen bond Or a production method by reacting a silicon oxide having a silicon-silicon bond with an alkali metal or alkaline earth metal hydride, alkoxide, or amalgam
- Patent Document 4 Production method by discharge in monosilane gas
- Patent Document 6 Production method by condensation of monosilane using transition metal complex as catalyst
- Patent Documents 7, 8, and 9 a production method in which lower silane is converted into higher silane by, for example, thermal treatment has been reported.
- higher silane can be produced by heat-treating monosilane at 350 to 550 ° C.
- Patent Document 10 When thermal treatment is used, alumina, a composite oxide containing alumina, or alumina containing a noble metal element such as palladium or rhenium is used as a catalyst, and examples of producing disilane from monosilane even at about 300 ° C. are known. (Patent Document 10).
- the present invention provides a production catalyst that suppresses the formation of fine powder in the reaction for converting lower silane to higher silane and has high selectivity for the target product, and a method for producing higher silane using the catalyst. is there.
- the present inventors consider that a catalyst that promotes the reaction at a lower temperature is necessary in order to improve the above-described problems, and pay attention to a solid catalyst that can be easily separated by a gas phase reaction. We searched for compounds.
- a solid catalyst As a result, as a solid catalyst, a specific porous body having regularly arranged pores of a certain size on the surface of the solid, and acid points with controlled strength and distribution on the surface.
- silane for example, monosilane
- the effect of lowering the temperature of heat treatment is recognized, and it is extremely effective in suppressing the generation of solid silicon and improving the selectivity of the target product. As a result, the present invention has been completed.
- the present invention is a catalyst for producing higher silane and a method for producing higher silane using the catalyst, and includes the following items [1] to [19].
- a catalyst for producing a higher silane comprising a porous oxide, wherein the lower silane is converted into a higher silane having a silicon number higher than that of the lower silane by contacting with the lower silane.
- a higher silane having at least regularly arranged pores, mainly composed of silicon oxide, and having an alkali metal and alkaline earth metal content of 0.00 wt% or more and 2.00 wt% or less. Production catalyst.
- the porous oxide is an aluminosilicate, and the SiO 2 / Al 2 O 3 molar ratio in the porous oxide is 10 or more and 3,000 or less [4] to [6] ]
- the manufacturing catalyst of the higher silane in any one of.
- a process for producing a higher silane characterized by [10] The lower silane is brought into contact with the production catalyst of the higher silane at a temperature lower than a temperature at which the higher silane starts to be substantially formed by thermal decomposition of the lower silane under the condition where no catalyst is present.
- a process for producing higher silanes [11] The method for producing a higher silane according to [9], wherein a temperature at which the lower silane is brought into contact with the production catalyst for the higher silane is 100 ° C. or higher and 400 ° C. or lower. [12] The method for producing a higher silane according to [11], wherein the temperature is 120 ° C. or higher and 350 ° C. or lower.
- the reaction in the reaction for converting lower silane to higher silane, the reaction can be allowed to proceed at a relatively low temperature, the formation of solid silicon is suppressed, and the target product is higher Silane selectivity can be increased.
- FIG. 1 is a schematic diagram of an experimental apparatus.
- the present invention comprises a catalyst for producing a higher silane compound by reacting a lower silane at a relatively low temperature, and a method for producing a higher silane from the lower silane using the catalyst.
- the catalyst used when producing the higher silane from the lower silane of the present invention contains a porous oxide.
- the porous oxide is mainly composed of silicon oxide, and the content thereof is preferably 60% by weight or more and 100% by weight or less.
- the component contained in addition to the silicon oxide is not particularly limited as long as it is a component that is generally contained as a catalyst carrier.
- the porous oxide mainly composed of silicon oxide in the present invention has uniform pores. Uniform pores are pores arranged regularly, and the diameter of the regularly arranged pores is preferably 0.4 nm or more and 0.6 nm or less.
- the pores of the porous oxide can be obtained from a nitrogen adsorption method.
- numerical values described in Atlas of Zeolite Types, Sixth revised edition (Elsevier) of the International Zeolite Association were used.
- the case where there is at least one diameter falling within the range of 0.4 nm to 0.6 nm is described.
- the pores of the catalyst mainly composed of silicon oxide in the present invention are silicon-oxygen bonds, and other elements included as necessary (for example, the skeleton formed by the silicon-oxygen bonds). (Aluminum, titanium, zirconium, magnesium, zinc, etc.)-formed by repeated bonding of oxygen bonds. If the structure of this bond is the same, the pore diameter can be expected to be the same. In the present invention, when the number of oxygen is 8 to 12, that is, an 8- to 12-membered ring of oxygen, the pore diameter is almost the target size. A pore composed of an 8- to 12-membered ring is preferable. When a plurality of types of rings are present in one compound, it is preferable that the ring having the largest number of oxygens is an oxygen 8- to 12-membered ring.
- the reason why the catalyst needs pores and the size of the catalyst needs to be controlled is that the presence of such pores in the catalyst allows a reaction to convert lower silane to higher silane. Since it proceeds in the pores, not only does the reaction proceed rapidly by increasing the catalyst surface area to some extent, but also the size of the pores is limited to a degree, resulting in a higher silane that is the target product (for example, This is probably because the selectivity of disilane) can be improved.
- the content of alkali metal and alkaline earth metal contained in the porous oxide constituting the catalyst of the present invention is 0.00 wt% or more and 2.00 wt% or less, preferably 0.00 wt% or more. Yes, preferably 1.00% by weight or less, more preferably 0.5% by weight or less.
- the said value is content of the alkali metal and alkaline-earth metal seen as a metal contained in a catalyst, and can be measured by methods, such as ICP emission analysis, ICP mass spectrometry, and atomic absorption analysis.
- the silicon oxide used in the present invention can contain an alkali metal or an alkaline earth metal.
- this silicon oxide is treated with an acid, alkali metal ions or alkaline earth metal ions are removed, and the portion is replaced with hydrogen ions in order to maintain electrical neutrality.
- This hydrogen ion functions as a Bronsted acid, and by controlling the amount thereof, not only the acid amount distribution but also the acid strength can be controlled.
- the reaction converting the lower silane to the higher silane of the present invention is promoted when there is an acid point, and it is presumed that the reaction rate and reaction selectivity change depending on the strength and distribution state of the acid point.
- the porous oxide used in the catalyst of the present invention has uniform and regular pores as described above, but the porous oxide is crystalline, and is regularly derived from its crystal structure. It is preferable that the pores arranged in the same manner are formed. At this time, it is possible to form a crystal with only silicon oxide (silicon-oxygen bond). However, when aluminum and other metals coexist, they may be incorporated to form a crystal.
- Such porous oxides mainly containing silicon oxide include aluminosilicate containing aluminum and silicon, and other metals other than aluminum (for example, titanium, zirconium, zinc, iron, boron, gallium, etc. ) And silicon-containing metallosilicates are known.
- crystalline silicon oxides crystalline zeolite is preferably used in terms of having uniform pores.
- the crystalline zeolite preferably used as the catalyst of the present invention generally has a composition represented by the following formula (I).
- M 1 represents an alkali metal ion such as Li + , Na + , K + or a hydrogen ion
- M 2 represents an alkaline earth metal ion such as Ca 2+ , Mg 2+ , Ba 2+.
- M and n are integers, satisfying n ⁇ m, and x is an integer.
- the cations of M 1 and M 2 have a composition that compensates for the negative charge of the aluminum silicate skeleton formed by Al m Si n O 2 (m + n) .
- the structure is a basic unit of the zeolite is tetrahedral structure of SiO 4 or AlO 4, these contiguous with infinite three-dimensional direction to form a crystal.
- the zeolite may have a metallosilicate skeleton in which at least a part of the aluminum element of the formula (I) is replaced with another element such as zinc, iron, boron, gallium, or phosphorus.
- Synthetic zeolite generally uses water glass, sodium silicate, colloidal silica or the like as a silica source, and is used as an alumina source or an oxide source of elements such as iron, boron, titanium, gallium and phosphorus. Are mixed and hydrothermally synthesized in an aqueous alkali solution.
- the zeolite produced by hydrothermal synthesis as shown in the above formula (I), it remains to have an alkali metal such as sodium or potassium, and in this state, the lower silane is contacted and converted to a higher silane. Even if it performs, a catalyst activity is low.
