Abstract
An efficient and recyclable catalyst, namely phosphomolybdenum-based sulfonated ionic liquids (ILs) functionalized MIL-100(Fe) metal–organic framework (AIL/HPMo/MIL-100(Fe)), was developed for the production of biodiesel via the transesterification-esterifications of acidic oils. For this goal, the MIL-100(Fe) metal–organic framework (MOF) was initially modified with phosphomolybdic acid (HPMo), and then the acidic ionic liquid (AIL) was immobilized on the prepared HPMo/MIL-100(Fe) composite through ion-exchange of 1-(propyl-3-sulfonate)imidazolium hydrogen sulfate with HPMo. The as-developed AIL/HPMo/MIL-100(Fe) catalyst possessed enhanced surface acidities, endowing the merits of Lewis and Brönsted acids with a heterogeneous microreactor of MOFs and favoring the better catalytic performance. The characterization results corroborated that the polyoxometalate-based ILs were incorporated into the MIL-100(Fe), and the porous structure of the MIL-100(Fe) maintained nearly unchangeable after the synthesis processes. The AIL/HPMo/MIL-100(Fe) catalyst could perform simultaneous transesterification of soybean oil and esterification of free fatty acids (FFAs) with long-term catalytic durability. The conversion of acidic oils using this solid catalyst gave 92.3% oil conversion for the transesterification of soybean oil and full FFA conversion for the esterification of FFAs with the methanol/oil molar ratio of 30:1 at 120 °C, showing potential applications for the production of biodiesel particularly from acidic oil feedstocks.
Graphical Abstract
Synopsis: Phosphomolybdenum-based sulfonated ionic liquids (ILs) functionalized MIL-100(Fe) metal–organic framework composites are fabricated and then utilized as efficient and recyclable catalysts for the production of biodiesel via one-pot transesterification-esterifications of acidic oils.
Similar content being viewed by others
References
Aransiola EF, Ojumu TV, Oyekola OO, Madzimbamuto TF, Ikhuomoregbe DIO (2014) A review of current technology for biodiesel production: state of the art. Biomass Bioenergy 61:276–297. https://doi.org/10.1016/j.biombioe.2013.11.014
Xie W, Huang M (2018) Immobilization of Candida rugosa lipase onto graphene oxide Fe3O4 nanocomposite: characterization and application for biodiesel production. Energy Convers Manag 159:42–53. https://doi.org/10.1016/j.enconman.2018.01.021
Feyzi M, Hassankhani A, Rafiee HR (2013) Preparation and characterization of Cs/Al/Fe3O4 nanocatalysts for biodiesel production. Energy Convers Manag 71:62–68. https://doi.org/10.1016/j.enconman.2013.03.022
Gebremariam SN, Marchetti JM (2018) Techno-economic feasibility of producing biodiesel from acidic oil using sulfuric acid and calcium oxide as catalysts. Energy Convers Manag 171:1712–1720. https://doi.org/10.1016/j.enconman.2018.06.105
Ambat I, Srivastava V, Sillanpää M (2018) Recent advancement in biodiesel production methodologies using various feedstock: a review. Renew Sust Energy Rev 90:356–369. https://doi.org/10.1016/j.rser.2018.03.069
Dhawane SH, Kumar T, Halder G (2018) Recent advancement and prospective of heterogeneous carbonaceous catalysts in chemical and enzymatic transformation of biodiesel. Energy Convers Manag 167:176–202. https://doi.org/10.1016/j.enconman.2018.04.073
Mansir N, Taufiq-Yap YH, Rashid U, Lokman IM (2017) Investigation of heterogeneous solid acid catalyst performance on low grade feedstocks for biodiesel production: a review. Energy Convers Manag 141:171–182. https://doi.org/10.1016/j.enconman.2016.07.037
Lien YS, Hsieh LS, Wu JC (2010) Biodiesel synthesis by simultaneous esterification and transesterification using oleophilic acid catalyst. Ind Eng Chem Res 49:2118–2121. https://doi.org/10.1021/ie901496h
D’Souza R, Vats T, Chattree A, Siril PF (2018) Graphene supported magnetically separable solid acid catalyst for the single step conversion of waste cooking oil to biodiesel. Renew Energy 126:1064–1073. https://doi.org/10.1016/j.renene.2018.04.035
Alcañiz-Monge J, El Bakkali B, Trautwein G, Reinoso S (2018) Zirconia-supported tungstophosphoric heteropolyacid as heterogeneous acid catalyst for biodiesel production. Appl Catal B 224:194–203. https://doi.org/10.1016/j.apcatb.2017.10.066
