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

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 637-647.doi: 10.16085/j.issn.1000-6613.2021-0671

微波与碳基催化剂协同促进果糖制5-羟甲基糠醛

吕孝琦¹(), 李洪¹, 赵振宇¹, 李鑫钢¹, 高鑫¹(), 范晓雷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.曼彻斯特大学工程学院，化学工程与;分析科学系，英国曼彻斯特 M13 9PL

收稿日期:2021-03-31 修回日期:2021-07-19 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 高鑫,范晓雷 E-mail:lxq77@tju.edu.cn;gaoxin@tju.edu.cn;xiaolei.fan@manchester.ac.uk
作者简介:吕孝琦（1996—），女，硕士研究生，研究方向为微波强化反应过程。E-mail：lxq77@tju.edu.cn。
基金资助:
国家自然科学基金面上项目(21878219);欧盟“地平线2020”研究与创新基金(872102)

Microwave-assisted carbon-based catalysts for fructose dehydration to 5-hydroxymethylfurfural

LYU Xiaoqi¹(), LI Hong¹, ZHAO Zhenyu¹, LI Xingang¹, GAO Xin¹(), FAN Xiaolei²()

^1.National Engineering Research Center of Distillation Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
^2.Department of Chemical Engineering and Analytical Science, School of Engineering, University of Manchester, Manchester M13 9PL, United Kingdom

Received:2021-03-31 Revised:2021-07-19 Online:2022-02-05 Published:2022-02-23
Contact: GAO Xin,FAN Xiaolei E-mail:lxq77@tju.edu.cn;gaoxin@tju.edu.cn;xiaolei.fan@manchester.ac.uk

