固定化离子液体高效催化废弃食用油合成生物柴油

doi:10.12034/j.issn.1009-606X.20180165

过程工程学报 ›› 2018, Vol. 18 ›› Issue (S1): 129-137.DOI: 10.12034/j.issn.1009-606X.20180165

固定化离子液体高效催化废弃食用油合成生物柴油

晏冬霞^1,2,3，石春艳²，吕兴梅^2,3，辛加余^2*，王公应^1*

1. 中国科学院成都有机化学研究所催化与环境工程研究中心，四川成都 610041 2. 中国科学院过程工程研究所离子液体清洁过程北京市重点实验室，北京 100190 3. 中国科学院大学化工学院，北京 100049

收稿日期:2018-05-08 修回日期:2018-06-19 出版日期:2018-11-22 发布日期:2018-11-19
通讯作者: 晏冬霞 dxyan@ipe.ac.cn
基金资助:
国家自然科学基金;国家自然科学基金;四川省“千人计划”顶尖创新团队

Efficient conversion of waste cooking oil into biodiesel catalyzed by immobilized ionic liquid

Dongxia YAN^1,2,3, Chunyan SHI², Xingmei LÜ^2,3, Jiayu XIN^2*, Gongying WANG^1*

1. Catalytic and Environmental Engineering Research Center, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041, China 2. Beijing Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100090, China 3. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-05-08 Revised:2018-06-19 Online:2018-11-22 Published:2018-11-19

摘要/Abstract

摘要： 采用溶胶?凝胶技术和浸渍法制备了固定化1-(4-丁基磺酸)-3-甲基咪唑硫酸氢盐([(n-Bu-SO3H)MIm][HSO4])离子液体(IL)，得到了一种适用于游离脂肪酸和甲醇酯化反应的不溶性IL催化体系，对合成的催化剂进行了表征，并对其活性进行了系统评价. 结果表明，离子液体成功负载于载体上，该固定化Br?nsted性离子液体在油酸和甲醇酯化反应中具有非常好的催化活性，在最佳反应条件下，油酸的转化率高达98.4%. 该催化剂用于催化高游离脂肪酸含量的废弃食用油酯化时，经后续碱催化酯交换反应，可获得收率高达94.7%的生物柴油.

关键词: 生物柴油, 废弃食用油, 离子液体, 溶胶-凝胶技术, 浸渍法

Abstract: Ionic liquids possess excellent catalytic activities for various chemical reactions including esterification reaction, but the difficulty in phase separation is a major barrier. An immobilized ionic liquid (IL), 1-(4-butylsulfonic)-3-methylimidazolium hydrosulfate [(n-Bu-SO3H)MIm][HSO4], based on sol?gel technique and wetness impregnation method was developed in order to obtain an insoluble IL catalytic system suitable for the esterification of free fatty acids and methanol. The synthesized catalysts were characterized by various techniques and the catalytic properties were fully evaluated. The results demonstrated that the ionic liquid was successfully incorporated into the support. This immobilized Br?nsted ionic liquid catalysts displayed relatively high catalytic activity in esterification of oleic acid and methanol. Under the optimum reaction conditions, the conversion of oleic acid reached to 98.4%. The catalyst was also applied to catalyze the esterification of real waste cooking oil having high free fatty acid and followed by alkyli-catalyzed transesterification, a biodiesel yield of 94.7% was achieved.

Key words: biodiesel, waste cooking oil, ionic liquid, sol-gel technique, wetness impregnation method

晏冬霞石春艳吕兴梅辛加余王公应. 固定化离子液体高效催化废弃食用油合成生物柴油[J]. 过程工程学报, 2018, 18(S1): 129-137.

Dongxia YAN Chunyan SHI Xingmei Lü Jiayu XIN Gongying WANG. Efficient conversion of waste cooking oil into biodiesel catalyzed by immobilized ionic liquid[J]. Chin. J. Process Eng., 2018, 18(S1): 129-137.