- the framework structure of the above zeolite has been made into a database by the International Zeolite Society and expressed by a structure code consisting of three uppercase letters.
- Examples of the zeolite include BEA type zeolite, FER type zeolite, LTA type zeolite, MFI type zeolite, MOR type zeolite, MWW type zeolite, LTL type zeolite, FAU type zeolite, ERI type zeolite, CHA type zeolite, OFF type zeolite.
- BEA-type zeolite, FER-type zeolite, LTA-type zeolite, MFI-type zeolite, MOR-type zeolite, and MWW-type zeolite are preferable in that the conversion reaction of lower silane to higher silane is preferable. More preferred is type zeolite. These zeolites are presumed to have an appropriate acid distribution and acid strength for the above reaction.
- Examples of the BEA type zeolite include ⁇ type zeolite.
- Examples of the FER type zeolite include ferrierite.
- Examples of the LTA-type zeolite include A-type zeolite.
- Examples of the MFI type zeolite include ZSM-5.
- Examples of the MOR type zeolite include mordenites.
- Examples of the MWW type zeolite include MCM-22.
- Examples of the LTL-type zeolite include L-type zeolite.
- Examples of the FAU type zeolite include X type zeolite, Y type zeolite, and faujasite.
- Examples of the ERI type zeolite include erionite.
- Examples of the CHA-type zeolite include chabasite.
- Examples of the OFF type zeolite include offretite. Among these zeolites, MFI type zeolite is more preferable.
- the porous oxide of the present invention is a crystalline oxide containing an aluminosilicate or a metallosilicate
- the amount of hydrogen ions contained in the aluminosilicate or metallosilicate is contained in the aluminosilicate or metallosilicate from the total amount of ions necessary to compensate for the negative charge of the aluminosilicate or metallosilicate skeleton and maintain electrical neutrality. It can be calculated by subtracting the total amount of alkali metal ions and alkaline earth metal ions. Since hydrogen ions function as an acid as described above, the calculated amount of hydrogen ions is the amount of acid contained in the porous oxide.
- the porous oxide of the present invention is a crystalline oxide (typically zeolite) containing aluminosilicate or metallosilicate
- the alkaline earth metal ions can be exchanged for hydrogen ions according to a known method or a method according to a known method. For example, by treating the silicon composite oxide having an alkali metal ion or alkaline earth metal ion with an ammonium salt solution to exchange the alkali metal ion or alkaline earth metal ion with an ammonium ion, firing at a high temperature Thus, it can be converted into a form substituted with hydrogen ions.
- a fine powder silica can be used as a silica source in addition to the above-described ion exchange.
- Colloidal silica, tetraethoxysilane (TEOS), etc., and metal sources such as aluminum, aluminum sulfate, aluminum nitrate, sodium aluminate, etc., or oxidation of elements such as iron, boron, titanium, phosphorus, gallium, etc.
- TEOS tetraethoxysilane
- metal sources such as aluminum, aluminum sulfate, aluminum nitrate, sodium aluminate, etc., or oxidation of elements such as iron, boron, titanium, phosphorus, gallium, etc.
- a method is also possible in which a compound as a source is mixed, an organic structure directing agent such as a quaternary ammonium salt and water are added, and hydrothermal synthesis is carried out.
- the SiO 2 / Al 2 O 3 molar ratio can take any value, Usually, it is 5 or more, preferably 10 or more, more preferably 20 or more, and usually 5,000 or less, preferably 3,000 or less, more preferably 2,000 or less.
- the SiO 2 / Al 2 O 3 molar ratio is within the above range, the acid strength tends to be suitable for a reaction for producing a higher silane such as disilane.
- the SiO 2 / Al 2 O 3 molar ratio can be determined by, for example, fluorescent X-ray analysis.
- the amount of hydrogen ions is determined based on the total amount of ions necessary to compensate for the negative charge of the skeleton and maintain electrical neutrality, and alkali metal ions and alkaline earth metal ions contained in the aluminosilicate or metallosilicate. This can be calculated by subtracting the total amount, but a specific calculation method example will be described here.
- ZSM-5 zeolite having a SiO 2 / Al 2 O 3 molar ratio of 1500 contains 0.01% by weight of Na.
- the amount of Al contained in 1 g of ZSM-5 zeolite is 83.8 micromol, which is the total amount of ions necessary to compensate for the negative charge of the framework and maintain electrical neutrality.
- the amount of Na contained in 1 g of ZSM-5 zeolite is 4.3 ⁇ mol.
- the amount of hydrogen ions contained in 1 g of ZSM-5 zeolite is calculated to be 79.5 micromol.
- the specific surface area of the porous oxide used as a catalyst of the present invention by the BET method is preferably 100 m 2 / g or more, more preferably It is 200 m 2 / g or more, preferably 1,000 m 2 / g or less, more preferably 800 m 2 / g or less.
- the porous oxide used as the catalyst of the present invention includes, for example, platinum, palladium, ruthenium, rhodium, copper, silver, molybdenum, nickel in order to further improve the performance and characteristics as a catalyst.
- An appropriate transition metal element having a catalytic function such as iron or cobalt may be appropriately introduced by an ion exchange method or an impregnation method.
- the porous oxide When the porous oxide needs to be molded, it can be molded by various methods according to a known method or a method according to a known method.
- an appropriate binder such as alumina, silica, silica alumina, zirconia, magnesia, titania, clay mineral or the like may be mixed with the porous oxide, and the resulting mixture may be formed by a method such as extrusion.
- mold a porous oxide for example by a compression molding method etc., without using a binder. By forming in this way, it can be made into an appropriate size and shape, and can be adapted according to the reaction mode, process, etc. in producing the higher silane in the present invention.
- the method for producing a higher silane of the present invention is a method for converting the lower silane into a higher silane having a higher number of silicon than the lower silane by bringing the lower silane into contact with the higher silane production catalyst.
- an appropriate lower silane can be used as a raw material according to the intended higher silane.
- the lower silane used as a raw material include silanes such as monosilane, disilane, and trisilane (Si n H 2n + 2 ; n is an integer of 1 or more). These silanes can be used alone or in combination of two or more. For example, when disilane is used as a target product (higher silane), monosilane is used as a raw material (lower silane).
- the lower silane used as a raw material may be used as it is without being diluted, or may be used after being diluted with another diluent gas.
- the dilution gas for dilution is not particularly limited as long as it is a gas inert to lower silane, such as nitrogen, hydrogen, argon, and helium.
- the concentration of the lower silane in the raw material gas is usually 1 vol% or more, preferably 10 vol% or more, more preferably 20 vol% or more, and usually 95 vol% or less, preferably 90 vol% or less, more preferably 80 vol% or less.
- the concentration of the lower silane in the raw material gas is preferably 50 vol% or more, and preferably 100 vol% or less.
- a method of coexisting hydrogen with the raw material gas may be used in order to suppress silicon deposition.
- the necessity of coexisting hydrogen in the raw material gas is low, and the non-catalytic system Compared with this manufacturing method, productivity can be improved by reducing the size of the manufacturing apparatus and reducing the manufacturing cost.
- the lower silane used as the raw material and the target product higher silane are not particularly limited.
- the lower silane is monosilane, the higher silane is disilane and trisilane, and the monosilane
- a lower silane is disilane and a higher silane is trisilane.
- the method for producing trisilane from disilane can be preferably applied.
- the lower silane used for the raw material may contain impurities as long as it is inert to the reaction.
- oxygen, carbon dioxide, carbon monoxide, nitrogen-containing compounds such as amines and nitriles, oxygen-containing compounds such as water, alcohols, aldehydes and ketones, olefins such as ethylene and acetylene, and phosphine may inhibit the catalytic activity. Therefore, it is preferable to reduce as much as possible.
- the temperature at which the lower silane is brought into contact with the production catalyst is the same as the pressure, residence time, lower silane concentration in the raw material gas, reaction mode, etc., except that the production catalyst is not used. Below, the temperature is lower than the temperature at which higher silane begins to substantially form due to thermal decomposition of lower silane. According to the present invention, higher silane can be produced from lower silane at such a low temperature.
