Page 180 - 《精细化工》2023年第4期

g866g ㇫㏳ࡃጒ FINE CHEMICALS す 40 ࢤ

⮱㙞䭱ምᄦ℁जВࣾ⣝喑ᵤ৮⮱㙞䭱ምाᑞ䚥ࡧ䲍 AlPO 4 ͧיࡃݯᬣ喑㠜䒙ࡃ⢴হ㠜䚇䔶᠖ᕔ䓫ݝᰭ
᠏喑䔆᭜䚥ᕔ⅔ࡃ➖ V 2 O 5 ౴࠭䉌䒪ݝ䒪Ҁ̷喑Ҭڣ ๔喑ܳݘͧ 53.4%হ 98.4%ȡڣ࣌఍ज㘪᭜䮼Ɑ䦿
䚥ᕔࣾ⩌γᩦअ喑́䮼Ɑ䦿⅔ࡃ➖䉌䒪䛼⮱෋ߍי ⅔ࡃ➖䉌䒪䛼⮱෋ߍ喑יࡃݯ⮱≨ᕔѺ◦෋ߍ喑ह
ࡃݯᵤ৮⮱㙞䭱ምाᑞ䚥ࡧռ⼨Ꮣᰡ๔喑ౕ䦿⅔ࡃ ᬣᵦᢛ BET 㶕ᒮ᭫⹧喑䮼Ɑ䉌䒪䛼෋ߍיࡃݯ⮱℁
➖䉌䒪䛼ͧ 18%ᬣ喑ڣ㙞䭱ምܧ⣝ౕ 200 Ďጓठั 㶕䲏⼜Ό෋๔喑ᬍ⪾Ό෋ߍγיࡃݯ̻ࣺᏁҀ㈨⮱
⮱ᑞ䚥ࡧ喑ₑᬣיࡃݯጟ㏼ڤᰶᑞ䚥ᕔȡ ᣒ㼓䲏⼜喠ڣ⁎喑䮼Ɑ䉌䒪䛼⮱෋ߍיࡃݯڤᰶ䒰
4+
ఫ 8 ͧ VO x /AlPO 4 ㈨݄יࡃݯ⮱ FTIR 䅞ఫȡ 倅⮱ V क़䛼В̻ࣺࣷᏁࡦ䙺⮱ᑞ䚥ᕔȡ఍ₑ喑ധ
λ㠜㓌ധࡃݣ㠜䚇᝭䰭יࡃݯ㐀Ჱ➦◦喑16%VO x /
AlPO 4 ॵ⣝ܧ̻͸ࡦ䙺⮱䚥ᕔᓛ⣜ධ㔹ڤᰶ䒰倅⮱
יࡃ≨ᕔȡᒀיࡃݯ䦿⅔ࡃ➖䉌䒪䛼๔λ 16%ऻ喑
יࡃݯᕔ㘪̸䭺喑䓴็⮱䦿ज㘪ᄩ㜡≨ᕔ➖⻺ౕ䒪
5+
Ҁ㶕䲏ࣾ⩌γఏ㖇喑䒰็⮱䦿⅔ࡃ➖В V ᒏᐼႅౕ
Ꭳ㺳Ⰳγ̭Ⴧ䛼⮱䚥ᕔѺ◦ [34] 喑ᄩ㜡ᰶ᩵≨ᕔ㏱ܳ
5+
̺㘪㷘ٲܳݖ⩕喠हᬣ喑䓴็⮱ V ᄳчᄩ㜡 H 2O 2
ᔘ䕌ܳ㼐ϔ⩌䒰็㜗⩞ധ喑Ҭᓄ㠜䚇䔈̭ₒ⅔ࡃϻ㔹
䭺ѻγⰛᴴϔ➖⮱䔶᠖ᕔ [35] ȡ
2.3 יࡃݯᓗ⣜Ҭ⩕ᕔ㘪

