微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛

doi:10.16085/j.issn.1000-6613.2022-0197

化工进展 ›› 2022, Vol. 41 ›› Issue (11): 5858-5869.DOI: 10.16085/j.issn.1000-6613.2022-0197

微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛

慕诗芸¹(), 刘凯¹, 吕孝琦¹, 矫义来³(), 李鑫钢¹, 李洪¹, 范晓雷⁴, 高鑫¹^,²()

^1.天津大学化工学院，精馏技术国家工程研究中心，天津 300350
^2.物质绿色创造与制造海河实验室，天津 300192
^3.中国科学院金属研究所，辽宁沈阳 110016
^4.曼彻斯特大学工程学院化学工程系，英国曼彻斯特 M13 9PL

收稿日期:2022-02-06 修回日期:2022-04-23 出版日期:2022-11-25 发布日期:2022-11-28
通讯作者: 矫义来,高鑫
作者简介:慕诗芸（1997—），女，硕士研究生，研究方向为微波强化反应过程。E-mail：mushiyun1@163.com。
基金资助:
欧盟“地平线2020”研究与创新基金(872102);物质绿色创造与制造海河实验室项目

Conversion of fructose to 5-hydroxymethylfurfural catalyzed by microwave-assisted zirconia@carbon nanotubes

MU Shiyun¹(), LIU Kai¹, LYU Xiaoqi¹, JIAO Yilai³(), LI Xingang¹, LI Hong¹, FAN Xiaolei⁴, GAO Xin¹^,²()

^1.National Engineering Research Center of Distillation Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
^2.Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
^3.Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China
^4.Department of Chemical Engineering, School of Engineering, The University of Manchester, Manchester M13 9PL, United Kingdom

Received:2022-02-06 Revised:2022-04-23 Online:2022-11-25 Published:2022-11-28
Contact: JIAO Yilai, GAO Xin

摘要/Abstract

摘要：

糖类催化转化是生产生物质基燃料和高附加值化学品的重要途径，而微波能量的使用可使这一过程更具商业可行性。本文探究了微波辐射下微波响应型催化剂碳纳米管负载氧化锆［ZrO₂/MWCNTs(C)］催化的果糖高效分解制5-羟甲基糠醛（5-HMF）过程。首先，采用水热法制备了性能优异的氧化锆@碳纳米管催化剂，并对其进行表征；进一步考察了催化剂用量、果糖浓度、反应温度和反应时间对反应产物5-HMF收率的影响，并通过调节各组分在反应过程中的实际含量，探究微波强化的作用机理。研究结果表明在相对温和的条件下（120℃、常压），微波辐射下的5-HMF收率（约74%）远高于常规加热条件下的5-HMF收率（约31%）；采用最佳ZrO₂60/CNTs用量（ZrO₂质量分数约为60%），微波场中，140℃常压条件下反应10min，可以实现约98%的果糖转化率和92%的5-HMF收率。通过探究载体吸波性能与活性位点催化性能之间的耦合匹配关系，揭示了微波协同催化过程强化机理归因于具有强吸波性能碳质载体的选择性加热和活性位点ZrO₂之间的协同耦合作用。

关键词: 微波辐射, 催化, 多壁碳纳米管, 氧化锆, 果糖转化, 5-羟甲基糠醛

Abstract:

Catalytic conversion of saccharides is a promising way for the production of biomass-based fuel and high value-added chemical, and the utilization of microwave energy can make this process more commercially viable. In this paper, the efficient decomposition for fructose to 5-hydroxymethylfurfural (5-HMF) catalyzed over carbon nanotube-supported zirconia [ZrO₂/MWCNTs(C)] as a microwave response catalyst under microwave irradiation was investigated. Firstly, hydrothermal synthesis method was used to synthetize ZrO₂@MWCNTs(C) catalysts with high performance and then, they were characterized. Moreover, the effects of catalyst dosage, fructose concentration, reaction temperature and reaction time for the yield of 5-HMF were further investigated and lastly, by adjusting the participation of each component for composite catalyst during reaction, the microwave strengthening mechanism was revealed. Under a mild MW condition (at 120℃, atmospheric pressure), high 5-HMF yield about 74% after 10min reaction time was achieved which was significantly higher than that obtained under the conventional heating about 31%. With the optimum dosage of ZrO₂60/CNTs (50%), about 98% fructose conversion and about 92% 5-HMF yield could be achieved with microwave irradiation at 140℃ and atmospheric pressure for 10min. By exploring the coupling matching relation between the absorption performance of the supporting and the catalytic performance of the active site, the strengthening mechanism of the microwave synergistic catalytic process was revealed, which may be attributed to the combination of selective heating for carbon supporting and the active site of zirconia.