- the temperature at which the lower silane is brought into contact with the production catalyst is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher, usually 400 ° C. or lower, preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
- the temperature is too low, the conversion of the raw material lower silane is not insufficient, the reaction temperature is too high, the solid silicon precipitation becomes remarkable, the reactor Solid silicon adheres and accumulates on the inner wall and piping, so that stable operation is not difficult.
- the reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but is preferably 0.1 MPaG or more and 1.0 MPaG or less. To some extent, it is advantageous to reduce the size of the reactor and the equipment incidental to it under pressure. On the other hand, if the pressure is too high, the solid silicon may be easily generated. Therefore, the reaction is preferably performed at a pressure of 1.0 MPaG or less.
- the reaction mode is not particularly limited, and can be carried out in any of batch, semi-batch, and continuous methods. It is preferably carried out by a continuous distribution system using a moving bed or the like.
- a gas containing lower silane such as monosilane In the case of a fixed bed, specifically, it is preferable to continuously circulate a gas containing lower silane such as monosilane through a tubular reactor filled with a catalyst that is appropriately shaped as described above. Only one reactor may be used, and when a plurality of reactors are used, they may be connected in a continuous or parallel manner, or may be used in combination.
- a gas hourly space velocity (GHSV) is usually 50 hr -1 or more, preferably 100 hr -1 or more, and usually 5,000 hr -1 or less, preferably 2,000 hr -1 or less. Within this range, the gas space velocity is reduced, the amount of catalyst used relative to the production amount is increased, or the reactor size is not increased. On the contrary, the gas space velocity becomes too high, the conversion rate is lowered, the cost for the separation and recovery of the unreacted lower silane is increased, and there is no economical disadvantage.
- GHSV gas hourly space velocity
- the lower silane conversion rate when the conversion rate of the lower silane decreases due to the passage of the reaction time or the like, the lower silane conversion rate can be improved by performing a catalyst activation treatment.
- the catalyst activation treatment may be performed by removing the catalyst from the reactor or may be performed with the catalyst kept in the reactor, but the number of steps can be simplified. It is desirable to carry out the catalyst activation treatment while keeping the catalyst in the state.
- the method of catalyst activation treatment is not particularly limited, but the flow of lower silane is stopped from the state in which lower silane or a mixture of lower silane and a dilution gas such as hydrogen gas is passed, and the gas containing hydrogen gas is passed. It is preferable to make it.
- the gas to be circulated during the catalyst activation treatment is preferably 100% hydrogen gas, but may be diluted with an inert gas such as nitrogen or argon as necessary.
- the temperature during the catalyst activation treatment is not particularly limited, but is preferably 20 ° C or higher, more preferably 50 ° C or higher, further preferably 100 ° C or higher, preferably 600 ° C or lower, more preferably 400 ° C or lower, Preferably it is 300 degrees C or less.
- the pressure of the catalyst activation treatment may be any of reduced pressure, normal pressure, and increased pressure, but is preferably 0.01 PaG or more and 1.0 MPaG or less.
- the reaction gas coming out of a reactor for producing higher silane from lower silane is separated into unreacted lower silane and produced higher silane by a known method such as cooling or distillation.
- the lower silane used as the raw material for the higher silane can be recovered, recycled to the reactor, and used again for the production of the higher silane.
- higher silane can be produced with high productivity.
- It is also possible to produce higher silanes with higher selectivity by carrying out the reaction again using higher silanes produced from lower silanes as raw materials.
- it is possible to selectively produce a higher silane such as trisilane by carrying out the reaction again using disilane as a raw material after producing disilane from monosilane as a raw material.
- any higher silane can be produced with high selectivity and high efficiency by using the present invention and recycling the produced silanes again as raw materials.
- the experimental apparatus used in the present invention is shown in FIG.
- the reactor was filled with a catalyst, and the reactor was heated to a predetermined temperature in an electric furnace.
- the flow rate of the source gas was controlled by a mass flow meter.
- the gas obtained by the reaction was introduced online into a gas chromatograph (manufactured by Shimadzu Corporation), and the concentrations of monosilane, disilane, and trisilane were analyzed.
- the gas chromatography measurement was performed as follows.
- Analytical instrument Gas chromatograph GC-8A (manufactured by Shimadzu Corporation)
- Carrier-gas helium (40 ml / min) Column temperature: After holding at 70 ° C.
- the amount of MS supplied per hour (mol / min) and the content of each of the above components the amount of DS produced per hour (mol number of Si atoms / min) after the reaction and the amount of TS produced per hour (Si atom equivalent) mol number / min) and the unreacted MS residual amount (Si atom conversion mol number / min). In any case, no higher silane than tetrasilane was detected.
- DS conversion (mol%) TS production amount (mol) ⁇ 3 / (DS production amount (mol) ⁇ 2 + TS production amount (mol) ⁇ 3)
- DS conversion (mol%) (TS generation amount (mol) ⁇ 3) / (DS supply amount (mol) ⁇ 2)
- a mixed gas of monosilane gas and hydrogen gas (monosilane concentration: 80 vol%) was introduced into the reactor so that the gas space velocity was 140 h ⁇ 1, and the reaction was performed at 200 ° C. and 0.12 MPaG.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. From these values, the MS conversion was 1.06 (mol%). Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. The results are shown in Table 1.
- Example 2 The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 250 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. MS conversion was 1.88 (mol%). The results are shown in Table 1.
- Example 4 The reaction was conducted in the same manner as in Example 3 except that the reaction temperature was 250 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. MS conversion was 4.20 (mol%). The results are shown in Table 1.
- the reaction was conducted in the same manner as in Example 1 except that 5 mm pellets and binder type: alumina) were used and the reaction temperature was 150 ° C.
- Example 1 the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. The MS conversion was 2.97 (mol%). The results are shown in Table 1.
- Example 6 The reaction was conducted in the same manner as in Example 5 except that the reaction temperature was 200 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. The MS conversion was 6.79 (mol%). The results are shown in Table 1.
- the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit.
- MS conversion was 1.74 (mol%).
- Table 1 The results are shown in Table 1.
- Example 8 The reaction was conducted in the same manner as in Example 7 except that the reaction temperature was 250 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. MS conversion was 2.15 (mol%). The results are shown in Table 1.
- Example 10 The reaction was performed in the same manner as in Example 9 except that the reaction temperature was 200 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 6.21 (mol%), and no precipitation of solid silicon on the wall surface of the reaction tube was visually observed. The results are shown in Table 2.
- Example 2 Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 2.89 (mol%), and no precipitation of solid silicon on the wall surface of the reaction tube was visually observed. The results are shown in Table 2.
- Example 12 The reaction was conducted in the same manner as in Example 11 except that the reaction temperature was 200 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 6.81 (mol%), and no precipitation of solid silicon on the wall surface of the reaction tube was visually observed. The results are shown in Table 2.
- Example 2 Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 3.02 (mol%), and no precipitation of solid silicon on the wall surface of the reaction tube was visually observed. The results are shown in Table 2.
- Example 14 The reaction was conducted in the same manner as in Example 13 except that the reaction temperature was 200 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 6.94 (mol%), and no precipitation of solid silicon on the wall surface of the reaction tube was visually observed. The results are shown in Table 2.
- a mixed gas of monosilane gas and hydrogen gas (monosilane concentration: 80 vol%) was introduced into the reactor so that the gas space velocity was 467 h ⁇ 1, and the reaction was performed at 150 ° C. and 0.2 MPaG.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 2.37 (mol%), the DS selectivity was 88.9 (mol%), and the TS selectivity was 11.1 (mol%). The results are shown in Table 3.
- Example 16 The reaction was conducted in the same manner as in Example 15 except that the reaction temperature was 200 ° C. Similarly to Example 15, the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 4.28 (mol%), the DS selectivity was 84.1 (mol%), and the TS selectivity was 15.9%. The results are shown in Table 3.
- a mixed gas of monosilane gas and hydrogen gas (monosilane concentration: 80 vol%) was introduced into the reactor so that the gas space velocity was 467 h ⁇ 1, and the reaction was performed at 150 ° C. and 0.2 MPaG.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that MS conversion was 2.35 (mol%), DS selectivity was 88.6 (mol%), and TS selectivity was 11.5 (mol%). The results are shown in Table 3.
- Example 18 The reaction was conducted in the same manner as in Example 17 except that the reaction temperature was 200 ° C.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 4.33 (mol%), the DS selectivity was 84.2 (mol%), and the TS selectivity was 15.9 (mol%). The results are shown in Table 3.
- Example 19 The reaction was conducted in the same manner as in Example 17 except that the reaction pressure was 0.3 MPaG.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 2.28 (mol%), the DS selectivity was 89.3 (mol%), and the TS selectivity was 10.7 (mol%). The results are shown in Table 3.
- Example 20 The reaction was conducted in the same manner as in Example 19 except that the reaction temperature was 200 ° C.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 4.70 (mol%), the DS selectivity was 83.0 (mol%), and the TS selectivity was 17.0 (mol%). The results are shown in Table 3.
- Example 21 The reaction was conducted in the same manner as in Example 17 except that the reaction pressure was 0.4 MPaG.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 2.41 (mol%), the DS selectivity was 89.0 (mol%), and the TS selectivity was 11.0 (mol%). The results are shown in Table 3.
- Example 22 The reaction was conducted in the same manner as in Example 21 except that the reaction temperature was 200 ° C. Similarly to Example 21, the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, MS conversion was 4.93 (mol%), DS selectivity was 82.0 (mol%), and TS selectivity was 18.0 (mol%). The results are shown in Table 3.
- Example 23 The reaction was performed in the same manner as in Example 17 except that the monosilane concentration was 95%.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, the MS conversion rate was 1.80 (mol%), the DS selectivity was 91.5 (mol%), and the TS selectivity was 8.5 (mol%).
- Table 3 The results are shown in Table 3.
- Example 24 The reaction was conducted in the same manner as in Example 23 except that the reaction temperature was 200 ° C. Similarly to Example 23, the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 3.88 (mol%), the DS selectivity was 85.6 (mol%), and the TS selectivity was 14.4 (mol%). The results are shown in Table 3.
- Example 25 The reaction was performed in the same manner as in Example 17 except that the monosilane concentration was 100%.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion was 1.67 (mol%), the DS selectivity was 92.1 (mol%), and the TS selectivity was 7.9 (mol%). The results are shown in Table 3.
- Example 26 The reaction was conducted in the same manner as in Example 25 except that the reaction temperature was 200 ° C.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, MS conversion was determined to be 3.72 (mol%), DS selectivity 85.8 (mol%), and TS selectivity 14.2 (mol%). The results are shown in Table 3.
- Example 27 The reaction was performed in the same manner as in Example 17 except that the gas empty constant velocity was 233 h ⁇ 1 .
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that the MS conversion rate was 2.34 (mol%), the DS selectivity was 89.3 (mol%), and the TS selectivity was 10.7 (mol%). The results are shown in Table 3.
- Example 28 The reaction was conducted in the same manner as in Example 27 except that the reaction temperature was 200 ° C.
- the reaction product was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. From these values, it was determined that MS conversion was 5.52 (mol%), DS selectivity was 80.8 (mol%), and TS selectivity was 19.2 (mol%). The results are shown in Table 3.
- a mixed gas of monosilane gas and hydrogen gas (monosilane concentration: 80 vol%) was introduced into the reactor so that the gas space velocity was 467 h ⁇ 1, and the reaction was performed at 180 ° C. and 0.4 MPaG.
- the reaction product 10 hours after the start of the reaction was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined.
- the MS conversion was 4.26 (mol%)
- the DS selectivity was 82.1 (mol%)
- the TS selectivity was 17.9 (mol%).
- Example 30 (Regeneration test of production catalyst) After 200 hours from the start of the reaction described in Example 29, the supply of monosilane was stopped, and the catalyst activation treatment was performed for 3 hours at 180 ° C. under a flow of only hydrogen gas and normal pressure. After the catalyst activation treatment, the reaction was performed under the same conditions as in Example 29. The reaction product 1 hour after the resumption of the reaction was introduced online into a gas chromatograph GC-8A (manufactured by Shimadzu Corporation), and the contents of monosilane, disilane, and trisilane were determined. The MS conversion was 3.77 (mol%), The DS selectivity was 84.8 (mol%), and the TS selectivity was 15.2 (mol%).
- Comparative Example 2 The reaction was performed in the same manner as in Comparative Example 1 except that the reaction temperature was 250 ° C. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. The amount of trisilane produced was below the detection limit. Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. MS conversion was 0.13 (mol%), DS selectivity was 100 (mol%), and TS selectivity was 0 (mol%).
- Example 1 The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 350 ° C., 375 ° C., 400 ° C., and 425 ° C. without charging the catalyst. Similarly to Example 1, the reaction product was introduced online into a gas chromatograph, and the contents of monosilane, disilane, and trisilane were determined. Below 300 ° C., no conversion of monosilane was observed, and a high temperature of 350 ° C. was required to produce disilane. Further, at a temperature of 400 ° C. or higher, generation of trisilane was confirmed, and precipitation of solid silicon on the wall of the reaction tube was observed.
- Reference Example 3 The reaction was conducted in the same manner as in Reference Example 2 except that the reaction temperature was 200 ° C. Similarly to Reference Example 2, the reaction product was introduced into a gas chromatograph online, and the content of monosilane, disilane, and trisilane was determined. The MS conversion was 0.48 (mol%). Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. The results are shown in Table 5.