aÿAlPO 4喠bÿ14%VO x/AlPO 4喠cÿ16%VO x/AlPO 4喠dÿ18%VO x/ יࡃݯ⮱Ҭ⩕ᄬপຯఫ 9 ᝭⹧喠יࡃݯҬ⩕ݺ
AlPO 4 হҬ⩕ 5 ⁎ऻ⮱ XRD 䅞ఫহ FTIR 䅞ఫܳݘ㻮ఫ 10
ఫ 8 AlPO 4 䒪Ҁহ VO x /AlPO 4 ㈨݄יࡃݯ⮱ FTIR 䅞ఫ হఫ 11ȡ
Fig. 8 FTIR spectra of AlPO 4 carrier and VO x /AlPO 4
series catalysts ⩞ఫ 9 जВⰸܧ喑יࡃݯҬ⩕ 5 ⁎ऻ喑㠜䒙ࡃ
⢴๔፲̸䭺喑㔹㠜䚇䔶᠖ᕔ㐡ᠮౕ̭͗䒰倅⮱ⅡᎠȡ
–1
ϻఫ 8a जВⰸܧ喑ౕ 508.05 হ 1132.32 cm ั 䕇䓴 ICP ≸䄂जⴒ喑יࡃݯ͚䦿⮱䉕䛼ܳ᪝ϻҬ⩕
ምܳݘᑿᆋλ䒪Ҁ AlPO 4 ͚ PÿO হ AlÿO ⮱̺ᄦ⼝ ݺ⮱ 5.74%䭺ݝҬ⩕ 5 ⁎ऻ⮱ 1.23%ȡ⩞ఫ 10 जВ
–1
ѥ㑖হᄦ⼝ᩣ㑖ᡜߕ [30] 喑㔹ౕ 3500 cm ัምᣕ≸ͧ ⰸܧ喑Ҭ⩕ऻיࡃݯౕ 2ș=13.6° [22] ぶัܧ⣝⮱䦿⅔
ܳၽ䬡⅏䩛⮱ѥ㑖ᡜߕȡᒀ䉌䒪 V 2O 5 ऻ喑В̷➦ᒮም ࡃ➖➦ᒮምጟ㏼⊵๞喑ϲޖ̸ 2ș=20.0~25.2° [19] ัᄦ
–1
౴ܧ⣝ౕיࡃݯᵤ৮͚喑ѳౕ 707.16 cm 䭱䓾ܧ⣝γ Ꮑλ䒪Ҁ AlPO 4 ⮱➦ᒮም喑䄡ᬻౕᓗ⣜Ҭ⩕䓴⼸͚
᫝ም喑ڣᑿᆋλᮣᔮ䦿⅔ࡃ➖⮱➦ᒮ॥ᩣም [33] ȡ ≨ᕔ͚ᓰ䦿ࣾ⩌≮๞⣝䆎ȡౕ 2ș=10.9° [20] ั➦ᒮም
2.2 יࡃݯᕔ㘪䃱Ф ⮱⊵๞䄡ᬻ喑יࡃݯ͚⮱ VO 2 ᝃ≮๞ᝃ㷘䓴⅔ࡃ⅏
㶕 2 ̺ͧहיࡃݯᄦ㠜㓌ധࡃࣺᏁ⮱יࡃᕔ㘪ȡ ⅔ࡃݯ䒙ࡃͧ V ȡहᬣ⩞ఫ 11 ज㻮喑707.16 cm –1
5+
ั⮱䦿➦ᒮምϓ⊵๞喑Όѽ䃮γ XRD ܳᲽ㐀᳉ȡ䮑
㶕 2 ̺हיࡃݯᄦ㠜㓌ࡃࣺᏁיࡃᕔ㘪 ₑ͸ใ喑יࡃݯ㶕䲏ᰶज㘪॥䭱ࣺᏁҀ㈨͚ᰶᱧ➖喑
Table 2 Catalytic performnces of different catalysts for
hydroxylation of benzene 㺳Ⰳγיࡃݯ⮱≨ᕔѺ◦喑ۼᄾγיࡃݯ⮱℁㶕䲏
יࡃݯ 㠜䒙ࡃ⢴/% 㠜䚇䔶᠖ᕔ/% 㠜䚇ϔ⢴/% ⼜喑Όज㘪ᒞ৺γיࡃݯ⮱Ҭ⩕ᄬপȡ16%VO x /AlPO 4
6.6 79.3 5.2 㮪♣ڤᰶ䒰ສ⮱יࡃ≨ᕔѳיࡃݯҬ⩕ᄬপ᭜̭͗
AlPO 4
22.3 90.5 20.2
V 2O 5 䰭㺮㼐۠⮱䬛䷅ȡ
28.7 97.7 28.0
12%VO x/AlPO 4
14%VO x/AlPO 4 33.2 99.5 33.0
53.4 98.4 52.5
16%VO x/AlPO 4
50.9 98.1 49.9
18%VO x/AlPO 4
35.9 97.1 34.9
20%VO x/AlPO 4
ࣺᏁ᲎У喟יࡃݯ 0.2 g喑㠜 4 mL喑䉕䛼ܳ᪝ 30%⮱ H 2O 2
12.5 mL喑Ά㙵 15 mL喑ࣺᏁ⍖Ꮣ 70 Ď喑ࣺᏁᬣ䬡 7 hȡ

⩞㶕 2 जВⰸݝ喑䒪Ҁ AlPO 4 ᄦ㠜㓌ധࡃ⮱י
ࡃ≨ᕔᒵѻ喑ϲ⩕ V 2 O 5 ҉יࡃݯ喑ڣיࡃݯᕔ㘪Ό
䒰ጛȡᄳ V 2 O 5 䉌䒪ݝ䒪Ҁ AlPO 4 ऻ喑䮼Ɑ䉌䒪䛼⮱

෋ߍ喑㠜䚇⮱䔶᠖ᕔ㐡ᠮౕ䒰倅ⅡᎠ喑㔹㠜⮱䒙ࡃ ఫ 9 יࡃݯ⮱ᓗ⣜⽠Ⴧᕔ
⢴হ㠜䚇ϔ⢴ܧ⣝ٵࡴऻ䭺⮱䊸߬ȡᒀ 16%VO x / Fig. 9 Cycling stability of catalysts