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1P057 ゼオライトり媒による 29* 反応に関する理論的よ析
1P057 ࢭ࢛ࣚࢹり፳࡞ࡻࡾ 29* ཬᚺ࡞㛭ࡌࡾ⌦ㄵⓏよᯊ ஐኬᑙ◂ ې୕ಆᚠࠉሲ⏛ᾼொࠉྚ⃕ୌᠺ ࠘ᗆ ㄵ ࠙ ᖳࠉ▴ἔ༱ᶭ࡞ࡻࡾ࢝ࢮࣛࣤ㊂࠵ࡽࠉ▴ἔ⢥⿿࡞ࢂࡾ᩺ࡒ࢝ࢮࣛࣤࡡ⏍ᠺἪ ᚪさ࡛ࡖ࡙࠷ࡒࠊࡐࡆ࡚ࠉ2RGLO ♣ࡢࢭ࢛ࣚࢹり፳ࢅ⏕࠷࡙࣒ࢰࢿ࣭ࣜࢅࣀ࢛ࢠࢰࣤ࢝ࢮ ࣛࣤ㌹ᥦࡌࡾ 29,2HWKFQROWR,FVROLQHཬᚺࢅ㛜Ⓠࡊࡒࠊ29, ཬᚺࡢࠉᏭ౮࣒ࢰࢿ࣭ࣜ࠾ ࡼ࢝ࢮࣛࣤࢅྙᠺ࡚ࡀࡾࡒࡴࠉ⏐ᴏⓏ࡞㟸ᖏ࡞Ἰ┘ࡈࡿ࡙࠷ࡾ㔔さཬᚺ࡚࠵ࡖࡒࠊࡱࡒࠉᏕ⾙ Ⓩ㟻࡞࠽࠷࡙ࡵࠉ࣒ࢰࢿ࣭ࣜࡡ (4 ⤎ྙࡡ㛜࡛ࠉ࢛ࣝࣆࣤࡷࣜ࢜ࣤᙟᠺࡡ➠ୌṹ㝭࡚࠵ ࡾ (( ⤎ྙࡡᙟᠺࡡ࣒࢜ࢼࢫ࣑࡞㛭ᚨᐞࡎࡼࡿ࡙࠷ࡒࠊ 29, ཬᚺ࡚⏍ᠺࡈࡿࡾ࢝ࢮࣛࣤࡢࠉⰶ㤮᪐ᠺฦࡡྙ㧏ࡂẐᛮᙁ࠷ࡒࡴࠉࡵࡢࡷ⎌ሾ㟻࡚ ᭻ࡱࡿࡾࡵࡡ࡚ࡢ࠾ࡖࡒࠊࡓࠉࢭ࢛ࣚࢹࢅ⏕࠷ࡒ࣒ࢰࢿ࣭ࣜ㌹ཬᚺࡢࠉ㔔さ◂✪ࢷ࣭ ࣏࡛ࡊ࡙ṟࡖࡒࠊࡐࡡ୯࡚ࡵࡱࡒࠉࢭ࢛ࣚࢹり፳ࢅ⏕࠷࡙࣒ࢰࢿ࣭ࣜ࠾ࡼ࢛ࣝࣆࣤࢅ⏍ᠺࡌ ࡾ 2942HWKFQROWR4OHILQVཬᚺἸ┘ࡈࡿ࡙࠷ࡾ@Bࠊ n CH3OH catalyst CnH2n + n H2O 294 ཬᚺࡢࠉࢭ࢛ࣚࢹࡡᙟ≟ࡷ⤄ᠺࠉࡈࡼ࡞ཬᚺῺᗐࡷ࣒ࢰࢿ࣭ࣜࡡฦᅸ࡞ࡻࡽࠉ࢛ࣝࣆ ࣤࡡ㐽ᢝᛮ␏ࡾࠊୌ⯙Ⓩ࡞ࠉ⣵Ꮗࡡኬࡀࢭ࢛ࣚࢹ࡚ࠉ࣒ࢰࢿ࣭ࣜࡡฦᅸࠉ㧏Ὼ㸝⣑ Υ㸞 ࡡ᮪௲࡚ཬᚺࡈࡎࡾ࡛ฦᏄ㔖ࡡኬࡀ࢛ࣝࣆࣤ⏍ᠺࡌࡾࡆ࡛ሒ࿈ࡈࡿ࡙࠷ࡾ@Bࠊ⣵Ꮗኬ ࡀࢭ࢛ࣚࢹࡡౚ࡛ࡊ࡙ࠉ8&54ࠉ?82ࠉ+*7 ࢭ࢛ࣚࢹ࠵ࡾࠊࡱࡒࠉ㔘ᒌ㸝,F(U; 2Q3L+H㸞ࢅྱࡳࢭ࢛ࣚࢹ࡚ࡢࠉ⏍ᠺ∸ࡡ㐽ᢝᛮࡻࡽ㧏ࡂࡾࡆ࡛ሒ࿈ࡈࡿ࡙࠷ࡾࠊࡆ ࡡࡒࡴࠉ294 