- Reference Example 4 The reaction was performed in the same manner as in Reference Example 2 except that the reaction temperature was 250 ° C. As in Reference Example 2, the reaction product was introduced into a gas chromatograph online and the monosilane, disilane, and trisilane contents were determined. The MS conversion was 0.89 (mol%). Moreover, the precipitation of the solid silicon on the wall surface of the reaction tube was not visually observed. The results are shown in Table 5.
- silane for example, disilane when the lower silane is monosilane
- high-purity higher silane for example, disilane when the lower silane is monosilane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nanotechnology (AREA)
- Silicon Compounds (AREA)
Abstract
Description
従来から知られているジシランなどの高級シランの製造方法としては、次に例示するようないくつかの方法がある。
[1] 多孔質酸化物を含む、低級シランに接触することにより、該低級シランを、該低級シランよりケイ素数が多い高級シランへ変換させる高級シランの製造触媒であり、該多孔質酸化物が、規則的に配列する細孔を少なくとも有し、主としてケイ素酸化物からなり、かつ、アルカリ金属およびアルカリ土類金属の含有量が0.00重量%以上2.00重量%以下である高級シランの製造触媒。
[2] 前記多孔質酸化物の細孔の直径が0.4nm以上0.6nm以下である、[1]記載の高級シランの製造触媒。
[3] 前記多孔質酸化物の細孔が酸素の8~12員環で構成された細孔である、[1]または[2]に記載の高級シランの製造触媒。
[4] 前記多孔質酸化物がアルミノシリケートまたはメタロシリケートからなる結晶性ゼオライト構造を有する[1]~[3]のいずれかに記載の高級シランの製造触媒。
[5] 前記結晶性ゼオライト構造が、BEA型、FER型、LTA型、MFI型、MOR型、MWW型のなかの少なくともいずれか1種である[4]に記載の高級シランの製造触媒。
[6] 前記多孔質酸化物中のアルミノシリケートまたはメタロシリケート骨格の負電荷を補償するアルカリ金属イオンまたはアルカリ土類金属イオンが水素イオンに置換されていることを特徴とする、[4]または[5]に記載の高級シランの製造触媒。
[7] 前記多孔質酸化物がアルミノシリケートであり、該多孔質酸化物中のSiO2/Al2O3モル比が10以上3,000以下であることを特徴とする[4]~[6]のいずれかに記載の高級シランの製造触媒。
[8] 前記SiO2/Al2O3モル比が20以上2,000以下であることを特徴とする[7]に記載の高級シランの製造触媒。
[9] [1]~[8]のいずれかに記載の高級シランの製造触媒に、低級シランを接触させることにより、該低級シランを、該低級シランよりケイ素数が多い高級シランへ変換させることを特徴とする高級シランの製造方法。
[10] 触媒が存在しない条件下で、低級シランの熱的分解により高級シランが実質的に生成し始める温度より低い温度で前記高級シランの製造触媒に低級シランを接触させる、[9]に記載の高級シランの製造方法。
[11] 前記高級シランの製造触媒に低級シランを接触させる温度が、100℃以上400℃以下であることを特徴とする[9]記載の高級シランの製造方法。
[12] 前記温度が、120℃以上350℃以下であることを特徴とする[11]記載の高級シランの製造方法。
[13] 前記温度が、140℃以上300℃以下であることを特徴とする[11]記載の高級シランの製造方法。
[14] 前記低級シランは、低級シランを含む原料ガスによって供給され、原料ガス中の低級シランの濃度は、50vol%以上100vol%以下である[9]~[13]のいずれか一項に記載の高級シランの製造方法。
[15] 低級シランがモノシランであり、高級シランがジシランおよびトリシランであることを特徴とする[9]~[14]のいずれか一項に記載の高級シランの製造方法。
[16] 低級シランがモノシランであり、高級シランがジシランであることを特徴とする[9]~[14]のいずれかに記載の高級シランの製造方法。
[17] 低級シランがジシランであり、高級シランがトリシランであることを特徴とする[9]~[14]のいずれかに記載の高級シランの製造方法。
[18] 高級シランの製造触媒を水素含有ガスで賦活処理する工程を含むことを特徴とする[9]~[14]のいずれかに記載の高級シランの製造方法。
[19] 高級シランの製造触媒を水素含有ガスで賦活処理する工程の処理温度が20℃以上であることを特徴とする[18]に記載の高級シランの製造方法。
本発明は、低級シランを比較的低温で反応させて高級シラン化合物を製造するための触媒、及び、該触媒を用いた低級シランからの高級シランの製造方法からなる。
本発明の低級シランから高級シランを製造する際に用いられる触媒は、多孔質酸化物を含む。この多孔質酸化物は主としてケイ素酸化物からなるが、その含有量は60重量%以上100重量%以下であることが好ましい。ケイ素酸化物以外に含まれる成分としては、一般的に触媒担体として含まれる成分であれば特に制限はなく、例えば、アルミニウム酸化物、チタン酸化物、ジルコニウム酸化物、亜鉛酸化物、マグネシウム酸化物、鉄酸化物、ホウ素酸化物、ガリウム酸化物などが挙げられる。これら成分は、ケイ素酸化物と物理的に混合した状態で含まれていてもよく、あるいは化学的に複合化した状態(複合酸化物の状態)で含まれていてもよい。
(M1,M2 1/2)m(AlmSinO2(m+n))・xH2O (I)
上記式(I)中、M1はLi+、Na+、K+等のアルカリ金属イオンまたは水素イオンを表し、M2はCa2+、Mg2+、Ba2+等のアルカリ土類金属イオンを表し、mおよびnは整数であり、n≧mを満たし、xは整数である。
なお、本発明の触媒として用いる多孔質酸化物には、触媒としての性能や特性をさらに改善するために、必要に応じて、例えば、白金、パラジウム、ルテニウム、ロジウム、銅、銀、モリブデン、ニッケル、鉄、コバルト等の触媒機能を有する適当な遷移金属元素を適宜、イオン交換法や含浸法等により導入してもよい。
本発明の高級シランの製造方法は、上記高級シランの製造触媒に、低級シランを接触させることにより、該低級シランを、該低級シランよりケイ素数が多い高級シランへ変換させる方法である。
また、低級シランから製造した高級シランを原料として再度、反応を実施することにより、より高い選択率で高級シランを製造することも可能である。例えばモノシランを原料としてジシランを製造した後に、ジシランを原料として再度、反応を実施することにより、トリシラン等のさらなる高級シランを選択的に製造することが可能となる。
前記したように、本発明を利用し、製造したシラン類を再度原料としてリサイクルすれば、任意の高級シランを高選択率、高効率で製造することが可能となる。
本発明で使用した実験装置を図1に示す。反応器内部に触媒を充填し、反応器を電気炉内で所定の温度へ昇温した。原料ガスの流量はマスフローメーターで制御した。
分析機器:ガスクロマトグラフ GC-8A(島津製作所社製)
カラム:Porapak-QS(Waters社製)、長さ1メートル、直径3mm
分析対象物の滞留時間(リテンションタイム):モノシラン=7.5分、ジシラン=12.5分、トリシラン=21.0分
キャリア-ガス:ヘリウム(40ml/min)
カラム温度:70℃5分保持後、16℃/分で180℃まで昇温
注入口温度:200℃
TCD検出器温度:200℃
TCD検出器電流:ミリアンペア
原料、生成物の定量方法:
上述のガスクロマトグラフの測定結果から、反応したガス中に含まれるモノシラン(MS)、ジシラン(DS)、トリシラン(TS)の含有量(mol%)を求めた。時間当りのMS供給量(mol/min)および上記各成分の含有量から、反応後の、時間当たりのDS生成量(Si原子換算mol数/min)、時間当たりのTS生成量(Si原子換算mol数/min)、未反応のMS残存量(Si原子換算mol数/min)を求めた。なお、いずれの場合も、テトラシラン以上の高級シランは検出されなかった。
MS転化率(mol%)=(DS生成量(mol)×2+TS生成量(mol)×3)/MS供給量(mol)
DS選択率(mol%)=DS生成量(mol)×2/(DS生成量(mol)×2+TS生成量(mol)×3)
TS選択率(mol%)=TS生成量(mol)×3/(DS生成量(mol)×2+TS生成量(mol)×3)
また、ジシランを原料とした場合には、以下のようにして、DS転化率(mol%)を求めた。
DS転化率(mol%)=(TS生成量(mol)×3)/(DS供給量(mol)×2)
モルデナイト(SiO2/Al2O3モル比=18、Na含有量[wt%]=0.04、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.48nm、0.57nm(0.4nm以上0.6nm以以下である)、形状:1.5mmペレット、バインダー種:アルミナ)を、内径が8mmの反応管に45cc充填した後、窒素流通下400℃で加熱することで触媒の前処理を実施した。モノシランガスと水素ガスとの混合ガス(モノシラン濃度:80vol%)を、ガス空間速度が140h-1となるように反応器に導入し、200℃、0.12MPaGで反応を行った。10時間後に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。これらの値から、MS転化率1.06(mol%)であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表1に示す。
反応温度を250℃とした以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は1.88(mol%)であった。結果を表1に示す。
実施例1の触媒の替わりにZSM-5(SiO2/Al2O3モル比=23、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:3mmペレット、バインダー種:アルミナ)を使用した以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は0.93(mol%)であった。結果を表1に示す。
反応温度を250℃とした以外は、実施例3と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は4.20(mol%)であった。結果を表1に示す。
実施例1の触媒の替わりに実施例3、4とは異なる性質を有するZSM-5(SiO2/Al2O3モル比=1,500、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:1.5mmペレット、バインダー種:アルミナ)を使用し、反応温度を150℃とした以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は2.97(mol%)であった。結果を表1に示す。
反応温度を200℃とした以外は、実施例5と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は6.79(mol%)であった。結果を表1に示す。
実施例1の触媒の替わりにβ型(SiO2/Al2O3モル比=500、Na含有量[wt%]=0.07、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.56nm(0.4nm以上0.6nm以下である)、形状:1.5mmペレット、バインダー種:粘土)を使用した以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は1.74(mol%)であった。結果を表1に示す。
反応温度を250℃とした以外は、実施例7と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は2.15(mol%)であった。結果を表1に示す。
