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Optimization and kinetics study for the conversion of furfuryl alcohol towards ethyl levulinate using sulfonic acid functionalized catalyst

  • Rahul V. Prajapati , Sanjay Srivastava , Girirajsinh C. Jadeja and Jigisha Parikh EMAIL logo
Published/Copyright: January 8, 2024

Abstract

In the present work, furfuryl alcohol (FAL) alcoholysis towards ethyl levulinate (EL) was studied over a mesoporous SO3H-SBA-15 catalyst. The effect of various operating parameters i.e., temperature, catalyst dose, furfuryl alcohol amount, and time was studied and optimized via robust Response Surface Methodology through central composite rotatable designs (CCRD) method on the conversion of FAL to EL. According to Response Surface Methodology, under optimum reaction conditions viz. temperature 110 °C, catalyst dose 0.42 g, time 3 h, and FAL amount of 1.46 g, maximum EL yield (95 %) was recorded. Further, the effect of reaction parameters on the kinetics of the said reaction was also examined, suggesting the second-order kinetic concerning all operating parameters. Eventually, the reusability of the catalyst is evident in a decrease of almost 40 % yield towards EL in the fourth cycle.


Corresponding author: Jigisha Parikh, Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat-395007, Gujarat, India, E-mail:

  1. Research ethics: Not applicable.

  2. Author contributions: The authors confirm contribution to the paper as follows: Experimental work, analysis and interpretation of results and draft manuscript preparation: Rahul V. Prajapati; draft manuscript preparation, analysis and interpretation of results: Sanjay Srivastava; Concept, Design, Supervision, Manuscript review: Girirajsinh C. Jadeja and Jigisha Parikh. All authors reviewed the results and approved the final version of the manuscript.

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: None declared.

  5. Data availability: Not applicable.

References

[1] G. W. Huber, S. Iborra, and A. Corma, “Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering,” Chem. Rev., vol. 106, no. 9, pp. 4044–4098, 2006, https://doi.org/10.1021/cr068360d.Search in Google Scholar PubMed

[2] J. H. Badia, E. Ramírez, R. Soto, R. Bringué, J. Tejero, and F. Cunill, “Optimization and green metrics analysis of the liquid-phase synthesis of sec-butyl levulinate by esterification of levulinic acid with 1-butene over ion-exchange resins,” Fuel Process. Technol., vol. 220, p. 106893, 2021. https://doi.org/10.1016/j.fuproc.2021.106893.Search in Google Scholar

[3] C. Canon, N. Sanchez, and M. Cobo, “Sustainable production of ethyl levulinate by levulinic acid esterification obtained from Colombian rice straw,” J. Clean. Prod., vol. 377, p. 134276, 2022, https://doi.org/10.1016/j.jclepro.2022.134276.Search in Google Scholar

[4] S. Hansen, A. Mirkouei, and L. A. Diaz, “A comprehensive state-of-technology review for upgrading bio-oil to renewable or blended hydrocarbon fuels,” Renew. Sustain. Energy Rev., vol. 118, p. 109548, 2020. https://doi.org/10.1016/j.rser.2019.109548.Search in Google Scholar

[5] A. Hu, H. Wang, and J. Ding, “Novel sulfonic acid polystyrene microspheres for alcoholysis of furfuryl alcohol to ethyl levulinate,” Catal. Lett., vol. 152, no. 1, pp. 3158–3167, 2022. https://doi.org/10.1007/s10562-021-03881-5.Search in Google Scholar

[6] D. Zhao, et al., “Continuous flow alcoholysis of furfuryl alcohol to alkyl levulinates using zeolites,” ACS Sustain. Chem. Eng., vol. 6, no. 5, pp. 6901–6909, 2018, https://doi.org/10.1021/acssuschemeng.8b00726.Search in Google Scholar

[7] A. T. Adeleye, H. Louis, O. U. Akakuru, I. Joseph, O. C. Enudi, and D. P. Michael, “A review on the conversion of levulinic acid and its esters to various useful chemicals,” AIMS Energy, vol. 7, no. 2, pp. 165–185, 2019, https://doi.org/10.3934/energy.2019.2.165.Search in Google Scholar

[8] H. Chen, et al., “A review on the pretreatment of lignocellulose for high-value chemicals,” Fuel Process. Technol., vol. 160, pp. 196–206, 2017, https://doi.org/10.1016/j.fuproc.2016.12.007.Search in Google Scholar

[9] Y. Wang, D. Zhao, K. S. Triantafyllidis, W. Ouyang, R. Luque, and C. Len, “Microwave-assisted catalytic upgrading of bio-based furfuryl alcohol to alkyl levulinate over commercial non-metal activated carbon,” Mol. Catal., vol. 480, p. 110630, 2020, https://doi.org/10.1016/j.mcat.2019.110630.Search in Google Scholar

[10] D. R. Jones, et al., “The conversion of levulinic acid into γ-valerolactone using Cu–ZrO2 catalysts,” Catal. Sci. Technol., vol. 6, no. 15, pp. 6022–6030, 2016, https://doi.org/10.1039/c6cy00382f.Search in Google Scholar