Chaveanghong S, Smith SM, Smith CB, Luengnaruemitchai A, Boonyuen S (2018) Simultaneous transesterification and esterification of acidic oil feedstocks catalyzed by heterogeneous tungsten loaded bovine bone under mild conditions. Renew Energy 126:156–162. https://doi.org/10.1016/j.renene.2018.03.036
Li Y, Zhang XD, Sun L, Xu M, Zhou WG, Liang XH (2010) Solid superacid catalyzed fatty acid methyl esters production from acid oil. Appl Energy 87:2369–2373. https://doi.org/10.1016/j.apenergy.2010.01.017
Sandouqa A, Al-Hamamre Z, Asfar J (2019) Preparation and performance investigation of a lignin-based solid acid catalyst manufactured from olive cake for biodiesel production. Renew Energy 132:667–682. https://doi.org/10.1016/j.renene.2018.08.029
Huang M, Luo J, Fang Z, Li H (2016) Biodiesel production catalyzed by highly acidic carbonaceous catalysts synthesized via carbonizing lignin in sub-and super-critical ethanol. Appl Catal B 190:103–114. https://doi.org/10.1016/j.apcatb.2016.02.069
Rattanaphra D, Harvey AP, Thanapimmetha A, Srinophakun P (2012) Simultaneous transesterification and esterification for biodiesel production with and without a sulphated zirconia catalyst. Fuel 97:467–475. https://doi.org/10.1016/j.fuel.2012.01.031
Shu Q, Gao J, Nawaz Z, Liao Y, Wang D, Wang J (2010) Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbonbased solid acid catalyst. Appl Energy 87:2589–2596. https://doi.org/10.1016/j.apenergy.2010.03.024
da Conceição LRV, Carneiro LM, Rivaldi JD, de Castro HF (2016) Solid acid as catalyst for biodiesel production via simultaneous esterification and transesterification of macaw palm oil. Ind Crop Prod 89:416–424. https://doi.org/10.1016/j.indcrop.2016.05.044
Chughtai AH, Ahmad N, Younus HA, Laypkov A, Verpoort F (2015) Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem Soc Rev 44:6804–6849. https://doi.org/10.1039/c4cs00395k
Huang YB, Liang J, Wang XS, Cao R (2017) Multifunctional metal-organic framework catalysts: synergistic catalysis and tandem reactions. Chem Soc Rev 46:126–157. https://doi.org/10.1039/c6cs00250a
Cohen SM (2012) Postsynthetic methods for the functionalization of metal-organic frameworks. Chem Rev 112:970–1000. https://doi.org/10.1021/cr200179u
Abednatanzi S, Abbasi A, Masteri-Farahani M (2017) Immobilization of catalytically active polyoxotungstate into ionic liquid-modified MIL-100 (Fe): a recyclable catalyst for selective oxidation of benzyl alcohol. Catal Commun 96:6–10. https://doi.org/10.1016/j.catcom.2017.03.011
Rafiee E, Eavani S (2017) Polyoxometalates as heterogeneous catalysts for organic reactions. Curr Org Chem 21:752–778. https://doi.org/10.2174/1385272821666170126162936
Rafiee E, Eavani S (2016) Heterogenization of heteropoly compounds: a review of their structure and synthesis. RSC Adv 6:46433–46466. https://doi.org/10.1039/c6ra04891a
Zhang F, Jin Y, Shi J, Zhong Y, Zhu W, El-Shall MS (2015) Polyoxometalates confined in the mesoporous cages of metal–organic framework MIL-100(Fe): efficient heterogeneous catalysts for esterification and acetalization reactions. Chem Eng J 269:236–244. https://doi.org/10.1016/j.cej.2015.01.092
Granadeiro CM, Barbosa AD, Silva P, Paz FAA, Saini VK, Pires J et al (2013) Monovacant polyoxometalates incorporated into MIL-101(Cr): novel heterogeneous catalysts for liquid phase oxidation. Appl Catal A 453:316–326. https://doi.org/10.1016/j.apcata.2012.12.039
Hoo PY, Abdullah AZ (2014) Direct synthesis of mesoporous 12-tungstophosphoric acid SBA-15 catalyst for selective esterification of glycerol and lauric acid to monolaurate. Chem Eng J 250:274–287. https://doi.org/10.1016/j.cej.2014.04.016
Ullah Z, Khan AS, Muhammad N, Ullah R, Alqahtani AS, Shah SN et al (2018) A review on ionic liquids as perspective catalysts in transesterification of different feedstock oil into biodiesel. J Mol Liq 266:673–686. https://doi.org/10.1016/j.molliq.2018.06.024
Li J, Guo Z (2017) Structure evolution of synthetic amino acids-derived basic ionic liquids for catalytic production of biodiesel. ACS Sustain Chem Eng 5:1237–1247. https://doi.org/10.1021/acssuschemeng.6b02732
