Page 46 - 《精细化工》2023年第4期

g732g ㇫㏳ࡃጒ FINE CHEMICALS す 40 ࢤ

ౕ⾧䕌喍GHSV喎ͧ 13081/h হ 480 Ď⮱ࣺᏁ
᲎У̸喑MP ⮱䒙ࡃ⢴䓫 71.5%喑2-⅝ധ৹ଗ喍CP喎
⮱䔶᠖ᕔ倅䓫 93.7%喑⾧ᬣϔ⢴喍STY CP 喎ͧ 1724~
77082 g CP /(kg cat ·h)ȡₑㆨࣺᏁக䓾ѩλэ㐌⮱ధჇ
ᎷࣺᏁக喑יࡃݯ⮱ㆿᒱᒞ৺⋟Ҁ➖᫆⮱ڲใព᪐喑

ఫ 9 ᓛ䕇䖀ࣺᏁக͚ܳၽ⅔䔶᠖ᕔ⅔ࡃ䗨⅜⩟㠜⩌᜽ ㆿᒱ䓴ᄼ̺ݖλใព᪐喑ᄩ㜡䓴๔⮱ࢸ䭺ȡओใ喑
䗨⅜㠜⩟䛈 [33] ຯ҂Ԋ䃮᫆⋟ౕࣺᏁகڲ⮱౴࠭ܳጰΌ᭜䰭㺮∕ᘼ
Fig. 9 Selective aerobic-oxidation of o-chlorotoluene to ⮱䬛䷅ȡ
o-chlorobenzaldehyde in microchannel reactor [33]
䓴⅔ࡃ⅏᭜ओ̭⻺㐬㞟⅔ࡃݯ喑̻ܳၽ⅔҉⅔
ႌᎳь䄫䷅㏱ [37] 䔈㵹γⰥ䓾⮱ⵁ⾣ጒ҉喑ౕᓛ ࡃݯㆨѩ喑⅔ࡃࣺᏁ⮱ޜϔ➖गᰶⅡ喑ౕ⋟Ⱕ⅔ࡃ
䕇䖀ࣺᏁக͚ВҀ⼜℁ 1ń1 ⮱ MeCN-Me 2 CO ⌤व ࣺᏁ͚ऄݝ䱿ⱽȡധλ䓴⅔ࡃ⅏⅔ࡃݯ⮱㐬㞟⅔ࡃ
➖҉ͧ⏣ݯ喑N-㓌ധ䗨㠜ι⩟䚝χ㘧喍NHPI喎হχ ጒ㞧ᄳ䔽⌽ᰬА⣝ᰶ᜽⛌⮱ࡃጒጒ㞧喑ຯ⣜⅔͆☤Ƞ
ⶊ 䚥ँ̮䚜 喍 TBN 喎Ჱ ᜽⮱ᬍ䛾 ᆋ יࡃҀ ㈨ ጞڲ䚝㘧হ㠜䚇ぶࡃጒϔ৮⮱⩌ϔ [40] ȡ⤳䃧̷喑㠜
NHPI/TBN יࡃܳၽ⅔ᄦఈ⅏ࡃ㥅ぶ☤ധ㠜ㆨࡃव Ⱑᣒ⅔ࡃ⩌᜽㠜䚇᭜ᰭキ∮⮱㠜䚇व᜽䌜㏬喑䓴⅔
➖䔈㵹㟱ധ䔶᠖ᕔ⅔ࡃ喍ఫ 10喎喑ౕ n(Ꮒ➖)ń ࡃ⅏᭜仃䔶⅔ࡃݯ͸̭ [41-42] ȡ䕇፥喑䓴⅔ࡃ⅏ౕ䜉
n(TBN)ńn(NHPI)=1ń1.5ń0.75ȠࣺᏁ⍖Ꮣ 100 ĎȠ ᐼࣺᏁக͚Ҭ⩕䰭㺮ᣔݣ䒰ѻ⮱⊀ᏓВ䭟₏✳◥⮱
ࣺᏁࢸ߈ 1.0 MPaȠ⋟Ҁ≮䕌 1.0 mL/minȠO 2 ≮䕌 ࣾ⩌喑㔹́䓴䪬⮱։⪆ᬣ䬡䔅䕍᜽䓴⅔ࡃ⅏䓴็ܳ
20 mL/min ⮱хࡃࣺᏁ᲎У̸喑В 41.2%~90.3%⮱ 㼐ȡᰭ䓾喑㟼䔉⊤䄫䷅㏱ [43] ౕ䕇⩕⮱℈㏳ノᓛ䕇䖀
ᩣ⢴ᓄݝⰥᏁ⮱䚛ȡᓛ䕇䖀ࣺᏁக͚⅔ࡃࣺᏁ⮱᩵ ࣺᏁக͚ⵁ⾣γౕռ䦿䚥䧍יࡃ̸䓴⅔ࡃ⅏Ⱑᣒ⅔
⢴䒰䜉ᐼࣺᏁக͚᣽倅 466 Ժ喑́יࡃݯजᓗ⣜Ҭ ࡃ㠜⩌᜽㠜䚇喍ఫ 12喎⮱ࣺᏁጒ㞧হߕ߈႓喑ࣾ⣝
⩕喑㶕ᬻࣺᏁጒ㞧⮱ጕ๔х߬হ⒉ౕ⮱Ꮑ⩕Фթȡ ࣺᏁౕ 55 Ďᣔݣ։⪆ᬣ䬡 60 h ᬣ喑㠜䚇⮱ᩣ⢴হ