[11] H. Joshi, B. R. Moser, J. Toler, W. F. Smith, and T. Walker, “Ethyl levulinate: A potential bio-based diluent for biodiesel which improves cold flow properties,” Biomass Bioenergy, vol. 35, no. 7, pp. 3262–3266, 2011, https://doi.org/10.1016/j.biombioe.2011.04.020.Search in Google Scholar

[12] A. S. Piskun, J. E. de Haan, E. Wilbers, H. H. van de Bovenkamp, Z. Tang, and H. J. Heeres, “Hydrogenation of levulinic acid to γ-valerolactone in water using millimeter sized supported Ru catalysts in a packed bed reactor,” ACS Sustain. Chem. Eng., vol. 4, no. 6, pp. 2939–2950, 2016, https://doi.org/10.1021/acssuschemeng.5b00774.Search in Google Scholar

[13] A. M. Raspolli Galletti, C. Antonetti, V. De Luise, D. Licursi, and N. Nassi, “Levulinic acid production from waste biomass,” BioResources, vol. 7, no. 2, pp. 1824–1835, 2012, https://doi.org/10.15376/biores.7.2.1824-1835.Search in Google Scholar

[14] C. Chang, P. Cen, and X. Ma, “Levulinic acid production from wheat straw,” Bioresour. Technol., vol. 98, no. 7, pp. 1448–1453, 2007, https://doi.org/10.1016/j.biortech.2006.03.031.Search in Google Scholar PubMed

[15] L. Mao, L. Zhang, N. Gao, and A. Li, “FeCl3 and acetic acid co-catalyzed hydrolysis of corncob for improving furfural production and lignin removal from residue,” Bioresour. Technol., vol. 123, pp. 324–331, 2012, https://doi.org/10.1016/j.biortech.2012.07.058.Search in Google Scholar PubMed

[16] G. M. González Maldonado, R. S. Assary, J. A. Dumesic, and L. A. Curtiss, “Acid-catalyzed conversion of furfuryl alcohol to ethyl levulinate in liquid ethanol,” Energy Environ. Sci., vol. 5, no. 10, p. 8990, 2012, https://doi.org/10.1039/c2ee22486k.Search in Google Scholar PubMed PubMed Central

[17] J.-P. Lange, W. D. van de Graaf, and R. J. Haan, “Conversion of furfuryl alcohol into ethyl levulinate using solid acid catalysts,” ChemSusChem, vol. 2, no. 5, pp. 437–441, 2009, https://doi.org/10.1002/cssc.200800216.Search in Google Scholar PubMed

[18] P. Neves, S. Lima, M. Pillinger, S. M. Rocha, J. Rocha, and A. A. Valente, “Conversion of furfuryl alcohol to ethyl levulinate using porous aluminosilicate acid catalysts,” Catal. Today, vols. 218–219, pp. 76–84, 2013, https://doi.org/10.1016/j.cattod.2013.04.035.Search in Google Scholar

[19] S. Srivastava, N. Solanki, P. Mohanty, K. A. Shah, J. K. Parikh, and A. K. Dalai, “Optimization and Kinetic studies on hydrogenation of furfural to furfuryl alcohol over SBA-15 supported bimetallic copper–cobalt catalyst,” Catal. Lett., vol. 145, no. 3, pp. 816–823, 2015, https://doi.org/10.1007/s10562-015-1488-5.Search in Google Scholar

[20] F. Zhou, et al., “Efficient cyclohexyl acrylate production by direct addition of acrylic acid and cyclohexene over SBA-15-SO3H,” J. Porous Mater., vol. 21, no. 2, pp. 149–155, 2014, https://doi.org/10.1007/s10934-013-9759-2.Search in Google Scholar

[21] Yogita, B. S. Rao, C. Subrahmanyam, and N. Lingaiah, “The selective conversion of furfuryl alcohol to ethyl levulinate over Zr-modified tungstophosphoric acid supported on β-zeolites,” New J. Chem., vol. 45, no. 6, pp. 3224–3233, 2021, https://doi.org/10.1039/d0nj05296e.Search in Google Scholar

[22] S. An, D. Song, B. Lu, X. Yang, and Y.-H. Guo, “Morphology tailoring of sulfonic acid functionalized organosilica nanohybrids for the synthesis of biomass-derived alkyl levulinates,” Chem. A Eur. J., vol. 21, no. 30, pp. 10786–10798, 2015, https://doi.org/10.1002/chem.201501219.Search in Google Scholar PubMed

[23] M. Przypis, K. Matuszek, A. Chrobok, M. Swadźba-Kwaśny, and D. Gillner, “Inexpensive and tuneable protic ionic liquids based on sulfuric acid for the biphasic synthesis of alkyl levulinates,” J. Mol. Liq., vol. 308, p. 113166, 2020, https://doi.org/10.1016/j.molliq.2020.113166.Search in Google Scholar

[24] W. Zhu, C. Chang, C. Ma, and F. Du, “Kinetics of glucose ethanolysis catalyzed by extremely low sulfuric acid in ethanol medium,” Chinese J. Chem. Eng., vol. 22, no. 2, pp. 238–242, 2014, https://doi.org/10.1016/s1004-9541(14)60049-5.Search in Google Scholar

