Page 47 - 《精细化工》2023年第4期
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す 4 ᑍუᏤ喑ぶ: ᓛ䕇䖀ࣺᏁக͚㏳ࡃ႓৮व࢞䮖ጒ㞧ⵁ⾣䔈ᆂ g733g
⋟喎⮱хࡃጒ㞧̸࣯喑͆☜䚥⮱䒙ࡃ⢴䓫 97.1%喑 ⮱䛺⅛⯽᭜็⩕䕁ᰶᱧव͚䬡Ҁ [49-50] ȡ䛺⅛ࡃࣺ
Ά䛈䚥⮱䔶᠖ᕔͧ 91.4%ȡ䒰λ䜉ᐼ䬡⁴⅔ࡃࣺ Ꮑ᭜ᑧᩫ☚ࣺᏁ喑Ꭳ́䛺⅛⯽ࣵ䲋፥≨∩喑ऄ☚Ხ
Ꮑ喑䔋㐚ࣺᏁڤᰶ᩵⢴倅Ƞᬣ䬡ⴚȠღᭀᣔݣ≮ᔮ ᭀࣾ⩌ޔ◵ܳ㼐喑ࣾ⩌✳◥喑㔹喑䜉ᐼࣺᏁக͚
ぶх◦喑⊵䮑γ⅔ࡃ䓴⼸͚ࣹ⅔Ⅱܳ㼐ፓᲒ⮱Ⴖڕ ⮱䛺⅛ࡃࣺᏁ䕇፥ౕ 0~5 Ď䒰ѻ⮱ࣺᏁ⍖Ꮣহޔ
䮽ᗐহ㏼≻ᢌȡ ◵ᤲ៹̸䔈㵹喑⩌ϔ᩵⢴ѻȡₑใ喑㮪♣̭ψ䛺⅛
⯽ౕ䒰ѻ⍖Ꮣ℁䒰⽠Ⴧ喑ѳ㠒ऻ㐚ࣺᏁ⍖Ꮣ䒰倅喑
ϺႅౕႶڕ䮽ᗐȡᓛ䕇䖀ࣺᏁகឭᱜ⮱䔈ₒͧࣾᆂ
倅᩵Ƞजᣔ⮱䛺⅛ࡃࣺᏁহ䛺⅛⯽ࣺᏁጒ㞧ӈγ
ᰶ᩵⮱䕁ᒱȡ
ݺጟ䔝ࣷ喑2,4,5-̶⅌⏡㠜᭜䛺㺮⮱ࡨ㢜͚䬡
Ҁ喑ज⩞ 1,2,4-̶⅌㠜Ⱑᣒ⏡ࡃवȡ䮑γݺ䔝∂喑
ఫ 13 ᓛ䕇䖀͚͆☜䚥⅔ࡃ⩌Ά䛈䚥 [44] ᑍݖ䯱䄫䷅㏱ [51] 䔅ݖ⩕㏼ڥ⮱ Gatterman ࣺᏁౕᓛ
Fig. 13 Oxidation of acrylic acid to glyoxylic acid in
microchannel reactor [44] 䕇䖀ࣺᏁக̻䜉ᐼࣺᏁகⰥ㐀व⮱ࣺᏁ㷲㒛͚⩞
2,4,5-̶⅌㠜㘧倅᩵वγ 2,4,5-̶⅌⏡㠜喍ఫ 15喎ȡ
㏑㐡㉍⩌ϔ㏑㐡⮱㣞䊈ᅁጒ㞧喍Lyocell process喎 ᓛ䕇䖀ࣺᏁகͧڲᒱ 1 mm ⮱㖇ఈ⅌Ά☜℈㏳ノ㏬
͚В N-⩟ധॄ੶-N-⅔ࡃ➖喍NMMO喎ͧ⏣ݯ [45] ȡ వȡຯఫ 15 喑2,4,5-̶⅌㠜㘧̻ NaNO 2 ౕ HBr
Ⱋݺ喑NMMO ⩞ι⅔ࡃⷠיࡃ䓴⅔ࡃ⅏⅔ࡃ N-⩟ ႅ̸ౕ⮱䛺⅛ࡃࣺᏁౕݺ㒛 T ಸ⌤वக⮱ᓛ䕇䖀ࣺ
ധॄ੶⩌ϔ喑ࣺᏁౕ䜉ᐼࣺᏁக͚䔈㵹 [46-47] ȡͧ Ꮑக͚λ–10 Ď䶧ݖ䔈㵹ȡᅪノ⤳䃧̷ HBr ̻ 2,4,5-
倅ڣ⩌ϔ⮱Ⴖڕᕔ喑BAUMEISTER ぶ [48] 䛴⩕ノ䖀 ̶⅌㠜㘧⮱➖䉕⮱䛼℁ͧ 2ń1喑ѳ䭲̷ι㔲ᰭҠ
ڲᒱͧ 1 mm ⮱ࣺᏁக಄喑㏱㷲ᕨ䪬ͧ 750 mm ➖䉕⮱䛼℁ͧ 4ń1喑ѻλₑթчᄩ㜡ޜࣺᏁࣾ⩌ൢ
⮱ᓛ䕇䖀ࣺᏁக喑䔈㔹ౕₑࣺᏁக͚ⵁ⾣γ⩞䓴⅔ උᓛ䕇䖀ࣺᏁகȡᄳ̺⽠Ⴧ⮱ 2,4,5-̶⅌㠜ധ䛺⅛⯽
