固定化离子液体高效催化废弃食用油合成生物柴油（英文）
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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-SO_3H)MIm][HSO_4])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.
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-SO3 H)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 catalystswere 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.
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-SO3 H)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 catalystswere 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.
引文
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[17]Yan D,Wang G,Gao K,et al.One-pot synthesis of2,5-furandicarboxylic acid from fructose in ionic liquids[J].Industrial and Engineering Chemistry Research,2018,57:1851-1858.
[18]Quental M V,Caban M,Pereira M M,et al.Enhanced extraction of proteins using cholinium-based ionic liquids as phase-forming components of aqueous biphasic systems[J].Biotechnology Journal,2015,10:1457-1466.
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[23]Wu Q,Chen H,Han M,et al.Transesterification of cottonseed oil catalyzed by Br?nsted acidic ionic liquids[J].Industrial and Engineering Chemistry Research,2007,46:7955-7960.
[24]Guo F,Fang Z,Tian X F,et al.One-step production of biodiesel from jatropha oil with high-acid value in ionic liquids[J].Bioresource Technology,2011,102:6469-6472.
[25]Zhang L,Cui Y,Zhang C,et al.Biodiesel production by esterification of oleic acid over Br?nsted acidic ionic liquid supported onto Fe-incorporated SBA-15[J].Industrial and Engineering Chemistry Research,2012,51:16590-16596.
[26]Elsheikh Y A,Man Z,Bustam M A,et al.Br?nsted imidazolium ionic liquids:synthesis and comparison of their catalytic activities as pre-catalyst for biodiesel production through two stage process[J].Energy Conversion and Management,2011,52:804-809.
[27]Zhao H,Yu N,Ding Y,et al.Task-specific basic ionic liquid immobilized on mesoporous silicas:efficient and reusable catalysts for knoevenagel condensation in aqueous media[J].Microporous Mesoporous Material,2010,136:10-17.
[28]Yang Y,Du Z,Ma J,et al.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].Chemical Society Reviews,2013,42:5963-5977.
[30]Dong K,Zhang S.Hydrogen bonds:a structural insight into ionic liquids[J].Chemistry:A European Journal,2012,18:2748-2761.
[31]Shu Q,Gao J,Nawaz Z,et al.Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst[J].Applied Energy,2010,87:2589-2596.
[32]Zhang W,Li M,Wang J,et al.Heterogeneous poly(ionic liquids)catalyst on nanofiber-like palygorskite supports for biodiesel production[J].Applied Clay Science,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].Chemical Engineering and Technology,2018,41:845-852.
[34]Prinsen P,Luque R,González-Arellano C.Zeolite catalyzed palmitic acid esterification[J].Microporous and Mesoporous Materials,2018,262:133-139.
[35]Shu Q,Tang G,Lesmana H,et al.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].Renewable Energy,2018,119:253-261.
[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].Chemical Engineering Journal,2014,250:35-41.
[3]Zou C,Zhao P,Shi L,et al.Biodiesel fuel production from waste cooking oil by the inclusion complex of heteropoly acid with bridged bis-cyclodextrin[J].Bioresource Technology,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 Review,2016,58:871-875.
[5]Farooq M,Ramli A,Subbarao D.Biodiesel production from waste cooking oil using bifunctional heterogeneous solid catalysts[J].Journal of Cleaner Production,2013,59:131-140.
[6]Adewuyi A,Oderinde R A,Rao B V S K,et al.Blighia unijugata and Luffa cylindrica seed oils:renewable sources of energy for sustainable development in rural Africa[J].Bioenergy Research,2012,5:713-718.
[7]Lotero E,Liu Y J,Lopez D E,et al.Synthesis of biodiesel via acid catalysis[J].Industrial and Engineering Chemistry Research,2005,44:5353-5363.
[8]Alca?iz-Monge J,Bakkali B E,Trautwein G,et al.Zirconia-supported tungstophosphoric heteropolyacid as heterogeneous acid catalyst for biodiesel production[J].Applied Catalysis B:Environmental,2018,224:194-203.
[9]Patel A,Brahmkhatri V,Singh N.Biodiesel production by esterification of free fatty acid over sulfated zirconia[J].Renewable Energy,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].Topics in Catalysis,2010,53:805-810.
[11]Mo X,López D E,Suwannakarn K,et al.Activation and deactivation characteristics of sulfonated carbon catalysts[J].Journal of Catalysis,2008,254:332-338.