Kraus GA, Guney T (2012) A direct synthesis of 5-alkoxymethylfurfural ethers from fructose via sulfonic acid-functionalized ionic liquids. Green Chem 14:1593–1596. https://doi.org/10.1039/c2gc35175g
Yuan C, Huang Z, Chen J (2012) Basic ionic liquid supported on mesoporous SBA-15: an efficient heterogeneous catalyst for epoxidation of olefins with H2O2 as oxidant. Catal Commun 24:56–60. https://doi.org/10.1016/j.catcom.2012.03.003
Cheng W, Chen X, Sun J, Wang J, Zhang S (2013) SBA-15 supported triazolium-based ionic liquids as highly efficient and recyclable catalysts for fixation of CO2 with epoxides. Catal Today 200:117–124. https://doi.org/10.1016/j.cattod.2012.10.001
Xie W, Wan F (2018) Basic ionic liquid functionalized magnetically responsive Fe3O4@HKUST-1 composites used for biodiesel production. Fuel 220:248–256. https://doi.org/10.1016/j.fuel.2018.02.014
Luo QX, An BW, Ji M, Park SE, Hao C, Li YQ (2015) Metal-organic frameworks HKUST-1 as porous matrix for encapsulation of basic ionic liquid catalyst: effect of chemical behaviour of ionic liquid in solvent. J Porous Mat 22:247–259. https://doi.org/10.1007/s10934-014-9891-7
Huang W, Zhu W, Li H, Shi H, Zhu G, Liu H et al (2010) Heteropolyanion-based ionic liquid for deep desulfurization of fuels in ionic liquids. Ind Eng Chem Res 49:8998–9003. https://doi.org/10.1021/ie100234d
Rafiee E, Eavani S (2014) A new organic–inorganic hybrid ionic liquid polyoxometalate for biodiesel production. J Mol Liq 199:96–101. https://doi.org/10.1016/j.molliq.2014.08.034
Wu J, Gao Y, Zhang W, Tan Y, Tang A, Men Y et al (2015) Deep desulfurization by oxidation using an active ionic liquid-supported Zr metal–organic framework as catalyst. Appl Organomet Chem 29:96–100. https://doi.org/10.1002/aoc.3251
Nobakht N, Faramarzi MA, Shafiee A, Khoobi M, Rafiee E (2018) Polyoxometalate-metal organic framework-lipase: an efficient green catalyst for synthesis of benzyl cinnamate by enzymatic esterification of cinnamic acid. Int J Biol Macromol 113:8–19. https://doi.org/10.1016/j.ijbiomac.2018.02.023
Wu Z, Li Z, Wu G, Wang L, Lu S, Wang L et al (2014) Brønsted acidic ionic liquid modified magnetic nanoparticle: an efficient and green catalyst for biodiesel production. Ind Eng Chem Res 53:3040–3046. https://doi.org/10.1021/ie4040016
Amoozadeh A, Rahmani S (2015) Nano-WO3-supported sulfonic acid: new, efficient and high reusable heterogeneous nano catalyst. J Mol Catal A 396:96–107. https://doi.org/10.1016/j.molcata.2014.09.020
Standards, B. Fat and oil derivatives. Fatty acid methyl esters (FAME). Determination of ester and linolenic acid methyl ester contents, Standards Policy and Strategy Committee, British Standards Institute,2003
Zhao J, Anjali J, Yan Y, Lee JM (2017) Cr-MIL-101-encapsulated Keggin phosphomolybdic acid as a catalyst for the one-pot synthesis of 2,5-diformylfuran from fructose. ChemCatChem 9:1187–1191. https://doi.org/10.1002/cctc.201601546
Karimi Z, Mahjoub AR, Aghdam FD (2009) SBA immobilized phosphomolybdic acid: efficient hybrid mesostructured heterogeneous catalysts. Inorg Chim Acta 362:3725–3730. https://doi.org/10.1016/j.ica.2009.04.029
Han M, Gu Z, Chen C, Wu Z, Que Y, Wang Q et al (2016) Efficient confinement of ionic liquids in MIL-100(Fe) frameworks by the “impregnation-reaction-encapsulation” strategy for biodiesel production. RSC Adv 6:37110–37117. https://doi.org/10.1039/c6ra00579a
Gopinath S, Kumar PV, Kumar PSM, Arafath KY, Sivanesan S, Baskaralingam P (2018) Cs-tungstosilicic acid/Zr-KIT-6 for esterification of oleic acid and transesterification of non-edible oils for green diesel production. Fuel 234:824–835. https://doi.org/10.1016/j.fuel.2018.07.018
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 21776062) and the Key Scientific Projects of Universities in Henan Province of China (Grant No. 19zx002).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Xie, W., Wan, F. Biodiesel Production from Acidic Oils Using Polyoxometalate-Based Sulfonated Ionic Liquids Functionalized Metal–Organic Frameworks. Catal Lett 149, 2916–2929 (2019). https://doi.org/10.1007/s10562-019-02800-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-019-02800-z