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

表1

图2

表2

图3

图4

表3

图5

表4

图6

图7

图8

图9

图10

参考文献 43

1	JING Y X, GUO Y, XIA Q N, et al. Catalytic production of value-added chemicals and liquid fuels from lignocellulosic biomass[J]. Chem, 2019, 5(10): 2520-2546.
2	WANG J J, XU W J, REN J W, et al. Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid[J]. Green Chemistry, 2011, 13(10): 2678-2681.
3	HUBER G W, CHHEDA J N, BARRETT C J, et al. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates[J]. Science, 2005, 308(5727): 1446-1450.
4	WEI Z J, LOU J T, LI Z B, et al. One-pot production of 2, 5-dimethylfuran from fructose over Ru/C and a Lewis–Brønsted acid mixture in N,N-dimethylformamide[J]. Catalysis Science & Technology, 2016, 6(16): 6217-6225.
5	TOFTGAARD PEDERSEN A, RINGBORG R, GROTKJÆR T, et al. Synthesis of 5-hydroxymethylfurfural (HMF) by acid catalyzed dehydration of glucose-fructose mixtures[J]. Chemical Engineering Journal, 2015, 273: 455-464.
6	MARULLO S, RIZZO C, MELI A, et al. Ionic liquid binary mixtures, zeolites, and ultrasound irradiation: a combination to promote carbohydrate conversion into 5-hydroxymethylfurfural[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(6): 5818-5826.
7	BESSON M, GALLEZOT P, PINEL C. Conversion of biomass into chemicals over metal catalysts[J]. Chemical Reviews, 2014, 114(3): 1827-1870.
8	TEMPELMAN C, JACOBS U, HUT T, et al. Sn exchanged acidic ion exchange resin for the stable and continuous production of 5-HMF from glucose at low temperature[J]. Applied Catalysis A: General, 2019, 588: 117267.
9	SHAHANGI F, NAJAFI CHERMAHINI A, SARAJI M. Dehydration of fructose and glucose to 5-hydroxymethylfurfural over Al-KCC-1 silica[J]. Journal of Energy Chemistry, 2018, 27(3): 769-780.
10	LAM E, LUONG J H T. Carbon materials as catalyst supports and catalysts in the transformation of biomass to fuels and chemicals[J]. ACS Catalysis, 2014, 4(10): 3393-3410.
11	CHHABRA T, BAHUGUNA A, DHANKHAR S S, et al. Sulfonated graphitic carbon nitride as a highly selective and efficient heterogeneous catalyst for the conversion of biomass-derived saccharides to 5-hydroxymethylfurfural in green solvents[J]. Green Chemistry, 2019, 21(21): 6012-6026.
12	YU X, CHU Y Y, ZHANG L, et al. Adjacent acid sites cooperatively catalyze fructose to 5-hydroxymethylfurfural in a new, facile pathway[J]. Journal of Energy Chemistry, 2020, 47: 112-117.
13	CRISCI A J, TUCKER M H, LEE M Y, et al. Acid-functionalized SBA-15-type silica catalysts for carbohydrate dehydration[J]. ACS Catalysis, 2011, 1(7): 719-728.
14	CAO Z, FAN Z X, CHEN Y, et al. Efficient preparation of 5-hydroxymethylfurfural from cellulose in a biphasic system over hafnyl phosphates[J]. Applied Catalysis B: Environmental, 2019, 244: 170-177.
15	DE BRUYN M, FAN J, BUDARIN V L, et al. A new perspective in bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides[J]. Energy & Environmental Science, 2016, 9(8): 2571-2574.
16	赵振宇, 李洪, 李鑫钢, 等. 基于介电性质差异的微波诱导强化蒸馏分离[J]. 化工进展, 2020, 39(6): 2275-2283.
	ZHAO Zhenyu, LI Hong, LI Xingang, et al. Microwave-induced enhancement of distillation separation based on dielectric properties difference[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2275-2283.
17	WANG Q F, HAO J Q, ZHAO Z B. Microwave-assisted conversion of fructose to 5-hydroxymethylfurfural using sulfonated porous carbon derived from biomass[J]. Australian Journal of Chemistry, 2018, 71(1): 24.
18	JIA X C, YU I K M, TSANG D C W, et al. Functionalized zeolite-solvent catalytic systems for microwave-assisted dehydration of fructose to 5-hydroxymethylfurfural[J]. Microporous and Mesoporous Materials, 2019, 284: 43-52.
19	QI X H, WATANABE M, AIDA T M, et al. Selective conversion of D-fructose to 5-hydroxymethylfurfural by ion-exchange resin in acetone/dimethyl sulfoxide solvent mixtures[J]. Industrial & Engineering Chemistry Research, 2008, 47(23): 9234-9239.
20	UMRIGAR V R, CHAKRABORTY M, PARIKH P. Catalytic activity of zeolite Hβ for the preparation of fuels’ additives: its product distribution and scale up calculation for the biofuel formation in a microwave assisted batch reactor[J]. Journal of Environmental Chemical Engineering, 2018, 6(6): 6816-6827.
21	JI T, TU R, MU L W, et al. Structurally tuning microwave absorption of core/shell structured CNT/polyaniline catalysts for energy efficient saccharide-HMF conversion[J]. Applied Catalysis B: Environmental, 2018, 220: 581-588.