実施例1の触媒の替わりに実施例3、4とは異なる性質を有するZSM-5(SiO2/Al2O3モル比=80、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:1.5mmペレット、バインダー種:アルミナ)を使用し、反応温度を150℃とした以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は2.23(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
反応温度を200℃とした以外は、実施例9と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は6.21(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
実施例1の触媒の替わりに実施例3、4とは異なる性質を有するZSM-5(SiO2/Al2O3モル比=280、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:1.5mmペレット、バインダー種:アルミナ)を使用し、反応温度を150℃とした以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は2.89(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
反応温度を200℃とした以外は、実施例11と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は6.81(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
実施例1の触媒の替わりに実施例3、4とは異なる性質を有するZSM-5(SiO2/Al2O3モル比=280、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:1.5mmペレット、バインダー種:アルミナ)を使用し、反応温度を150℃とした以外は、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は3.02(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
反応温度を200℃とした以外は、実施例13と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。MS転化率は6.94(mol%)であり、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表2に示す。
ZSM-5(SiO2/Al2O3モル比=1500、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:3mmペレット、バインダー種:アルミナ)を内径が8mmの反応管に6.4cc充填した後、窒素流通下400℃で加熱することで触媒の前処理を実施した。モノシランガスと水素ガスとの混合ガス(モノシラン濃度:80vol%)を、ガス空間速度が467h-1となるように反応器に導入し、150℃、0.2MPaGで反応を行った。反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率2.37(mol%)、DS選択率88.9(mol%)、TS選択率11.1(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例15と同様に反応を行った。実施例15と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率4.28(mol%)、DS選択率84.1(mol%)、TS選択率15.9%)と求められた。結果を表3に示す。
ZSM-5(SiO2/Al2O3モル比=1500、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:3mmペレット、バインダー種:アルミナ)を内径が8mmの反応管に6.4cc充填した後、窒素流通下200℃で加熱することで触媒の前処理を実施した。モノシランガスと水素ガスとの混合ガス(モノシラン濃度:80vol%)を、ガス空間速度が467h-1となるように反応器に導入し、150℃、0.2MPaGで反応を行った。反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率2.35(mol%)、DS選択率88.6(mol%)、TS選択率11.5(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率4.33(mol%)、DS選択率84.2(mol%)、TS選択率15.9(mol%)と求められた。結果を表3に示す。
反応圧力を0.3MPaGとした以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率2.28(mol%)、DS選択率89.3(mol%)、TS選択率10.7(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例19と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率4.70(mol%)、DS選択率83.0(mol%)、TS選択率17.0(mol%)と求められた。結果を表3に示す。
反応圧力を0.4MPaGとした以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率2.41(mol%)、DS選択率89.0(mol%)、TS選択率11.0(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例21と同様に反応を行った。実施例21と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率4.93(mol%)、DS選択率82.0(mol%)、TS選択率18.0(mol%)と求められた。結果を表3に示す。
モノシラン濃度を95%とする以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率1.80(mol%)、DS選択率91.5(mol%)、TS選択率8.5(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例23と同様に反応を行った。実施例23と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率3.88(mol%)、DS選択率85.6(mol%)、TS選択率14.4(mol%)と求められた。結果を表3に示す。
モノシラン濃度を100%とする以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率1.67(mol%)、DS選択率92.1(mol%)、TS選択率7.9(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例25と同様に反応を行った。実施例25と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率3.72(mol%)、DS選択率85.8(mol%)、TS選択率14.2(mol%)と求められた。結果を表3に示す。
ガス空等速度を233h-1とする以外は、実施例17と同様に反応を行った。実施例17と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率2.34(mol%)、DS選択率89.3(mol%)、TS選択率10.7(mol%)と求められた。結果を表3に示す。
反応温度を200℃とした以外は、実施例27と同様に反応を行った。実施例27と同様に、反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。これらの値から、MS転化率5.52(mol%)、DS選択率80.8(mol%)、TS選択率19.2(mol%)と求められた。結果を表3に示す。
ZSM-5(SiO2/Al2O3モル比=1500、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.51nm、0.53nm、0.55nm、0.56nm(0.4nm以上0.6nm以下である)、形状:3mmペレット、バインダー種:アルミナ)を内径が8mmの反応管に6.4cc充填した後、窒素流通下200℃で加熱することで触媒の前処理を実施した。モノシランガスと水素ガスとの混合ガス(モノシラン濃度:80vol%)を、ガス空間速度が467h-1となるように反応器に導入し、180℃、0.4MPaGで反応を行った。反応開始10時間後の反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率4.26(mol%)、DS選択率82.1(mol%)、TS選択率17.9(mol%)であった。反応を継続し、反応開始200時間後の反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率2.32(mol%)、DS選択率89.3(mol%)、TS選択率10.7(mol%)であった。結果を表4に示す。
実施例29に記載の反応開始200時間後に、モノシランの供給を停止し、水素ガスのみ流通、常圧下、180℃で、触媒賦活処理を3時間行った。触媒賦活処理後、実施例29と同等の条件で反応を行った。反応再開1時間後の反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率3.77(mol%)、DS選択率84.8(mol%)、TS選択率15.2(mol%)であった。再度、モノシランの供給を停止し、水素ガスのみ流通、常圧下、180℃で、触媒賦活処理を72時間行った。触媒賦活処理後、実施例29と同等の条件で反応を行った。反応再開1時間後の反応生成物をオンラインでガスクロマトグラフGC-8A(島津製作所製)へ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率4.24(mol%)、DS選択率81.5(mol%)、TS選択率18.5(mol%)であった。結果を表4に示す。
実施例1の触媒の替わりに実施例1とは異なる性質を有するモルデナイト(SiO2/Al2O3モル比=18、Na含有量[wt%]=3.7、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.48nm、0.57nm(0.4nm以上0.6nm以下である)、形状:1.2mmペレット、バインダー種:粘土)を使用し、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は0.07(mol%)、DS選択率は100(mol%)、TS選択率は0(mol%)であった。この結果からも分かるように、同じモルデナイトでもそのモルデナイトに含まれるナトリウムイオンが水素イオンに置換された形態であるモルデナイトを使用して同じ条件にて反応を行った実施例1と比較して、モノシランの転化率は非常に低い結果となった。結果を表5に示す。
反応温度を250℃とした以外は、比較例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は0.13(mol%)、DS選択率は100(mol%)、TS選択率は0(mol%)であった。この結果からも分かるように、同じモルデナイトでもそのモルデナイトに含まれるナトリウムイオンが水素イオンに置換された形態であるモルデナイトを使用して同じ条件にて反応を行った実施例1と比較して、モノシランの転化率は非常に低い結果となった。結果を表5に示す。
γ―アルミナ(住化アルケム製FD-24;2~4mm球状、BET比表面積=330m2/g)を使用し、実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。トリシランの生成量は検出下限界以下であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。MS転化率は0.15(mol%)、DS選択率は100(mol%)、TS選択率は0(mol%)であった。この結果からも分かるように、同じ条件にて反応を行った実施例1、3、6、7と比較して、モノシランの転化率は非常に低い結果となった。結果を表5に示す。
触媒を充填せずに、反応温度を350℃、375℃、400℃、425℃とした以外は実施例1と同様に反応を行った。実施例1と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めた。300℃以下ではモノシランの転化は全く認められず、ジシランを生成させるためには350℃の高温が必要であった。また400℃以上の温度では、トリシランの生成が確認されるとともに、反応管の壁面での固体ケイ素の析出が認められた。反応温度350℃では、MS転化率0.04(mol%)、DS選択率100(mol%)、TS選択率0(mol%)であり、反応温度375℃では、MS転化率0.25(mol%)、DS選択率100(mol%)、TS選択率0(mol%)であった。また、反応温度400℃では、MS転化率1.13(mol%)、DS選択率89.0(mol%)、TS選択率10.8(mol%)であり、反応温度425℃では、MS転化率4.75(mol%)、DS選択率82.6(mol%)、TS選択率17.2(mol%)であった。結果を表5に示す。
