强吸波催化剂协同微波能强化果糖脱水制5-羟甲基糠醛

doi:10.11949/0438-1157.20240105

摘要/Abstract

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比常规分别提升了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。

关键词: 微波辐照, 果糖水解, 多相反应, 动力学, 介电损耗, 催化

Abstract:

Multihole hollow carbon spheres (MHCS) were prepared by using a hard template method. The effects of heat treatment temperature, metal loading, and etching on the electromagnetic parameters of MHCS were systematically studied. Among the prepared carbon spheres, MHCS-800 with high dielectric loss (ε″ = 213) was selected as the support for catalysts, while SCS-800 (ε″ = 50) and SCS (ε″ = 0.08) served as control groups. These carbons after sulfonation were used to catalyze the hydrolysis of fructose. Based on the reaction kinetics under microwave (MW) and conventional heating conditions, the influence of dielectric loss on the MW-assisted catalytic effect was investigated. The results showed that the conversion rate can reach 97.7% within 5 min using MHCS-800-SO₃H as catalysts under 80 W MW power irradiation. Besides, the reaction rate constant (k) under MW is 0.76 min^-1, which is 8.97 times of that under conventional heating (k=0.0847 min^-1). The MW enhancement effect occurred in MHCS-800-SO₃H is much more significant compared with SCS-800-SO₃H and SCS-SO₃H (where k values were increased by 164.9% and 11.9%, respectively). The above results can be attributed to the combination of the hollow porous structure and the high graphitization degree of MHCS-800, which is conducive to the formation of “hotspots” on the surface of catalyst particles, thereby accelerating catalytic reactions.

Key words: microwave irradiation, fructose dehydration, multiphase reaction, kinetics, dielectric loss, catalysis

中图分类号:

TQ 032.4

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, 2024, 75(4): 1565-1577.

Anran XU, Kai LIU, Na WANG, Zhenyu ZHAO, Hong LI, Xin GAO. Strong wave-absorbing catalyst cooperates with microwave energy to enhance fructose dehydration to produce 5-hydroxymethylfurfural[J]. CIESC Journal, 2024, 75(4): 1565-1577.

图/表 15

图1 常规加热和微波加热催化果糖水解反应装置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

图2 MHCS-800刻蚀前 (a) 以及刻蚀后 (b) 的SEM图片

Fig.2 SEM images of MHCS-800 before (a) and after (b)etching

图3 不同合成温度下MHCS的XRD谱图

Fig.3 XRD patterns of MHCS at different synthesis temperatures

图4 MHCS-800的TEM图(a) 及EDS元素分布[(b)~(d)]

Fig.4 TEM image (a) and element distribution [(b)—(d)] of MHCS-800

图5 不同合成条件对MHCS复介电常数以及复磁导率的影响

Fig.5 Effects of different synthesis conditions on complex permittivity and complex permeability of MHCS

图6 MHCS-800刻蚀前后的复介电常数（a）和复磁导率（b）

Fig.6 Complex permittivity（a）and complex permeability（b）of MHCS-800 before and after etching

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/GHz
MHCS-800-SO₃H	39	213	5.46	2.45
SCS-800-SO₃H	40	50	1.25	2.45
SCS-SO₃H	3	0.08	0.03	2.45

图7 不同催化剂的红外谱图

Fig.7 FTIR spectra of different catalysts

图8 不同催化剂的XPS谱图

Fig.8 XPS spectra of different catalysts

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/% （质量分数）		磺化后/% （质量分数）
样品	Fe含量	Co含量	Fe含量	Co含量
MHCS-800-SO₃H	10.60	5.93	5.39	2.98

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/(μmol/g)	Brønsted酸度/(μmol/g)	Lewis酸度/(μmol/g)
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3种催化剂的果糖转化率（a）、5-HMF收率（b）及5-HMF选择性（c）

Fig.9 Fructose conversion rate (a), 5-HMF yield (b) and 5-HMF selectivity (c) of three catalysts under conventional heating at 120℃

图10 不同加热条件下反应溶液表观温度随时间变化情况

Fig.10 Time-varying curves of apparent temperatures for reaction solutions under different heating conditions

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

图12 微波响应催化剂强化果糖催化转化机理

Fig.12 Mechanism of microwave responsive catalyst enhanced fructose catalytic conversion

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