[25] K. Y. Nandiwale, A. M. Pande, and V. V. Bokade, “One step synthesis of ethyl levulinate biofuel by ethanolysis of renewable furfuryl alcohol over hierarchical zeolite catalyst,” RSC Adv., vol. 5, no. 97, pp. 79224–79231, 2015, https://doi.org/10.1039/c5ra13520f.Search in Google Scholar

[26] P. Neves, et al., “Mesoporous zirconia-based mixed oxides as versatile acid catalysts for producing bio-additives from furfuryl alcohol and glycerol,” Appl. Catal. A: Gen., vol. 487, pp. 148–157, 2014, https://doi.org/10.1016/j.apcata.2014.08.042.Search in Google Scholar

[27] R. Prajapati, S. Srivastava, G. C. Jadeja, and J. Parikh, “A novel SBA-15/H-ZSM-5 composite catalyst for conversion of furfuryl alcohol to ethyl levulinate,” Waste Biomass Valoriz., vol. 14, no. 2, pp. 609–618, 2022. https://doi.org/10.1007/s12649-022-01707-y.Search in Google Scholar

[28] R. Prajapati, S. Srivastava, G. Jadeja, and J. Parikh, “Functionalized mesostructured silicas towards efficient conversion of furfuryl alcohol to ethyl levulinate,” Iran. J. Catal., vol. 13, no. 3, pp. 271–284, 2023.Search in Google Scholar

[29] X. Kong, X. Zhang, C. Han, C. Li, L. Yu, and J. Liu, “Ethanolysis of biomass based furfuryl alcohol to ethyl levulinate over Fe modified USY catalyst,” Mol. Catal., vol. 443, pp. 186–192, 2017, https://doi.org/10.1016/j.mcat.2017.10.011.Search in Google Scholar

[30] X.-F. Liu, et al., “Efficient conversion of furfuryl alcohol to ethyl levulinate with sulfonic acid-functionalized MIL-101(Cr),” RSC Adv., vol. 6, no. 93, pp. 90232–90238, 2016, https://doi.org/10.1039/c6ra19116a.Search in Google Scholar

[31] M. B. Kokare, R. V, and C. S. Mathpati, “Response surface optimization, kinetic study and process design of n-butyl levulinate synthesis,” Chem. Eng. Res. Des., vol. 137, pp. 577–588, 2018, https://doi.org/10.1016/j.cherd.2018.07.036.Search in Google Scholar

[32] R. H. Myers, D. C. Montgomery, G. G. Vining, C. M. Borror, and S. M. Kowalski, “Response surface methodology: a retrospective and literature survey,” J. Qual. Technol., vol. 36, no. 1, pp. 53–77, 2004, https://doi.org/10.1080/00224065.2004.11980252.Search in Google Scholar

[33] S. P. Saha and D. Mazumdar, “Optimization of process parameter for alpha-amylase produced by Bacillus cereus amy3 using one factor at a time (OFAT) and central composite rotatable (CCRD) design based response surface methodology (RSM),” Biocatal. Agric. Biotechnol., vol. 19, p. 101168, 2019, https://doi.org/10.1016/j.bcab.2019.101168.Search in Google Scholar

[34] Y. Zhang, X. Wang, T. Hou, H. Liu, L. Han, and W. Xiao, “Efficient microwave-assisted production of biofuel ethyl levulinate from corn stover in ethanol medium,” J. Energy Chem., vol. 27, no. 3, pp. 890–897, 2018, https://doi.org/10.1016/j.jechem.2017.06.010.Search in Google Scholar

[35] Z. Zhang, H. Yuan, Y. Wang, and Y. Ke, “Preparation and characterisation of ordered mesoporous SO42−/Al2O3 and its catalytic activity in the conversion of furfuryl alcohol to ethyl levulinate,” J. Solid State Chem., vol. 280, p. 120991, 2019, https://doi.org/10.1016/j.jssc.2019.120991.Search in Google Scholar

[36] E. Siva Sankar, K. Saidulu Reddy, Y. Jyothi, B. David Raju, and K. S. Rama Rao, “Alcoholysis of furfuryl alcohol into n-butyl levulinate over SBA-16 supported heteropoly acid catalyst,” Catal. Lett., vol. 147, no. 11, pp. 2807–2816, 2017, https://doi.org/10.1007/s10562-017-2155-9.Search in Google Scholar

[37] M. S. Tiwari, A. B. Gawade, and G. D. Yadav, “Magnetically separable sulfated zirconia as highly active acidic catalysts for selective synthesis of ethyl levulinate from furfuryl alcohol,” Green Chem., vol. 19, no. 4, pp. 963–976, 2017, https://doi.org/10.1039/c6gc02466a.Search in Google Scholar


Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/ijcre-2023-0133).


Received: 2023-07-05
Accepted: 2023-12-20
Published Online: 2024-01-08

© 2023 Walter de Gruyter GmbH, Berlin/Boston

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