䔶᠖ᕔܳݘ䓫ݝ 15%হ 94.0%喠㠜䚇व᜽Ƞ䓴⅔ࡃ
⅏ܳ㼐Вࣷ㠜䚹⩌᜽⮱≨ࡃ㘪ܳݘͧ 99.52Ƞ99.43
হ 63.00 kJ/molȡ䔆ψ㐀᳉ͧ㠜Ⱑᣒ⅔ࡃव᜽㠜䚇ጒ
㞧ᩫ๔᣽ӈᓲ㺮⮱ᩜᦾȡౕ䄒ࣺᏁ͚喑יࡃݯ̻ࣺ
Ꮑ➖᫆οⰥ⏣㼐喑ᆋλ౴ⰥיࡃࣺᏁ㠰⪡喑఍㔹喑
䕇䓴ጒ㞧࣯᪝⮱䄰अ喑ౕ䕇⩕℈㏳ノࣺᏁக͚ღᭀ

䓫᜽䶱᱌ⰛᴴᎣᓄݝᩫ๔ȡ
ఫ 10 ᓛ䕇䖀ࣺᏁக͚ܳၽ⅔䔶᠖ᕔ⅔ࡃఈ⅏ࡃ㥅 [37]
Fig. 10 Selective aerobic-oxidation of tetrahydronaphthalene
in microchannel reactor [37]

ౕ⅕⅁ႅ̸ౕ㟠⩟ധज㷘ܳၽ⅔䔶᠖ᕔיࡃ⅔
ࡃ⩌᜽㟠⩟㙵喑ᆋλ⅕⅔ࡃࣺᏁ [38] ȡ䭵ᮀ䄫䷅㏱ [39]
ݖ⩕඘ٲγ็Ⱕיࡃݯ CrVPO/Ȗ-Al 2 O 3 ⮱඘ٲᎷᓛ

䕇䖀ࣺᏁகⵁ⾣γ 2-⩟ധ৹ଗ喍MP喎⮱⅕⅔ࡃࣺᏁ喑 ఫ 12 ᓛ䕇䖀ࣺᏁக͚䓴⅔ࡃ⅏⅔ࡃ㠜⩌᜽㠜䚇 [43]
䕇䓴ᄦࣺᏁ⍖ᏓȠ➖᫆℁Вࣷיࡃݯ⮱ᅧᄥぶ࣯᪝ Fig. 12 Oxidation of benzene to phenol with hydrogen
peroxide in microchannel reactor [43]
⮱㔰ᄌ喑㣤ᓄγхࡃ⮱ࣺᏁ᲎У喍ఫ 11喎ȡ

Ά䛈䚥᭜̭⻺䛺㺮⮱㇫㏳ࡃጒϔ৮喑⩕λ仆㇫Ƞ
仆᫆⮱⩌ϔহ㢜➖व᜽ȡВ䓴⅔ࡃ⅏ͧ⅔ࡃݯ⩞͆
☜䚥व᜽Ά䛈䚥㐬㞟⣜Ԋ喑ѳₑݺ౴䛴⩕䬡⁴ጒ㞧
⩌ϔ喑ႅౕႶڕ䮽ᗐȡᑍ䋰䄫䷅㏱ [44] ݖ⩕ᮛ䕇℈㏳
ノᥚᐧγ⩞䶱☚হࣺᏁ͑䘕ܳ㏱᜽⮱ᓛ䕇䖀ࣺᏁ㷲
㒛喑ⵁ⾣γВ䓴⅔ࡃ⅏ͧ⅔ࡃݯȠV 2 O 5 হ H 3 PW 12 O 40

ͧ㏱वיࡃݯ喑⩞͆☜䚥⅔ࡃव᜽Ά䛈䚥⮱䔋㐚ጒ
ఫ 11 ᓛ䕇䖀ࣺᏁக͚ 2-⩟ധॎଗ⅕⅔ࡃ⩌᜽ 2-⅝ധॎ 㞧喍ఫ 13喎ȡౕ n(͆☜䚥)ńn(H 2 O 2 )ńn(V 2 O 5 )ń
ଗ [39]
Fig. 11 Ammoxidation of 2-methylpyrazine to 2-cyanopyrazine n(H 3 PW 12 O 40 )=1ń6ń0.25ń0.0125ȠࣺᏁ⍖Ꮣ 55 ĎȠ
in microchannel reactor [39] ։⪆ᬣ䬡 6.5 minȠ䓴⅔ࡃ⅏䉕䛼ܳ᪝ͧ 35%喍Ⅱ⏣