混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯

doi:10.11949/j.issn.0438-1157.20151018

化工学报 ›› 2015, Vol. 66 ›› Issue (9): 3490-3495.DOI: 10.11949/j.issn.0438-1157.20151018

• 催化、动力学与反应器 • 上一篇下一篇

混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯

张阳阳, 罗璇, 庄绪丽, 仝新利

1 天津理工大学化学化工学院, 天津 300384;
2 天津出入境检验检疫局, 天津 300201

收稿日期:2015-06-29 修回日期:2015-07-06 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 仝新利
基金资助:
国家自然科学基金项目(21336008)。

Catalytic and selective transformation of glucose to methyl levulinate with mixed acids as catalysts

ZHANG Yangyang, LUO Xuan, ZHUANG Xuli, TONG Xinli

1 College of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China;
2 Tianjin Entry-Exit Inspection and Quarantine Bureau, Tianjin 300201, China

Received:2015-06-29 Revised:2015-07-06 Online:2015-09-05 Published:2015-09-05
Supported by:
supported by the National Natural Science Foundation of China (21366008).

摘要/Abstract

摘要：

将生物质原料直接转化制备乙酰丙酸甲酯(MLE)具有经济价值高、对环境友好和可持续性强等优点。详细研究了Lewis酸(Sn-β分子筛)、Brønsted酸(对甲苯磺酸,PTSA)及混合酸(Sn-β/PTSA)在葡萄糖直接转化合成乙酰丙酸甲酯中的催化效果,取得了较高的产物收率。首先,将各种分子筛和PTSA组合成催化体系并将其应用于葡萄糖醇解合成MLE的反应过程,发现Sn-β分子筛与PTSA的混合体系效果最佳(其中,Sn-β分子筛是借助简单的研磨法制备),产物MLE的收率可达68.3%左右。进而,对分子筛催化剂进行了XRD、FT-IR和TG-DTG等表征;由实验结果可知,Sn-β分子筛的主要作用在于将葡萄糖异构生成果糖,而PTSA的催化作用是加速醇解过程;最后,针对催化剂组分的比例、反应时间和反应温度进行了优化,得到了最佳反应条件。

关键词: 葡萄糖, 催化, 醇解, 混合酸, 乙酰丙酸甲酯

Abstract:

The efficient synthesis of methyl levulinate (MLE) from biomass feedstock using catalytic process is high economic, environment-friendly and sustainable in chemical industry. Herein, the catalytic performance of Lewis acid, Brøsted acid and mixed acid on the conversion of glucose to MLE is investigated in detail, and a satisfactory product yield is obtained. First, the different molecular sieves are combined with p-toluenesulfonic acid (PTSA) and employed as the catalysts for the direct transformation of glucose to MLE, in which the combination of Sn-β molecular sieve (being synthesized through a simple grinding method) and PTSA is the most efficient. The highest yield of MLE is about 68.3%. Furthermore, the catalyst is characterized by XRD, FT-IR and TG-DTG techniques. It is found that Sn-β can mediate the isomerization of glucose to fructose and PTSA mainly promote the alcoholysis reaction based on the experimental results and corresponding phenomena in the reaction. At last, the effects of Sn-β/PTSA ratio, reaction time and reaction temperature are studied, and the optimized conditions are obtained.

Key words: glucose, catalysis, alcoholysis, mixed-acid, methyl levulinate

中图分类号:

O643.3

张阳阳, 罗璇, 庄绪丽, 仝新利. 混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯[J]. 化工学报, 2015, 66(9): 3490-3495.

ZHANG Yangyang, LUO Xuan, ZHUANG Xuli, TONG Xinli. Catalytic and selective transformation of glucose to methyl levulinate with mixed acids as catalysts[J]. CIESC Journal, 2015, 66(9): 3490-3495.

