• •
徐安冉1(), 刘凯1, 王娜1, 赵振宇1(), 李洪1, 高鑫1,2()
收稿日期:
2024-01-23
修回日期:
2024-03-20
出版日期:
2024-03-25
通讯作者:
赵振宇,高鑫
作者简介:
徐安冉(1999.8—),男,硕士研究生,xuanran99@tju.edu.cn
基金资助:
Anran XU1(), Kai LIU1, Na WANG1, Zhenyu ZHAO1(), Hong LI1, Xin GAO1,2()
Received:
2024-01-23
Revised:
2024-03-20
Online:
2024-03-25
Contact:
Zhenyu ZHAO, Xin GAO
摘要:
利用硬模板法制备了中空多孔碳球(MHCS),系统研究了热处理温度、金属负载量、刻蚀前后对MHCS电磁参数的影响。从中选取高介电损耗值(ε’’)的MHCS-800(ε’’ = 213)作为催化剂载体并以SCS-800(ε’’ = 50)和SCS(ε’’ = 0.08)作为对比样品,经磺化后用于催化果糖水解制5-羟甲基糠醛。根据在微波加热和常规油浴条件下的反应动力学,探究了ε’’对微波催化效果的影响。结果表明,在80 W微波功率辐照下使用MHCS-800-SO3H作为催化剂,5 min转化率即可达97.7%;反应速率常数(k)为0.76 min-1,是常规加热(k = 0.0847 min-1)的8.97倍,该催化剂相较于SCS-800-SO3H和SCS-SO3H的微波催化效果(k比常规提升了164.9%、11.9%)更加显著。以上研究结果源于中空多孔结构和高的石墨化程度相耦合更有利于在催化剂颗粒表面形成“热点”从而加速催化反应。
中图分类号:
徐安冉, 刘凯, 王娜, 赵振宇, 李洪, 高鑫. 强吸波催化剂协同微波能强化果糖脱水制5-羟甲基糠醛[J]. 化工学报, DOI: 10.11949/0438-1157.20240105.
Anran XU, Kai LIU, Na WANG, Zhenyu ZHAO, Hong LI, Xin GAO. Fructose dehydration to produce 5-hydroxymethylfurfural enhanced by synergy of microwave energy and strong wave-absorbing catalysts[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240105.
图1 常规和微波加热催化果糖水解反应装置图1—连接管;2—磁子;3—红液温度计;4—油浴锅;5—冷凝管;6—微波腔;7—光纤温度计;8—带夹套的微波反应器;9—磁力搅拌器
Fig.1 Schematic illustration of experimental apparatuses for fructose dehydration under conventional heating and microwave irradiation
样品 | ε’ | ε’’ | tanδ | 频率 |
---|---|---|---|---|
MHCS-800-SO3H | 39 | 213 | 5.46 | 2.45GHz |
SCS-800-SO3H | 40 | 50 | 1.25 | 2.45GHz |
SCS-SO3H | 3 | 0.08 | 0.03 | 2.45GHz |
表1 不同吸波性能催化剂的介电参数
Table 1 Dielectric parameters of catalysts with different microwave absorbing properties
样品 | ε’ | ε’’ | tanδ | 频率 |
---|---|---|---|---|
MHCS-800-SO3H | 39 | 213 | 5.46 | 2.45GHz |
SCS-800-SO3H | 40 | 50 | 1.25 | 2.45GHz |
SCS-SO3H | 3 | 0.08 | 0.03 | 2.45GHz |
样品 | 磺化前(wt.%) | 磺化后(wt.%) | ||
---|---|---|---|---|
Fe含量 | Co含量 | Fe含量 | Co含量 | |
MHCS-800-SO3H | 10.6 | 5.93 | 5.39 | 2.98 |
表2 MHCS-800-SO3H磺化前后铁和钴的含量
Table 2 Fe and Co contents of MHCS-800-SO3H before and after sulfonation
样品 | 磺化前(wt.%) | 磺化后(wt.%) | ||
---|---|---|---|---|
Fe含量 | Co含量 | Fe含量 | Co含量 | |
MHCS-800-SO3H | 10.6 | 5.93 | 5.39 | 2.98 |
样品 | 总酸度 (μmolg-1) | Brønsted酸度(μmolg-1) | Lewis酸度 (μmolg-1) |
---|---|---|---|
MHCS-800-SO3H | 74.51 | 9.67 | 64.84 |
SCS-800-SO3H | 80.96 | 11.64 | 69.32 |
SCS-SO3H | 80.84 | 13.93 | 66.91 |
表3 不同吸波性能催化剂的酸性
Table 3 Acidic properties of catalysts with different microwave absorbing properties
样品 | 总酸度 (μmolg-1) | Brønsted酸度(μmolg-1) | Lewis酸度 (μmolg-1) |
---|---|---|---|
MHCS-800-SO3H | 74.51 | 9.67 | 64.84 |
SCS-800-SO3H | 80.96 | 11.64 | 69.32 |
SCS-SO3H | 80.84 | 13.93 | 66.91 |
图9 常规加热120℃条件下三种催化剂的果糖时变转化率(a)、5-HMF产率(b)及选择性(c)
Fig.9 The time-varying conversion rate (a), 5-HMF yield (b) and selectivity (c) of three catalysts under conventional heating at 120℃
图11 不同微波响应催化剂在常规加热和微波辐照下的催化效果
Fig.11 Catalytic performances of different microwave responsive catalysts under conventional heating and microwave irradiation
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