Y型ゼオライト(SiO2/Al2O3モル比=6、Na含有量[wt%]=0.01、Na以外のアルカリ金属およびアルカリ土類金属は検出限界以下、細孔直径=0.74nm、形状:1.5mmペレット、バインダー種:アルミナ)を使用し、実施例15と同様に反応を行った。実施例15と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率は0.26(mol%)であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表5に示す。
反応温度を200℃とした以外は、参考例2と同様に反応を行った。参考例2と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率は0.48(mol%)であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表5に示す。
反応温度を250℃とした以外は、参考例2と同様に反応を行った。参考例2と同様に、反応生成物をオンラインでガスクロマトグラフへ導入し、モノシラン、ジシラン、トリシランの含有量を求めたところ、MS転化率は0.89(mol%)であった。また、反応管の壁面での固体ケイ素の析出は目視上、認められなかった。結果を表5に示す。
2 H2流量計
3 反応器
4 冷却器
5 電気炉
Claims (19)
- 多孔質酸化物を含む、低級シランに接触することにより、該低級シランを、該低級シランよりケイ素数が多い高級シランへ変換させる高級シランの製造触媒であり、該多孔質酸化物が、規則的に配列する細孔を少なくとも有し、主としてケイ素酸化物からなり、かつ、アルカリ金属およびアルカリ土類金属の含有量が0.00重量%以上2.00重量%以下である高級シランの製造触媒。
- 前記多孔質酸化物の細孔の直径が0.4nm以上0.6nm以下である、請求項1記載の高級シランの製造触媒。
- 前記多孔質酸化物の細孔が酸素の8~12員環で構成された細孔である、請求項1または2に記載の高級シランの製造触媒。
- 前記多孔質酸化物がアルミノシリケートまたはメタロシリケートからなる結晶性ゼオライト構造を有する請求項1~3のいずれか一項に記載の高級シランの製造触媒。
- 前記結晶性ゼオライト構造が、BEA型、FER型、LTA型、MFI型、MOR型、MWW型のなかの少なくともいずれか1種である請求項4に記載の高級シランの製造触媒。
- 前記多孔質酸化物中のアルミノシリケートまたはメタロシリケート骨格の負電荷を補償するアルカリ金属イオンまたはアルカリ土類金属イオンが水素イオンに置換されていることを特徴とする、請求項4または5に記載の高級シランの製造触媒。
- 前記多孔質酸化物がアルミノシリケートであり、該多孔質酸化物中のSiO2/Al2O3モル比が10以上3,000以下であることを特徴とする請求項4~6のいずれか一項に記載の高級シランの製造触媒。
- 前記SiO2/Al2O3モル比が20以上2,000以下であることを特徴とする請求項7に記載の高級シランの製造触媒。
- 請求項1~8のいずれか一項に記載の高級シランの製造触媒に、低級シランを接触させることにより、該低級シランを、該低級シランよりケイ素数が多い高級シランへ変換させることを特徴とする高級シランの製造方法。
- 触媒が存在しない条件下で、低級シランの熱的分解により高級シランが実質的に生成し始める温度より低い温度で前記高級シランの製造触媒に低級シランを接触させる請求項9に記載の高級シランの製造方法。
- 前記高級シランの製造触媒に低級シランを接触させる温度が、100℃以上400℃以下であることを特徴とする請求項9記載の高級シランの製造方法。
- 前記温度が、120℃以上350℃以下であることを特徴とする請求項11記載の高級シランの製造方法。
- 前記温度が、140℃以上300℃以下であることを特徴とする請求項11記載の高級シランの製造方法。
- 前記低級シランは、低級シランを含む原料ガスによって供給され、原料ガス中の低級シランの濃度は、50vol%以上100vol%以下である請求項9~13のいずれか一項に記載の高級シランの製造方法。
- 低級シランがモノシランであり、高級シランがジシランおよびトリシランであることを特徴とする請求項9~14のいずれか一項に記載の高級シランの製造方法。
- 低級シランがモノシランであり、高級シランがジシランであることを特徴とする請求項9~14のいずれか一項に記載の高級シランの製造方法。
- 低級シランがジシランであり、高級シランがトリシランであることを特徴とする請求項9~14のいずれか一項に記載の高級シランの製造方法。
- 高級シランの製造触媒を水素含有ガスで賦活処理する工程を含むことを特徴とする請求項9~14のいずれか一項に記載の高級シランの製造方法。
- 高級シランの製造触媒を水素含有ガスで賦活処理する工程の処理温度が20℃以上であることを特徴とする請求項18に記載の高級シランの製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/030,802 US9567228B2 (en) | 2013-10-21 | 2014-10-16 | Catalyst for producing higher silane and process for producing higher silane |
CN201480057511.5A CN105658330B (zh) | 2013-10-21 | 2014-10-16 | 高级硅烷的制造催化剂及高级硅烷的制造方法 |
SG11201603098WA SG11201603098WA (en) | 2013-10-21 | 2014-10-16 | Catalyst for producing higher silane and method for producing higher silane |
EP14856547.6A EP3061524B1 (en) | 2013-10-21 | 2014-10-16 | Use of a catalyst for producing higher silane and method for producing higher silane |
KR1020167009872A KR101796881B1 (ko) | 2013-10-21 | 2014-10-16 | 고급 실란의 제조 촉매 및 고급 실란의 제조 방법 |
JP2015543814A JP6161719B2 (ja) | 2013-10-21 | 2014-10-16 | 高級シランの製造触媒および高級シランの製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013218262 | 2013-10-21 | ||
JP2013-218262 | 2013-10-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015060189A1 true WO2015060189A1 (ja) | 2015-04-30 |
Family
ID=52992788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/077538 WO2015060189A1 (ja) | 2013-10-21 | 2014-10-16 | 高級シランの製造触媒および高級シランの製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9567228B2 (ja) |
EP (1) | EP3061524B1 (ja) |
JP (1) | JP6161719B2 (ja) |
KR (1) | KR101796881B1 (ja) |
CN (1) | CN105658330B (ja) |
SG (1) | SG11201603098WA (ja) |
TW (1) | TWI589355B (ja) |
WO (1) | WO2015060189A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170275171A1 (en) * | 2014-08-20 | 2017-09-28 | Showa Denko K.K. | Method for producing oligosilane |
WO2017213155A1 (ja) * | 2016-06-10 | 2017-12-14 | 昭和電工株式会社 | オリゴシランの製造方法 |
WO2018056250A1 (ja) * | 2016-09-23 | 2018-03-29 | 昭和電工株式会社 | オリゴシランの製造方法 |
WO2018079484A1 (ja) * | 2016-10-27 | 2018-05-03 | 昭和電工株式会社 | オリゴシランの製造方法及びオリゴシランの製造装置 |
JP2018131354A (ja) * | 2017-02-15 | 2018-08-23 | デンカ株式会社 | ジシランの製造方法 |
KR101945215B1 (ko) * | 2016-02-16 | 2019-02-07 | 쇼와 덴코 가부시키가이샤 | 올리고실란의 제조 방법 |
JP2022501305A (ja) * | 2018-10-11 | 2022-01-06 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 液体ポリシラン及び異性体エンリッチド高級シランを製造するためのプロセス |
CN114772603A (zh) * | 2022-04-30 | 2022-07-22 | 浙江迅鼎半导体材料科技有限公司 | 一种高价硅烷的制造方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018067774A1 (en) * | 2016-10-05 | 2018-04-12 | Monsanto Technology Llc | Emission control during catalyst regeneration |
TWI683788B (zh) * | 2018-08-16 | 2020-02-01 | 台灣特品化學股份有限公司 | 高效率的高階矽烷轉化合成及純化回收方法 |
US11401166B2 (en) | 2018-10-11 | 2022-08-02 | L'Air Liaquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for producing isomer enriched higher silanes |
US11097953B2 (en) | 2018-10-11 | 2021-08-24 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for producing liquid polysilanes and isomer enriched higher silanes |
KR102313140B1 (ko) * | 2019-10-01 | 2021-10-15 | (주)원익머트리얼즈 | 실란합성을 위한 촉매 재생 방법 및 이 방법으로 제조된 촉매 |
CN112661161A (zh) * | 2020-12-28 | 2021-04-16 | 烟台万华电子材料有限公司 | 一种连续生产高阶硅烷的方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727915A (en) | 1980-06-11 | 1982-02-15 | Nat Res Dev | Synthesis of polysilane |
JPS60141613A (ja) | 1983-12-28 | 1985-07-26 | Mitsui Toatsu Chem Inc | 水素化ケイ素の製造方法 |
JPS60255612A (ja) | 1984-05-31 | 1985-12-17 | Mitsui Toatsu Chem Inc | 水素化ケイ素の製造方法 |
JPS62132720A (ja) | 1985-12-02 | 1987-06-16 | Fuji Electric Co Ltd | 高次シラン生成方法 |
JPH03183613A (ja) | 1989-12-08 | 1991-08-09 | Showa Denko Kk | ジシランの製造法 |
JPH03183614A (ja) | 1989-12-13 | 1991-08-09 | Showa Denko Kk | 高次シランの製造法 |
