微波与碳基催化剂协同促进果糖制5-羟甲基糠醛

doi:10.16085/j.issn.1000-6613.2021-0671

摘要/Abstract

摘要：

生物质转化为高附加值的化学品是替代石化产品的有效途径，微波与催化剂的协同作用有助于提升糖类的转化效率。碳材料具有良好的化学稳定性和介电性，是微波反应过程中理想的催化剂载体和吸波剂。为了探究碳基催化剂对微波场的响应能力，本文以4种碳材料为载体应用于果糖转化过程，包括碳纳米管（CNT）、碳纳米纤维（CNF）、炭黑（CB）和活性炭（AC）。以果糖转化率和5-羟甲基糠醛（5-HMF）收率为评价指标，对比不同催化剂在常规和微波加热条件下的催化性能，探究微波与不同载体的耦合作用对反应的强化效果。在微波场中测量不同碳材料悬浮液的温度曲线，评价碳基催化剂在微波场中的加热能力。通过表征样品结构和介电参数，解释载体与微波间耦合作用差异的原因。结果表明，碳基催化剂的微波诱导热效应可以有效提升反应转化率和收率，拥有高损耗角正切值和电导率的催化剂把微波能转化为热量的能力较强，更有助于将微波能量传递至反应表面。高比表面积、高长径比、低密度和高石墨化度的碳基催化剂也有利于产生微波热效应。另外，由于显著的微波热效应，碳纳米管基催化剂CNT-SA在4类催化剂中催化性能最优，以110℃微波辐射10min，5-HMF收率可达96.30%，且催化剂具有良好的循环使用性能。

关键词: 微波辐射, 催化, 碳基催化剂, 果糖转化, 5-羟甲基糠醛

Abstract:

Microwave(MW)-assisted biomass conversion is a promising method for the production of value-added chemicals. Carbon materials have good chemical stability and dielectric properties, which are ideal catalyst supports and microwave absorbers in the process of MW reaction. In view of this, four carbon materials, including carbon nanotubes(CNT), carbon nanofibers(CNF), carbon black(CB) and activated carbon(AC), were used to catalyst fructose conversion under conventional heating and MW irradiation conditions. The enhancement effects of MW coupling with different supports for the reaction performance were further explored. The heating behaviors of different carbon material suspensions were measured under MW condition, and the difference in their dielectric properties was explained by structural and physical properties. The results show that the MW induced thermal effect of carbon-based catalysts can effectively improve the reaction efficiency. The catalyst with high loss tangent and conductivity tends to have a strong heating ability, which is conductive to transfer MW energy to the catalyst surface. Carbon-based catalysts with high specific surface area, high aspect ratio, low density and high graphitization degree are also beneficial to the generation of thermal effect. In addition, CNT-SA is the most suitable catalyst among the four alternatives. The yield of 5-hydroxymethylfurfural(5-HMF) reaches 96.30% in 10min at 110℃ under MW irradiation, and the catalyst has a good recyclability.

Key words: microwave irradiation, catalysis, carbon-based catalyst, fructose dehydration, 5-hydroxymethylfurfural

中图分类号:

TQ032.4

吕孝琦, 李洪, 赵振宇, 李鑫钢, 高鑫, 范晓雷. 微波与碳基催化剂协同促进果糖制5-羟甲基糠醛[J]. 化工进展, 2022, 41(2): 637-647.

LYU Xiaoqi, LI Hong, ZHAO Zhenyu, LI Xingang, GAO Xin, FAN Xiaolei. Microwave-assisted carbon-based catalysts for fructose dehydration to 5-hydroxymethylfurfural[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 637-647.

图/表 14

图1 微波和常规加热果糖催化反应装置示意图1—磁力搅拌器；2—带夹套的微波反应器；3—光纤温度计；4—冷凝管；5—连接管；6—微波炉；7—油浴锅；8—红液温度计；9—磁子

表1 4种碳基催化剂的介电性能和电导率

样品	ε'	ε''	tanδ	σ/μS·cm^-1
DMSO	44.60	11.05	0.2478	0.17
AC-SA悬浮液	44.78	11.18	0.2497	1.64
CNF-SA悬浮液	44.84	11.24	0.2507	2.07
CB-SA悬浮液	45.09	11.41	0.2531	2.33
CNT-SA悬浮液	45.61	11.82	0.2591	4.35

图2 4种碳基催化剂的XRD谱图

表2 4种碳基催化剂的比表面及结构参数

样品名称	石墨化度/%	比表面积/m²·g^-1	孔容/cm³·g^-1	密度/g·cm^-3
AC-SA	31.32	1093.37	0.59	0.45
CNF-SA	66.24	37.52	0.17	2.10
CB-SA	16.38	103.37	0.43	0.28
CNT-SA	73.58	190.80	0.84	0.13

图3 碳基催化剂的SEM和TEM图

图4 4种碳基催化剂的FTIR谱图

表3 4种碳基催化剂的酸度分布

样品	总酸浓度 /mmol·g^-1	磺酸基团浓度 /mmol·g^-1	羧酸基团和酚羟基浓度 /mmol·g^-1
AC-SA	3.28	0.51	2.77
CNF-SA	4.14	0.62	3.52
CB-SA	3.86	0.56	3.30
CNT-SA	3.92	0.60	3.32

图5 在微波场中4种碳基催化剂悬浮液的温度曲线

表4 4种碳基催化剂的微波加热参数

样品	升温速率/℃·min^-1	稳定温度/℃	达到稳定时间/min
DMSO纯溶剂	25.41	109.52	3.49
AC-SA悬浮液	43.95	110.55	2.04
CNF-SA悬浮液	51.46	110.70	1.76
CB-SA悬浮液	56.54	112.06	1.62
CNT-SA悬浮液	68.05	112.30	1.35

图6 4种碳基催化剂常规和微波加热条件下对果糖转化的影响（反应条件：0.2g果糖、0.2g碳基催化剂、110℃、10min、20mL DMSO）

图7 微波场下反应温度对CNT-SA催化果糖脱水的影响（反应条件：0.2g果糖、0.2g CNT-SA、20mL DMSO、10min）

图8 微波场下反应时间对CNT-SA催化果糖脱水的影响（反应条件：0.2g果糖、0.2g CNT-SA、20mL DMSO、110℃）

图9 微波场下催化剂用量对CNT-SA催化果糖脱水的影响（反应条件：0.2g果糖、0.2g CNT-SA、20mL DMSO、110℃）

图10 微波场下CNT-SA对果糖脱水循环使用性能（反应条件：0.2g CNT-SA、0.2g果糖、0.2g CNT-SA、20mL DMSO、110℃、10min）

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