22	YU I K M, XIONG X N, TSANG D C W, et al. Graphite oxide- and graphene oxide-supported catalysts for microwave-assisted glucose isomerisation in water[J]. Green Chemistry, 2019, 21(16): 4341-4353.
23	DUTTA S, DE S, PATRA A K, et al. Microwave assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by mesoporous TiO₂ nanoparticles[J]. Applied Catalysis A: General, 2011, 409/410: 133-139.
24	WANG J, QU T, LIANG M S, et al. Microwave assisted rapid conversion of fructose into 5-HMF over solid acid catalysts[J]. RSC Advances, 2015, 5(128): 106053-106060.
25	VASUDEVAN S V, KONG X H, CAO M J, et al. Microwave-assisted liquefaction of carbohydrates for 5-hydroxymethylfurfural using tungstophosphoric acid encapsulated dendritic fibrous mesoporous silica as a catalyst[J]. Science of the Total Environment, 2021, 760: 143379.
26	SANTOS E J, KAXIRAS E. Electric-field dependence of the effective dielectric constant in graphene[J]. Nano Letters, 2013, 13(3): 898-902.
27	翟金鹏, 李鑫钢, 李洪, 等. 微波诱导热解废旧润滑油的研究[J]. 现代化工, 2020, 40(1): 77-80, 85.
	ZHAI Jinpeng, LI Xingang, LI Hong, et al. Microwave induced pyrolysis of waste lubricant oil[J]. Modern Chemical Industry, 2020, 40(1): 77-80, 85.
28	XU H, YIN X, ZHU M, et al. Carbon hollow microspheres with a designable mesoporous shell for high-performance electromagnetic wave absorption[J]. ACS Applied Materials & Interfaces, 2017, 9(7): 6332-6341.
29	CONTESCU A, CONTESCU C, PUTYERA K, et al. Surface acidity of carbons characterized by their continuous pK distribution and Boehm titration[J]. Carbon, 1997, 35(1): 83-94.
30	ZHANG X H, TAN C, MA Y H, et al. BaTiO₃@carbon/silicon carbide/poly(vinylidene fluoride-hexafluoropropylene) three-component nanocomposites with high dielectric constant and high thermal conductivity[J]. Composites Science and Technology, 2018, 162: 180-187.
31	LI X, TUO Y X, LI P, et al. Effects of carbon support on microwave-assisted catalytic dehydrogenation of decalin[J]. Carbon, 2014, 67: 775-783.
32	YANG J F, ZHANG H Y, AO Z F, et al. Hydrothermal carbon enriched with sulfonic and carboxyl groups as an efficient solid acid catalyst for butanolysis of furfuryl alcohol[J]. Catalysis Communications, 2019, 123: 109-113.
33	LIU H H, GU S L, CAO H, et al. A dense packing structure constructed by flake and spherical graphite: simultaneously enhanced in-plane and through-plane thermal conductivity of polypropylene/graphite composites[J]. Composites Communications, 2020, 19: 25-29.
34	WU K H, TING T H, WANG G P, et al. Effect of carbon black content on electrical and microwave absorbing properties of polyaniline/carbon black nanocomposites[J]. Polymer Degradation and Stability, 2008, 93(2): 483-488.
35	BALBERG I. A comprehensive picture of the electrical phenomena in carbon black-polymer composites[J]. Carbon, 2002, 40(2): 139-143.
36	QI W, HE C, WANG Q, et al. Carbon-based solid acid pretreatment in corncob saccharification: specific xylose production and efficient enzymatic hydrolysis[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(3): 3640-3648.
37	HU L, LI Z, WU Z, et al. Catalytic hydrolysis of microcrystalline and rice straw-derived cellulose over a chlorine-doped magnetic carbonaceous solid acid[J]. Industrial Crops and Products, 2016, 84: 408-417.
38	DURKA T, GERVEN T VAN, STANKIEWICZ A. Microwaves in heterogeneous gas-phase catalysis: experimental and numerical approaches[J]. Chemical Engineering & Technology, 2009, 32(9): 1301-1312.
39	QI X H, WATANABE M, AIDA T M, et al. Catalytic dehydration of fructose into 5-hydroxymethylfurfural by ion-exchange resin in mixed-aqueous system by microwave heating[J]. Green Chemistry, 2008, 10(7): 799.
40	MARULLO S, RIZZO C, D’ANNA F. Activity of a heterogeneous catalyst in deep eutectic solvents: the case of carbohydrate conversion into 5-hydroxymethylfurfural[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(15): 13359-13368.
41	KANG S M, FU J X, ZHANG G. From lignocellulosic biomass to levulinic acid: a review on acid-catalyzed hydrolysis[J]. Renewable and Sustainable Energy Reviews, 2018, 94: 340-362.
42	WHITAKER M R, PARULKAR A, RANADIVE P, et al. Examining acid formation during the selective dehydration of fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide and water[J]. ChemSusChem, 2019, 12(10): 2211-2219.
43	FRAILE J M, GARCÍA-BORDEJÉ E, PIRES E, et al. Catalytic performance and deactivation of sulfonated hydrothermal carbon in the esterification of fatty acids: comparison with sulfonic solids of different nature[J]. Journal of Catalysis, 2015, 324: 107-118.