参考文献 20

[1]	Balat M, Balat H. Progress in biodiesel processing [J]. Appl. Energy, 2010, 87: 1815-1835.
[2]	Naik S N, Goud V V, Rout P K, Dalai A K. Production of first and second generation biofuels: a comprehensive review [J]. Sust. Renew. Energy Rev., 2010, 14: 578-597.
[3]	Govindaswamy S, Vane L M. Multi-stage continuous culture fermentation of glucose-xylose mixtures to fuel ethanol using genetically engineered Saccharomyces cerevisiae 424A [J].Bioresour. Technol., 2010, 101: 1277-1284.
[4]	Su Fang, Ma Ling, Song Daiyu, Zhang Xianghuan, Guo Yihang. Design of a highly ordered mesoporous H3PW12O40/ ZrO2-Si(Ph)Si hybrid catalyst for methyl levulinate synthesis [J]. Green Chem., 2013, 15: 885-890.
[5]	Zhang J, Wu S, Li B, Zhang H. Advances in the catalytic production of valuable levulinic acid derivatives [J]. ChemCatChem, 2012, 4: 1230-1237.
[6]	Geilen F M A, Engendahl B, Harwardt A, Marquardt W, Klankermayer J, Leitner W. Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system [J]. Angew. Chem., Int. Ed., 2010, 49: 5510-5514.
[7]	Grote A F V, Tollens B. Untersuchungen über Kohlenhydrate(Ⅰ): Ueber die bei Einwirkung von Schwefelsäure auf Zucker entstehende Säure (levulinsäure) [J]. Justus Liebigs Ann. Chem., 1875, 175(1/2): 181-204.
[8]	Tominaga K, Mori A, Fukushima Y, Shimada S, Sato K. Mixed-acid systems for the catalytic synthesis of methyl levulinate from cellulose [J]. Green Chem., 2011, 13: 810-812.
[9]	Wu X, Fu J, Lu X. One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol [J]. Carbohydr. Res., 2012, 358: 37-39.
[10]	Fernandes D R, Rocha A S, Mai E F, Mota C J A, Silva V T. Levulinic acid esterification with ethanol to ethyl levulinate production over solid acid catalysts [J]. Appl. Catal. A, 2012, 425/426: 199-204.
[11]	Zhou L, Zou H, Nan J, Wu L, Yang X, Su Y, Lu T, Xu J. Conversion of carbohydrate biomass to methyl levulinate with Al2(SO4)3 as a simple, cheap and efficient catalyst [J]. Catal. Commun., 2014, 50: 13-16.
[12]	Mascal M, Nikitin E B. High-yield conversion of plant biomass into the key value-added feedstocks 5-(hydroxymethyl) furfural, levulinic acid, and levulinic esters via 5-(chloromethyl)furfural [J]. Green Chem., 2010, 12: 370-373.
[13]	Kean J R, Graham A E. Indium(Ⅲ) triflate promoted synthesis of alkyl levulinates from furyl alcohols and furyl aldehydes [J]. Catal. Commun., 2015, 59: 175-179.
[14]	Nevesa P, Lima S, Pillinger M, Rocha S M, Rocha J, Valente A A. Conversion of furfuryl alcohol to ethyl levulinate using porous aluminosilicate acid catalysts [J]. Catal. Today, 2013, 218/219: 76-84.
[15]	McKenzie B F. Levulinic acid [J]. Org. Synth., 1929, 9: 50-51.
[16]	Wu X, Fu J, Lu X. One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol [J]. Catal. Rev., 2012, 358: 37-39.
[17]	Peng L, Lin L, Li H. Extremely low sulfuric acid catalyst system for synthesis of methyl levulinate from glucose [J]. Ind. Crops. Prod., 2012, 40:136-144.
[18]	Peng L, Lin L, Li H, Yang Q. Conversion of carbohydrates biomass into levulinate esters using heterogeneous catalysts [J]. Appl. Energy, 2011,88: 4590-4596.
[19]	Njagi E C, Genuino H C, Kuo C H, Dharmarathna S, Gudz A, Suib S L. High-yield selective conversion of carbohydrates to methyl levulinate using mesoporous sulfated titania-based catalysts [J]. Micropor. Mesopor. Mat., 2015, 202: 68-72.
[20]	Chang C, Xu G, Zhu W, Bai J, Fang S. One-pot production of a liquid biofuel candidate-ethyl levulinate from glucose and furfural residues using a combination of extremely low sulfuric acid and zeolite USY [J]. Fuel, 2015, 140: 365-370.

混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯

Catalytic and selective transformation of glucose to methyl levulinate with mixed acids as catalysts

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[3]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[4]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[5]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[6]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[7]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[8]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[9]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[10]	陈雅鑫, 袁航, 刘冠章, 毛磊, 杨纯, 张瑞芳, 张光亚. 蛋白质纳米笼介导的酶自固定化研究进展[J]. 化工学报, 2023, 74(7): 2773-2782.
[11]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.
[12]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[13]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[14]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[15]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.