参考文献

[1] Ma F, Hanna M A. Biodiesel Production: a Review [J]. Bioresour. Technol., 1999, 70: 1-15.
[2] Vafaeezadeh M, Hashemi M M. Efficient Fatty Acid Esterification Using Silica Supported Br?nsted Acidic Ionic Liquid Catalyst: Experimental Study and DFT Modeling [J]. Chem. Eng. J., 2014, 250: 35-41.
[3] Zou C, Zhao P, Shi L, Huang S, Luo P. Biodiesel Fuel Production from Waste Cooking Oil by the Inclusion Complex of Heteropoly Acid with Bridged Bis-Cyclodextrin [J]. Bioresour. Technol., 2013, 146: 785-788.
[4] Cao Y, Zhou H, Li J. Preparation of a Supported Acidic Ionic Liquid on Silica-Gel and its Application to the Synthesis of Biodiesel from Waste Cooking Oil [J]. Renewable Sustainable Energy Rev., 2016, 58: 871-875.
[5] Farooq M, Ramli A, Subbarao D. Biodiesel Production from Waste Cooking Oil Using Bifunctional Heterogeneous Solid Catalysts [J]. J. Cleaner Prod., 2013, 59: 131-140.
[6] Adewuyi A, Oderinde R A, Rao B V S K, Prasad R B N, Anjaneyulu B. Blighia Unijugata and Luffa Cylindrica Seed Oils: Renewable Sources of Energy for Sustainable Development in Rural Africa [J]. BioEnergy Res., 2012, 5: 713-718.
[7] Lotero E, Liu Y J, Lopez D E, Suwannakarn K, Bruce D A, Goodwin J G. Synthesis of Biodiesel via Acid Catalysis [J]. Ind. Eng. Chem. Res., 2005, 44: 5353-5363.
[8] Alca?iz-Monge J, Bakkali B E, Trautwein G, Reinoso S. Zirconia-Supported Tungstophosphoric Heteropolyacid as Heterogeneous Acid Catalyst for Biodiesel Production [J]. Appl. Catal. B: Environ., 2018, 224: 194-203.
[9] Patel A, Brahmkhatri V, Singh N. Biodiesel Production by Esterification of Free Fatty Acid over Sulfated Zirconia [J]. Renew. Energ., 2013, 51: 227-233.
[10] Hara M. Biodiesel Production by Amorphous Carbon Bearing SO3H, COOH and Phenolic OH Groups, a Solid Br?nsted Acid Catalyst [J]. Top. Catal., 2010, 53: 805-810.
[11] Mo X, López D E, Suwannakarn K, Liu Y, Lotero E, Goodwin Jr J G, Lu C. Activation and Deactivation Characteristics of Sulfonated Carbon Catalysts [J]. J. Catal., 2008, 254: 332-338.
[12] Dawodu F A, Ayodele O O, Xin J, Zhang S, Yan D. Effective Conversion of non-Edible Oil with High Free Fatty Acid into Biodiesel by Sulphonated Carbon Catalyst [J]. Appl. Energy, 2014, 114: 819-826.
[13] Dawodu F A, Ayodele O O, Xin J, Zhang S. Application of Solid Acid Catalyst Derived from Low Value Biomass for a Cheaper Biodiesel Production [J]. J. Chem. Technol. Biotechnol., 2014, 89: 1898-1909.
[14] Okamura M, Takagaki A, Toda M, Kondo J N, Domen K, Tatsumi T, Hara M, Hayashi S. Acid-Catalyzed Reactions on Flexible Polycyclic Aromatic Carbon in Amorphous Carbon [J]. Chem. Mater., 2006, 18: 3039-3045.
[15] Wu Q, Wan H, Li H, Song H, Chu T. Bifunctional Temperature-Sensitive Amphiphilic Acidic Ionic Liquids for Preparation of Biodiesel [J]. Catal. Today, 2013, 200: 74-79.
[16] Yan D, Xin J, Shi C, Lu X, Ni L, Wang G, Zhang S. Base-Free Conversion of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid in Ionic Liquids [J]. Chem. Eng. J., 2017, 323: 473-482.
[17] Yan D, Wang G, Gao K, Lu X, Xin J, Zhang S. One-Pot Synthesis of 2,5-Furandicarboxylic Acid from Fructose in Ionic Liquids [J]. Ind. Eng. Chem. Res., 2018, 57: 1851-1858.
[18] Quental M V, Caban M, Pereira M M, Stepnowski P, Coutinho J A P, Freire M G. Enhanced Extraction of Proteins Using Cholinium-Based Ionic Liquids as Phase-Forming Components of Aqueous Biphasic Systems [J]. Biotechnol. J., 2015, 10: 1457-1466.
[19] Mohammad Fauzi A H, Saidina Amin N A. Optimization of Oleic Acid Esterification Catalyzed by Ionic Liquid for Green Biodiesel Synthesis [J]. Energy Convers. Manage., 2013, 76: 818-827.