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

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

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

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

[1]	关浩然, 朱丽娜, 朱凌岳, 苑丹丹, 张雨晴, 王宝辉. 利用不同氢源及氮源电化学合成氨研究进展与挑战[J]. 化工进展, 2022, 41(8): 4098-4110.
[2]	段毅, 邹烨, 周书葵, 杨柳. 过渡金属单原子催化剂活化H₂O₂/PMS/PDS降解有机污染物的研究进展[J]. 化工进展, 2022, 41(8): 4147-4158.
[3]	张鹏, 孟凡会, 杨贵楠, 李忠. 金属氧化物在OX-ZEO催化剂中催化CO _x 加氢制低碳烯烃研究进展[J]. 化工进展, 2022, 41(8): 4159-4172.
[4]	马静, 马子然, 林德海, 马少丹, 王宝冬. 活化液助溶剂对再生脱硝催化剂性能的影响[J]. 化工进展, 2022, 41(8): 4173-4180.
[5]	常耀萍, 官修帅, 郑谦, 靳山彪, 张长明, 张小超. 水热法制备3D花球状Bi₂SiO₅及其光催化油酸酯化反应[J]. 化工进展, 2022, 41(8): 4181-4191.
[6]	潘杰, 王明新, 高生旺, 夏训峰, 韩雪. 氮硫掺杂生物炭/过一硫酸盐体系降解水中磺胺异唑[J]. 化工进展, 2022, 41(8): 4204-4212.
[7]	张嘉琪, 林丽娜, 高文桂, 祝星. CeO₂的形貌对CuO/CeO₂催化剂CO₂加氢制甲醇性能的影响[J]. 化工进展, 2022, 41(8): 4213-4223.
[8]	周佳丽, 马子然, 赵俊平, 马静, 赵春林, 李歌, 王红妍, 王宝冬. 杂多酸改性V-Mo/Ti-W催化剂的宽温SCR脱硝性能[J]. 化工进展, 2022, 41(7): 3615-3623.
[9]	杨超, 矫庆泽, 冯彩虹, 赵芸. 废旧轮胎催化裂解研究进展[J]. 化工进展, 2022, 41(7): 3877-3889.
[10]	龙红明, 丁龙, 钱立新, 春铁军, 张洪亮, 余正伟. 烧结烟气中NO _x 和二英的减排现状及发展趋势[J]. 化工进展, 2022, 41(7): 3865-3876.
[11]	郑敏, 徐垒, 陈晨, 徐忠宁, 付明来. 稀硝酸催化还原工艺中Pd/AC制备条件优化[J]. 化工进展, 2022, 41(7): 3938-3946.
[12]	曾军建, 赵基钢. 乙炔氢氯化金基无汞催化剂的研究进展[J]. 化工进展, 2022, 41(7): 3589-3596.
[13]	杨希刚, 陈国庆, 黄林滨, 古世军, 李昌松, 张勇, 金保昇. 尿素法SNCR对大型电站煤粉锅炉运行影响的工业试验[J]. 化工进展, 2022, 41(7): 3573-3581.
[14]	赵愉生, 崔瑞利, 牛贵峰, 赵元生, 程涛, 何盛宝, 宋俊男, 张霖宙. 俄罗斯渣油加氢处理技术开发与工业应用[J]. 化工进展, 2022, 41(7): 3582-3588.
[15]	李玉峰, 王绍庆, 张安东, 毕冬梅, 李志合, 高亮, 万震. 催化型多孔陶瓷球制备及催化玉米秸秆热解[J]. 化工进展, 2022, 41(7): 3597-3607.

微波与碳基催化剂协同促进果糖制5-羟甲基糠醛

Microwave-assisted carbon-based catalysts for fructose dehydration to 5-hydroxymethylfurfural

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 43

相关文章 15

Metrics

本文评价

推荐阅读 0