ࡃ⅏⅔ࡃ N-⩟ധॄ੶व NMMO ⮱ࣺᏁጒ㞧হߕ ⰡᣒԿڒ㷲ᰶ⅏⏡䚥হ䨉ㆶ⮱ࣺᏁ䜉喑ޔ◵ᤲ៹̸
߈႓喍ఫ 14喎ȡࣺᏁ䓴⼸͚喑䶱☚ݝࣺᏁ⍖Ꮣ⮱ N- λ 70 Ď䓲䕌ࣾ⩌⏡ࡃࣺᏁ⩌ 2,4,5-̶⅌⏡㠜喑ᰭ
⩟ധॄ੶হ䓴⅔ࡃ⅏Ꭳ㵹∢ڒ⌤वக喑♣ऻ䔈ڒᓛ 倅ᩣ⢴ज䓫 93.3%ȡ䕇䓴䄰᪡ T ಸ⌤वகহᓛ䕇䖀
䕇䖀ࣺᏁக䔈㵹ࣺᏁȡᒀक़ᰶ䉕䛼ܳͧ 1%ι⅔ࡃ ࣺᏁக⮱ᅧᄥ喑व㻱ᒵღᭀᩫ๔ݝࡰٸ㏔ȡ䛴
ⷠ⮱ࣺᏁ⋟ౕ⍖Ꮣ 60 ĎȠ։⪆ᬣ䬡 13.90 min ⮱ ⩕ㆨѩ⮱ࣺᏁக䔈㵹ःА㠜㘧⮱䛺⅛ࡃ喑䔅जВВ
У̸≮㏼ࣺᏁகᬣ喑N-⩟ധॄ੶⮱䒙ࡃ⢴倅䓫 98%喑 хᐯ⮱ᩣ⢴喍88.2%喎वⰥᏁ⮱ⷅ㠜 [52] ȡ
NMMO ⮱ᩣ⢴ͧ 93.5%ȡ䕇䓴ߕ߈႓ⵁ⾣ჇࣺᏁ
⮱≨ࡃ㘪ͧ 69.5 kJ/mol喑㶕ᬻ⅔ࡃࣺᏁ̺ऄэ䉕䭽
ݣ喑䒙ࡃ⢴̻։⪆ᬣ䬡ჳܴⰥڠ喑㔹喑ࣺᏁ㻱
ज䕇䓴ߍࣺᏁக಄ᓄВౕ̭Ⴧ㠰డڲ䄰अȡϻ
㏼≻হႶڕ͑䲏㔰㭾喑䄒䔋㐚ࣺᏁጒ㞧जᰬАጒ
̷͇⣝㵹⮱䜉ᐼ䬡⁴ࣺᏁጒ㞧ȡ
ఫ 15 ᓛ䕇䖀ࣺᏁக͚ 2,4,5-̶⅌㠜㘧䛺⅛ࡃव 2,4,5-
[51]
̶⅌⏡㠜
Fig. 15 Synthesis of 2,4,5-trifluoro-bromobenzene by
diazotization of 2,4,5-trifluoroaniline in microchannel
reactor [51]
ᓄ⯷λ 3D ក࢝ឭᱜহ⓭ٶᓛߍጒឭᱜ⮱䔈ₒ喑
ఫ 14 ᓛ䕇䖀ࣺᏁக͚ N-⩟ധॄ੶⅔ࡃव N-⩟ധॄ ϧЙजВ䃫䃎ݣ䕍ฺᱯ㐀Ჱ⮱ᓛ≮ᣔ㟜❴喑Ჱᐧ⌤व᩵
੶-N-⅔ࡃ➖ [48] ᰡສȠ䕇䛼ᰡ๔⮱ᓛ䕇䖀ࣺᏁகȡప䋰䄫䷅㏱ [53]
Fig. 14 Synthesis of N-methylmorpholine-N-oxide by ݖ⩕下⓭ٶᓛߍጒឭᱜݣิܧฺᱯᲱಸ⮱倅ჳ
oxidation of N-methylmorpholine in microchannel
reactor [48] ᏓȠ๔Ҁ⼜ࣅㆠ㏔ⶩ䚥⯽ᱽ䉕⮱ᓛ≮Ҁ㟜❴
喍MFCs喎ȡ䄒㟜❴⮱̶㐡Ჱಸ仃ٵᄳ≮䔈⮱≮ܳ
3 䛺⅛̻֣⅛ࡃጒ㞧 㼐̷̸͑͗ܳ≮喑♣ऻ䔆͑͗ܳ≮ںϻጓठ
͑͗ा䛺㐀व喑ᰭ㏵ܳ㷯ͧ 8 ͗ᓛ≮喑Ꭳᒏ
ќ⅕ധ㟠ധࡃव➖̻χⶊ䚥䧍ౕ䚥ᕔϸ䉕͚ࣺ 7 ͗э䉕⩹䲏ȡ⩞ڣᲱᐧ⮱ࣺᏁகౕᄦ⩟㠜㘧⮱
Ꮑ⩌䛺⅛⯽⮱ࣺᏁ⼝ͧ䛺⅛ࡃࣺᏁ喑㔹ࣺᏁ⩌ 䛺⅛ࡃࣺᏁВࣷ䮼ऻ̻㖁ⶩ䚥䶾䗐䚴䚜喍B 2 pin 2 喎䔈