[20] Masri A N, Mutalib M I A, Aminuddin N F, Lévêque J M. Novel SO3H-Functionalized Dicationic Ionic Liquids-a Comparative Study for Esterification Reaction by Ultrasound Cavitation and Mechanical Stirring for Biodiesel Production [J]. Sep. Purif. Technol., 2018, 196: 106-114.
[21] Jamil F, Al-Haj L, Al-Muhtaseb A H, Al-Hinai M A, Baawain M, Rashid U, Ahmad M N M. Current Scenario of Catalysts for Biodiesel Production: a Critical Review [J]. Rev. Chem. Eng., 2018, 34: 267-297.
[22] Wang Y Q, Zhao D, Wang L L, Wang X Q, Li L J, Xing Z P, Ji N, Liu S J, Ding H. Immobilized Phosphotungstic Acid Based Ionic Liquid: Application for Heterogeneous Esterification of Palmitic Acid. Fuel, 2018, 216: 364-370.
[23] Wu Q, Chen H, Han M, Wang D, Wang J. Transesterification of Cottonseed Oil Catalyzed by Br?nsted Acidic Ionic Liquids [J]. Ind. Eng. Chem. Res., 2007, 46: 7955-7960.
[24] Guo F, Fang Z, Tian X-F, Long Y-D, Jiang L-Q. One-Step Production of Biodiesel from Jatropha Oil with High-Acid Value in Ionic Liquids [J]. Bioresour. Technol., 2011, 102: 6469-6472.
[25] Zhang L, Cui Y, Zhang C, Wang L, Wan H, Guan G. Biodiesel Production by Esterification of Oleic Acid over Br?nsted Acidic Ionic Liquid Supported onto Fe-Incorporated SBA-15 [J]. Ind. Eng. Chem. Res., 2012, 51: 16590-16596.
[26] Elsheikh Y A, Man Z, Bustam M A, Yusup S, Wilfred C D. Br?nsted Imidazolium Ionic Liquids: Synthesis and Comparison of Their Catalytic Activities as Pre-Catalyst for Biodiesel Production through Two Stage Process [J]. Energy Convers. Manage., 2011, 52: 804-809.
[27] Zhao H, Yu N, Ding Y, Tan R, Liu C, Yin D, Qiu H, Yin D. Task-Specific Basic Ionic Liquid Immobilized on Mesoporous Silicas: Efficient and Reusable Catalysts for Knoevenagel Condensation in Aqueous Media [J]. Microporous Mesoporous Mater., 2010, 136: 10-17.
[28] Yang Y, Du Z, Ma J, Lu F, Zhang J, Xu J. Biphasic Catalytic Conversion of Fructose by Continuous Hydrogenation of HMF over a Hydrophobic Ruthenium Catalyst [J]. ChemSuschem, 2014, 7: 1352-1356.
[29] Maton C, De Vos N, Stevens C V. Ionic Liquid Thermal Stabilities: Decomposition Mechanisms and Analysis Tools [J]. Chem. Soc. Rev., 2013, 42: 5963-5977.
[30] Dong K, Zhang S. Hydrogen Bonds: a Structural Insight into Ionic Liquids [J]. Chem. Eur. J., 2012, 18: 2748-2761.
[31] Shu Q, Gao J, Nawaz Z, Liao Y, Wang D, Wang J. Synthesis of Biodiesel from Waste Vegetable Oil with Large Amounts of Free Fatty Acids Using a Carbon-Based Solid Acid Catalyst [J]. Appl. Energy, 2010, 87: 2589-2596.
[32] Zhang W, Li M, Wang J, Zhao Y, Zhou S, Xing W. Heterogeneous Poly(Ionic Liquids) Catalyst on Nanofiber-Like Palygorskite Supports for Biodiesel Production [J]. Appl. Clay. Sci., 2017, 146: 167-175.
[33] Senoymak Tarakc? M I, Ilgen O. Esterification of Oleic Acid with Methanol Using Zr(SO4)2 as a Heterogeneous Catalyst [J]. Chem. Eng. Technol., 2018, 41: 845-852.
[34] Prinsen P, Luque R, González-Arellano C. Zeolite Catalyzed Palmitic Acid Esterification [J]. Microporous Mesoporous Mater., 2018, 262: 133-139.
[35] Shu Q, Tang G, Lesmana H, Zou L, Xiong D. Preparation, Characterization and Application of a Novel Solid Br?nsted Acid Catalyst SO42/La3+/C for Biodiesel Production via Esterification of Oleic Acid and Methanol [J]. Renew. Energ., 2018, 119: 253-261.

固定化离子液体高效催化废弃食用油合成生物柴油

Efficient conversion of waste cooking oil into biodiesel catalyzed by immobilized ionic liquid

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