ཬᚺࡢ㔘ᒌὩᛮࢦࢹ࢛ࣝࣆࣤࡡ㐽ᢝᛮ࡛ཬᚺᛮ࡞㔔さᙲࢅᢰࡖ࡙࠷ࡾ࡛ ⩻࠻ࡼࡿ࡙࠷ࡾࠊ 294 ཬᚺ࡞࠽࠷࡙᭩ࡵ⮾࠷Ⅴࡢࠔࡡࡻ࠹࡞ࡊ࡙࣒ࢰࢿ࣭ࣜࡡ (4 ⤎ྙ㛜ࡌࡾࡡ࠾㸴ࠕ ࠔ(( ⤎ྙ⏍ᠺ࡞ࡻࡾቌ⅛ཬᚺࡢ࠷࠾࡞㉫ࡆࡾ࠾㸴ࠕࡡⅤ࡚࠵ࡽࠉࡱ࡚ኣࡂࡡࡡ࣒࢜ࢼࢫ࣑ ᥞ᱄ࡈࡿ࡙ࡀࡒࠊࡊ࠾ࡊࡆࡿࡼࡡཬᚺᶭᵋࡢᐁ㥺Ⓩᐁ࠾ࡼࡡ㢦᥆࡞࡛ࡱࡽࠉᮅࡓ࡞ࡐࡡ࣒ ࢜ࢼࢫ࣑ࡢよ᪺ࡈࡿ࡙࠷࠷ࠊࡐࡆ࡚ᠻࠍࡢࠉᘟ࡚♟ࡈࡿࡾࡻ࠹ 294 ཬᚺࡡ୯࡚᭩ࡵ༟⣟ 29*2HWKFQROWR*WK^OHQHཬᚺ࡞ࡗ࠷࡙Ἰ┘ࡊࡒࠊ 2 CH3OH catalyst CH2 =CH2 + 2 H2O ᮇ◂✪ࡡ┘Ⓩࡢࠉࢭ࢛ࣚࢹ࣓ࢸࣜࡡ㔘ᒌὩᛮⅤ࡞ࡗ࠷࡙ᐠᗐỏ㛭ᩐゝ⟤ࢅ⾔࠷ࠉ࣎ࢷࣤࢨࣔ ࢙ࣜࢾ࣭ࣜ࢟ࡡふⅤ࠾ࡼࠉ29* ཬᚺࡡ࣒࢜ࢼࢫ࣑ࢅ᳠ゞࡌࡾࡆ࡛࡚࠵ࡾࠊ ࠘ゝ ⟤᪁ Ἢ ࠙ ゝ⟤᪁Ἢࡢ '1>5 Ἢࠉᇱᗇ㛭ᩐ࡛ࡊ࡙㕪ཋᏄ࡞ࡢ <FHKWHUV̽-F^ ᇱᗇࠉࡡཋᏄ࡞ࡢ )ᇱᗇ ࢅ⏕࠷ࡒࠊ㕪ὩᛮⅤࡡ࣓ࢸࣜࡢ -8L4+HϪ48L- ࡛ࡊࠉࡐࡿ࡞ᑊᚺࡌࡾࢪࣅࣤኣ㔔ᗐࡢᄿ㔔㡧 ≟ឺ࡛ඵ㔔㡧≟ឺࢅ⩻࠻ࡒࠊཬᚺ∸ࠉ㐼⛛≟ឺࠉ୯㛣⏍ᠺ∸ཀྵࡦ⏍ᠺ∸ࡡᵋ㏸᭩㐲ࢅᐁ⾔ࡊࡒࠊ ධ࡙ࡡゝ⟤࡞ࡢࠉ,&:88.&3 ࣈࣞࢡ࣑ࣚࢅ⏕࠷ࡒࠊ ࠘⤎ ᯕ࡛ ⩻ ᐳ࠙ ᠻࠍࡢࠉ࣒ࢰࢿ࣭࢙ࣜࢲࣝࣤ㌹ࡌࡾཬᚺᶭᵋࢅࠉ㔖ᏄᏕゝ⟤࡞ࡻࡽỬᏽࡊࡒࠊ࣒ࢰࢿ ࣭࢙ࣜ̾ࢲࣝࣤ㌹ཬᚺࡢࠉࢭ࢛ࣚࢹり፳ࡡ㔘ᒌὩᛮ୯ᚨ࡞࣒ࢰࢿ࣭ࣜฦᏄྺ╌ࡌࡾࡆ࡛࡞ࡻ ࡽ㛜ጙࡌࡾࠊᅒ ࡞♟ࡌࡻ࠹࡞ࠉࡆࡡり፳ࢦࢠࣜ࡞ࡢ (̽4 ⤎ྙࡡ㛜ࠉ࣒ࢲࣝࣤᙟᠺࠉ(̽( ⤎ ྙࡡᙟᠺࠉ࢙ࢲࣝࣤᙟᠺࡡᄿṹ㝭࠵ࡾࠊ➠ୌṹ㝭࡚ࡢࠉཬᚺ∸㘊మ & ࡡ (̽4 ⤎ྙ㛜ࡊࠉ୯ 㛣మ ' ᙟᠺࡈࡿࡾࠊ➠ṹ㝭࡚ࡢࠉ࣒ࢹ࢞ࢨᇱࡡỀ⣪ཋᏄࣃࢺࣞ࢞ࢨࣜᇱ㌹నࡊࠉ୯㛣మ ( ᙟᠺࡈࡿࡾࠊࡐࡡᚃࠉ୯㛣మ ( ࡞㒼నࡊ࡙࠷ࡾỀ࣒ࢰࢿ࣭࡛ࣜஹᥦࡈࡿࠉ୯㛣మ ) ᙟᠺ ࡈࡿࡾࠊ➠ṹ㝭࡚ࡢࠉ୯㛣మ ) ࡡ࣒ࢰࢿ࣭ࣜฦᏄࡡ࣒ࢲࣜᇱ࣒ࢲࣝࣤᇱ࡞㌹నࡊࠉ୯㛣మ * ᙟᠺࡈࡿࡾࠊ➠ᄿṹ㝭࡚ࡢࠉ࢙ࢹ࢞ࢨᇱࡡỀ⣪ཋᏄࣃࢺࣞ࢞ࢨࣜᇱ㌹నࡊࠉ⏍ᠺ∸㘊మ + ᙟᠺࡈࡿࡾࠊࡆࡡ⏍ᠺ∸㘊మ + ࡢࠉ࢙ࢲ࡛ࣝࣤỀ⬲㞫ࡊࠉ࣒ࢰࢿ࣭࡛ࣜྺ╌ࡌࡾࡆ࡛࡚ࠉ් ࡦཬᚺ∸㘊మ & ࡛ࡾࠊࡆࡡཬᚺࡢ㸦ࢦࢠࣜ࠵ࡒࡽࠉ⣑ NHFOPRO ࡡྺ⇍ཬᚺ࡚࠵ࡾࡆ࡛ ᪺ࡼ࠾࡛ࡖࡒࠊࢪࣅࣤཬ㌹ࡡྊ⬗ᛮࢅ HO ⩻៎ࡊࡒṹ㝭ࡡὩᛮ࢙ࢾ࣭ࣜ࢟ࡢࠉ Si ➠ୌṹ㝭࡚ NHFOPROࠉ➠ṹ㝭࡚ Fe CH3 O H2O Si B !"#$ %&'() *+, NHFOPRO ࠉ ➠ ṹ 㝭 ࡚ O Si O Fe CH2 O Si C !-#$ ./0123 CH3OH H2O CH3OH NHFOPROࠉ➠ᄿṹ㝭࡚ NHFOPRO ࡚ ࠵ࡾࠊࡆࡿࡻࡽࠉ➠ୌṹ㝭ࡡ࣒ࢰࢿ࣭ࣜ HO Si O Fe O Si Si O CH3 CH3 Fe O HO Si Si O A ࡡ (4 ⤎ྙࡡ㛜ࠉᚂ㏷࡛ࡾ࡛⩻࠻ ࡼࡿࡾࠊࡱࡒࠉࡆࡡᚂ㏷ṹ㝭ࡡὩᛮ࢙ࢾ ࣭ࣜ࢟ࡢ NHFOPRO ࡛࠾ࡽኬࡀ࠷ ࡒࡴࠉཬᚺ᮪௲࡞⣑ Υ࡛࠷࠹㧏࠷Ὼ CH2 O Si D CH2=CH2 + H2O CH3OH Fe H2C CH2 H2O Fe O O Si Si CH3 HO O Fe Si F !4#$ %&%() *23 CH2 O Si E !5#$ 6/0123 ᗐᚪさ࡞ࡽࠉῺ࡚ࡡཬᚺࡢ㞬ࡊ࠷ ࡛⩻࠻ࡼࡿࡾ ᅒ ࣒ࢰࢿ࣭࢙ࣜ̾ࢲࣝࣤ㌹ཬᚺࡡり፳ࢦࢠࣜ ࠘ཤ ⩻ᩝ ⊡ ࠙ @B-F\/+ 8RQJ< 2FUHXV)2 3LHKROFV/'&HH(KHP7HV @B.QXL9 2FWVXIF- >FPFVH4 3FJFWF- +XNXIF0 :NF\F9 2L^FPRWR&/(FWFO