Key words: microwave irradiation, catalysis, multi-walled carbon nanotubes, zirconia, fructose dehydration, 5-hydroxymethylfurfural

中图分类号:

TQ032.4

慕诗芸, 刘凯, 吕孝琦, 矫义来, 李鑫钢, 李洪, 范晓雷, 高鑫. 微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛[J]. 化工进展, 2022, 41(11): 5858-5869.

MU Shiyun, LIU Kai, LYU Xiaoqi, JIAO Yilai, LI Xingang, LI Hong, FAN Xiaolei, GAO Xin. Conversion of fructose to 5-hydroxymethylfurfural catalyzed by microwave-assisted zirconia@carbon nanotubes[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5858-5869.

图/表 14

表1 不同ZrO2负载量复合材料的介电性能参数

样品	ε′	ε″	tanδ
MWCNTs（C）	847.09	927.74	1.0952
ZrO₂20/CNTs	44.72	132.46	2.9620
ZrO₂40/CNTs	38.31	73.14	1.9092
ZrO₂60/CNTs	22.67	36.13	1.5937
ZrO₂80/CNTs	21.61	15.81	0.7316
ZrO₂90/CNTs	7.08	1.05	0.1483
ZrO₂	2.61	0.11	0.0421

图1 不同ZrO2负载量催化剂的XRD谱图

图2 催化剂MWCNTs(C)（a），ZrO220/CNTs（b），ZrO240/CNTs（c），ZrO260/CNTs（d、h），ZrO280/CNTs（e），ZrO290/CNTs（f）和ZrO2（g）的TEM图和ZrO260/CNTs的EDS图（i、j、k、l）

图3 不同ZrO2负载量催化剂的FTIR谱图

表2 ZrO2/MWCNTs(C)催化剂的Zr质量分数 (%)

催化剂样品	Zr测量值	Zr理论值	ZrO₂实际负载量
ZrO₂20CNTs	11.74	14.81	15.87
ZrO₂40/CNTs	27.96	29.61	37.78
ZrO₂60/CNTs	42.79	44.42	57.82
ZrO₂80/CNTs	57.31	59.23	77.45
ZrO₂90/CNTs	64.56	66.63	87.24
ZrO₂	74.15	74.03	100.00

图4 反应温度对微波辐射下ZrO260/CNTs催化果糖分解的影响（0.4g果糖，0.2g催化剂，10min，20mL DMSO）

图5 果糖浓度对微波辐射下ZrO260/CNTs催化果糖分解的影响（果糖/催化剂=1/2，120℃，10min，20mL DMSO）

图6 催化剂用量对微波辐射下ZrO260/CNTs催化果糖分解的影响（0.4g果糖，120℃，10min，20mL DMSO）

图7 反应时间对微波辐射下ZrO260/CNTs催化果糖分解的影响（0.4g果糖，0.2g催化剂，120℃，20mL DMSO）

表3 不同对照实验中复合催化剂ZrO2@MWCNTs(C)总用量

催化剂样品	ZrO₂@MWCNTs(C)总用量/g
催化剂样品	保持催化剂总量相同	保持氧化锆用量相同	保持碳纳米管用量相同
MWCNTs（C）	0.2000	—	0.0844
ZrO₂20/CNTs	0.2000	0.7289	0.1003
ZrO₂40/CNTs	0.2000	0.3061	0.1356
ZrO₂60/CNTs	0.2000	0.2000	0.2000
ZrO₂80/CNTs	0.2000	0.1493	0.3742
ZrO₂90/CNTs	0.2000	0.1325	0.6614
ZrO₂	0.2000	0.1154	—

图8 不同加热条件对ZrO260/CNTs催化果糖转化的影响（0.4g果糖，0.2g催化剂，120℃，20mL DMSO）

图9 不同催化剂在常规加热下的果糖转化反应（0.4g果糖，20mL DMSO，10min，120℃）

图10 不同催化剂在微波辐射下的果糖转化反应（0.4g果糖，20mL DMSO，10min，120℃）

图11 载体和活性位点协同对果糖催化转化的影响（0.2g催化剂，0.4g果糖，20mL DMSO，10min，120℃）

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微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛

Conversion of fructose to 5-hydroxymethylfurfural catalyzed by microwave-assisted zirconia@carbon nanotubes

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