JPH11260729A (ja) | 1998-01-08 | 1999-09-24 | Showa Denko Kk | 高次シランの製造法 |
JP2011524329A (ja) | 2008-06-17 | 2011-09-01 | エボニック デグサ ゲーエムベーハー | 高級ヒドリドシランの製造方法 |
JP4855462B2 (ja) | 2005-04-05 | 2012-01-18 | ボルテツクス・インコーポレイテツド | Si2h6およびより高次のシランを製造するためのシステムおよび方法 |
JP2013506541A (ja) * | 2009-10-02 | 2013-02-28 | エボニック デグサ ゲーエムベーハー | 高度に水素化されたシランの製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6027705A (en) | 1998-01-08 | 2000-02-22 | Showa Denko K.K. | Method for producing a higher silane |
CN1241684C (zh) * | 2002-12-03 | 2006-02-15 | 中国科学院大连化学物理研究所 | 烃类催化裂解制烯烃并联产芳烃催化剂及制法和应用 |
-
2014
- 2014-10-16 US US15/030,802 patent/US9567228B2/en active Active
- 2014-10-16 CN CN201480057511.5A patent/CN105658330B/zh active Active
- 2014-10-16 WO PCT/JP2014/077538 patent/WO2015060189A1/ja active Application Filing
- 2014-10-16 KR KR1020167009872A patent/KR101796881B1/ko active IP Right Grant
- 2014-10-16 JP JP2015543814A patent/JP6161719B2/ja active Active
- 2014-10-16 EP EP14856547.6A patent/EP3061524B1/en active Active
- 2014-10-16 SG SG11201603098WA patent/SG11201603098WA/en unknown
- 2014-10-20 TW TW103136200A patent/TWI589355B/zh active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727915A (en) | 1980-06-11 | 1982-02-15 | Nat Res Dev | Synthesis of polysilane |
JPS60141613A (ja) | 1983-12-28 | 1985-07-26 | Mitsui Toatsu Chem Inc | 水素化ケイ素の製造方法 |
JPS60255612A (ja) | 1984-05-31 | 1985-12-17 | Mitsui Toatsu Chem Inc | 水素化ケイ素の製造方法 |
JPS62132720A (ja) | 1985-12-02 | 1987-06-16 | Fuji Electric Co Ltd | 高次シラン生成方法 |
JPH03183613A (ja) | 1989-12-08 | 1991-08-09 | Showa Denko Kk | ジシランの製造法 |
JPH03183614A (ja) | 1989-12-13 | 1991-08-09 | Showa Denko Kk | 高次シランの製造法 |
JPH11260729A (ja) | 1998-01-08 | 1999-09-24 | Showa Denko Kk | 高次シランの製造法 |
JP4855462B2 (ja) | 2005-04-05 | 2012-01-18 | ボルテツクス・インコーポレイテツド | Si2h6およびより高次のシランを製造するためのシステムおよび方法 |
JP2011524329A (ja) | 2008-06-17 | 2011-09-01 | エボニック デグサ ゲーエムベーハー | 高級ヒドリドシランの製造方法 |
JP2013506541A (ja) * | 2009-10-02 | 2013-02-28 | エボニック デグサ ゲーエムベーハー | 高度に水素化されたシランの製造方法 |
Non-Patent Citations (2)
Title |
---|
"Atlas of Zeolite Framework Types, Sixth revised edition", 2007, ELSEVIER |
See also references of EP3061524A4 |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170275171A1 (en) * | 2014-08-20 | 2017-09-28 | Showa Denko K.K. | Method for producing oligosilane |
KR101945215B1 (ko) * | 2016-02-16 | 2019-02-07 | 쇼와 덴코 가부시키가이샤 | 올리고실란의 제조 방법 |
CN109219576B (zh) * | 2016-06-10 | 2022-06-07 | 昭和电工株式会社 | 低聚硅烷的制造方法 |
WO2017213155A1 (ja) * | 2016-06-10 | 2017-12-14 | 昭和電工株式会社 | オリゴシランの製造方法 |
KR20190004322A (ko) | 2016-06-10 | 2019-01-11 | 쇼와 덴코 가부시키가이샤 | 올리고실란의 제조 방법 |
CN109219576A (zh) * | 2016-06-10 | 2019-01-15 | 昭和电工株式会社 | 低聚硅烷的制造方法 |
JPWO2017213155A1 (ja) * | 2016-06-10 | 2019-05-09 | 昭和電工株式会社 | オリゴシランの製造方法 |
WO2018056250A1 (ja) * | 2016-09-23 | 2018-03-29 | 昭和電工株式会社 | オリゴシランの製造方法 |
KR20190041512A (ko) | 2016-09-23 | 2019-04-22 | 쇼와 덴코 가부시키가이샤 | 올리고실란의 제조 방법 |
JPWO2018056250A1 (ja) * | 2016-09-23 | 2019-07-04 | 昭和電工株式会社 | オリゴシランの製造方法 |
WO2018079484A1 (ja) * | 2016-10-27 | 2018-05-03 | 昭和電工株式会社 | オリゴシランの製造方法及びオリゴシランの製造装置 |
JPWO2018079484A1 (ja) * | 2016-10-27 | 2019-09-19 | 昭和電工株式会社 | オリゴシランの製造方法及びオリゴシランの製造装置 |
JP2018131354A (ja) * | 2017-02-15 | 2018-08-23 | デンカ株式会社 | ジシランの製造方法 |
JP2022501305A (ja) * | 2018-10-11 | 2022-01-06 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 液体ポリシラン及び異性体エンリッチド高級シランを製造するためのプロセス |
JP7203232B2 (ja) | 2018-10-11 | 2023-01-12 | レール・リキード-ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 液体ポリシラン及び異性体エンリッチド高級シランを製造するためのプロセス |
CN114772603A (zh) * | 2022-04-30 | 2022-07-22 | 浙江迅鼎半导体材料科技有限公司 | 一种高价硅烷的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105658330B (zh) | 2017-07-11 |
TWI589355B (zh) | 2017-07-01 |
EP3061524A1 (en) | 2016-08-31 |
US9567228B2 (en) | 2017-02-14 |
SG11201603098WA (en) | 2016-05-30 |
TW201521870A (zh) | 2015-06-16 |
US20160257571A1 (en) | 2016-09-08 |
EP3061524B1 (en) | 2020-12-02 |
KR101796881B1 (ko) | 2017-11-10 |
EP3061524A4 (en) | 2017-06-21 |
KR20160057448A (ko) | 2016-05-23 |
JPWO2015060189A1 (ja) | 2017-03-09 |
CN105658330A (zh) | 2016-06-08 |
JP6161719B2 (ja) | 2017-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6161719B2 (ja) | 高級シランの製造触媒および高級シランの製造方法 | |
TWI289475B (en) | Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst | |
CN105339342B (zh) | 用于二甲醚的羰基化的方法 | |
UA120086C2 (uk) | Спосіб карбонілювання | |
JP5069880B2 (ja) | トルエン形状選択的アルキル化によるパラキシレン製造に使用される触媒の製造法 | |
CN105358521B (zh) | 羰基化方法 | |
EP3141553B1 (en) | Method for producing tetraalkoxysilane | |
TWI636956B (zh) | 寡聚矽烷之製造方法 | |
JP5668422B2 (ja) | アルミノシリケートの製造方法 | |
EP1974812A1 (en) | Catalysts and process for the production of olefins with the same | |
JP2014024007A (ja) | ゼオライト触媒、ゼオライト触媒の製造方法および低級オレフィンの製造方法 | |
JP5914240B2 (ja) | 多結晶シリコンの製造方法 | |
JP5747326B2 (ja) | プロピレンの製造方法 | |
CN115650240A (zh) | 一氯硅烷的制备方法 | |
WO2018178831A1 (en) | Process for production of phenol using zeolite supported catalysts | |
CN112138724B (zh) | 加氢烷基化催化剂及其方法 | |
JP5104618B2 (ja) | 1,2−ジクロロエタンの製造方法 | |
JPH0859566A (ja) | メチルアミン類の製造方法 | |
JP6251788B2 (ja) | ゼオライト触媒、ゼオライト触媒の製造方法および低級オレフィンの製造方法 | |
WO2014116341A1 (en) | Mehtod for preparing a trihalosilane | |
JP4663079B2 (ja) | トリアルコキシシランからシランの製造方法およびテトラアルコキシシランからトリアルコキシシランの製造方法 | |
JP3489869B2 (ja) | メチルアミン類の製造方法 | |
CN104437418B (zh) | 负载聚乙烯亚胺的层状材料及其制备方法 | |
JPH08193057A (ja) | メチルアミン類の製造方法 | |
JPH07145145A (ja) | δ−バレロラクタムの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14856547 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015543814 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167009872 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15030802 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014856547 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014856547 Country of ref document: EP |