[12]Dawodu F A,Ayodele O O,Xin J,et al.Effective conversion of non-edible oil with high free fatty acid into biodiesel by sulphonated carbon catalyst[J].Applied Energy,2014,114:819-826.
[13]Dawodu F A,Ayodele O O,Xin J,et al.Application of solid acid catalyst derived from low value biomass for a cheaper biodiesel production[J].Journal of Chemical Technology and Biotechnology,2014,89:1898-1909.
[14]Okamura M,Takagaki A,Toda M,et al.Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon[J].Chemistry of Materials,2006,18:3039-3045.
[15]Wu Q,Wan H,Li H,et al.Bifunctional temperature-sensitive amphiphilic acidic ionic liquids for preparation of biodiesel[J].Catalysis Today,2013,200:74-79.
[16]Yan D,Xin J,Shi C,et al.Base-free conversion of5-hydroxymethylfurfural to 2,5-furandicarboxylic acid in ionic liquids[J].Chemical Engineering Journal,2017,323:473-482.
[17]Yan D,Wang G,Gao K,et al.One-pot synthesis of2,5-furandicarboxylic acid from fructose in ionic liquids[J].Industrial and Engineering Chemistry Research,2018,57:1851-1858.
[18]Quental M V,Caban M,Pereira M M,et al.Enhanced extraction of proteins using cholinium-based ionic liquids as phase-forming components of aqueous biphasic systems[J].Biotechnology Journal,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 Conversion and Management,2013,76:818-827.
[20]Masri A N,Mutalib M I A,Aminuddin N F,et al.Novel SO3H-functionalized dicationic ionic liquids-a comparative study for esterification reaction by ultrasound cavitation and mechanical stirring for biodiesel production[J].Separation and Purification Technology,2018,196:106-114.
[21]Jamil F,Al-Haj L,Al-Muhtaseb A H,et al.Current scenario of catalysts for biodiesel production:a critical review[J].Reviews in Chemical Engineering,2018,34:267-297.
[22]Wang Y Q,Zhao D,Wang L L,et al.Immobilized phosphotungstic acid based ionic liquid:application for heterogeneous esterification of palmitic acid[J].Fuel,2018,216:364-370.
[23]Wu Q,Chen H,Han M,et al.Transesterification of cottonseed oil catalyzed by Br?nsted acidic ionic liquids[J].Industrial and Engineering Chemistry Research,2007,46:7955-7960.
[24]Guo F,Fang Z,Tian X F,et al.One-step production of biodiesel from jatropha oil with high-acid value in ionic liquids[J].Bioresource Technology,2011,102:6469-6472.
[25]Zhang L,Cui Y,Zhang C,et al.Biodiesel production by esterification of oleic acid over Br?nsted acidic ionic liquid supported onto Fe-incorporated SBA-15[J].Industrial and Engineering Chemistry Research,2012,51:16590-16596.
[26]Elsheikh Y A,Man Z,Bustam M A,et al.Br?nsted imidazolium ionic liquids:synthesis and comparison of their catalytic activities as pre-catalyst for biodiesel production through two stage process[J].Energy Conversion and Management,2011,52:804-809.
[27]Zhao H,Yu N,Ding Y,et al.Task-specific basic ionic liquid immobilized on mesoporous silicas:efficient and reusable catalysts for knoevenagel condensation in aqueous media[J].Microporous Mesoporous Material,2010,136:10-17.
[28]Yang Y,Du Z,Ma J,et al.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].Chemical Society Reviews,2013,42:5963-5977.
[30]Dong K,Zhang S.Hydrogen bonds:a structural insight into ionic liquids[J].Chemistry:A European Journal,2012,18:2748-2761.
[31]Shu Q,Gao J,Nawaz Z,et al.Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst[J].Applied Energy,2010,87:2589-2596.
[32]Zhang W,Li M,Wang J,et al.Heterogeneous poly(ionic liquids)catalyst on nanofiber-like palygorskite supports for biodiesel production[J].Applied Clay Science,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].Chemical Engineering and Technology,2018,41:845-852.
[34]Prinsen P,Luque R,González-Arellano C.Zeolite catalyzed palmitic acid esterification[J].Microporous and Mesoporous Materials,2018,262:133-139.
[35]Shu Q,Tang G,Lesmana H,et al.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].Renewable Energy,2018,119:253-261.