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Esterification of Levulinic Acid into n-Butyl levulinate Catalyzed by Sulfonic Acid-Functionalized Lignin-Montmorillonite Complex

  • Received Date: 2020-04-15
    Accepted Date: 2020-06-12
    Fund Project:

    The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Nos. 21606082, 21776068 and 21975070), Hunan Provincial Natural Science Foundation of China (No. 2018JJ3334), and China Postdoctoral Science Foundation (No. 2019M662787).

  • In this study, sulfonic acid-functionalized lignin-montmorillonite complex (LMT-SO3H) was prepared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid (LA) into n-butyl levulinate (BL). An intermediate pseudo-butyl levulinate (p-BL) was determined by distilled water treatment and nuclear magnetic resonance (NMR) analysis, and a possible mechanism for the esterification of LA is proposed. The effects of various process parameters were studied and the results showed that the LMT-SO3H catalyst had the excellent catalytic performance for esterification of the LA. Under optimum reaction conditions, the yield of BL was 99.3% and the conversion of LA was 99.8%. The LMT-SO3H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage. Furthermore, esterification of the LA with various alcohols over the LMT-SO3H was further investigated.
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  • [1]

    Badgujar, K.C., Badgujar, V.C., Bhanage, B.M., 2020. A review on catalytic synthesis of energy rich fuel additive levulinate compounds from biomass derived levulinic acid. Fuel Process. Technol. 197, 106213.
    [2]

    Bonacci, S., Nardi, M., Costanzo, P., de Nino, A., Gioia, M.L.D., Oliverio, M., Procopio, A, 2019. Montmorillonite K10-catalyzed solvent-free conversion of furfural into cyclopentenones. Catalysts 9, 301.
    [3]

    Cao, J.J., Ma, M.W., Liu, J.C., Yang, Y.Q., Liu, H., Xu, X.L., Huang, J.H., Yue, H.J., Tian, G., Feng, S.H., 2019. Highly effective transformation of carbohydrates to 5-Hydroxymethylfurfural with Al-montmorillonite as catalyst. Appl. Catal. A:Gen. 571, 96-101.
    [4]

    Najafi Chermahini, A., Nazeri, M, 2017. Esterification of the levulinic acid with n-butyl and isobutyl alcohols over aluminum-containing MCM-41. Fuel Process. Technol. 167, 442-450.
    [5]

    Christensen, E., Williams, A., Paul, S., Burton, S., McCormick, R.L., 2011. Properties and performance of levulinate esters as diesel blend components. Energy Fuels 25, 5422-5428.
    [6]

    Ciptonugroho, W., Al-Shaal, M.G., Mensah, J.B., Palkovits, R., 2016. One pot synthesis of WOx/mesoporous-ZrO2 catalysts for the production of levulinic-acid esters. J. Catal. 340, 17-29.
    [7]

    Cirujano, F.G., Corma, A., Llabrés i Xamena, F.X., 2015. Conversion of levulinic acid into chemicals:synthesis of biomass derived levulinate esters over Zr-containing MOFs. Chem. Eng. Sci. 124, 52-60.
    [8]

    Das, J., Parida, K.M., 2007. Heteropoly acid intercalated Zn/Al HTlc as efficient catalyst for esterification of acetic acid using n-butanol. J. Mol. Catal. A:Chem. 264, 248-254.
    [9]

    Demolis, A., Essayem, N., Rataboul, F, 2014. Synthesis and applications of alkyl levulinates. ACS Sustain. Chem. Eng. 2, 1338-1352.
    [10]

    Dharne, S., Bokade, V.V., 2011. Esterification of levulinic acid to n-butyl levulinate over heteropolyacid supported on acid-treated clay. J. Nat. Gas Chem. 20, 18-24.
    [11]

    Enumula, S.S., Gurram, V.R.B., Chada, R.R., Burri, D.R., Kamaraju, S.R.R., 2017. Clean synthesis of alkyl levulinates from levulinic acid over one pot synthesized WO3-SBA-16 catalyst. J. Mol. Catal. A:Chem. 426, 30-38.
    [12]

    Gao, J., Kong, W.X., Zhou, L.Y., He, Y., Ma, L., Wang, Y., Yin, L.Y., Jiang, Y.J., 2017. Monodisperse core-shell magnetic organosilica nanoflowers with radial wrinkle for lipase immobilization. Chem. Eng. J. 309, 70-79.
    [13]

    Gao, Y., Yue, Q.Y., Gao, B.Y., Sun, Y.Y., Wang, W., Li, Q., Wang, Y., 2013. Preparation of high surface area-activated carbon from lignin of papermaking black liquor by KOH activation for Ni(Ⅱ) adsorption. Chem. Eng. J. 217, 345-353.
    [14]

    Iborra, M., Tejero, J., Fité, C., Ramírez, E., Cunill, F., 2019. Liquid-phase synthesis of butyl levulinate with simultaneous water removal catalyzed by acid Ion exchange resins. J. Ind. Eng. Chem. 78, 222-231.
    [15]

    Kalghatgi, S.G., Bhanage, B.M., 2019. Green syntheses of levulinate esters using ionic liquid 1-Methyl imidazolium hydrogen sulphate[MIM] [HSO4] in solvent free system. J. Mol. Liq. 281, 70-80.
    [16]

    Kang, S.M., Fu, J.X., Zhang, G., 2018. From lignocellulosic biomass to levulinic acid:a review on acid-catalyzed hydrolysis. Renew. Sustain. Energy Rev. 94, 340-362.
    [17]

    Kolvari, E., Koukabi, N., Hosseini, M.M., 2015. Perlite:a cheap natural support for immobilization of sulfonic acid as a heterogeneous solid acid catalyst for the heterocyclic multicomponent reaction. J. Mol. Catal. A:Chem. 397, 68-75.
    [18]

    Maheria, K.C., Kozinski, J., Dalai, A., 2013. Esterification of levulinic acid to n-butyl levulinate over various acidic zeolites. Catal. Lett. 143, 1220-1225.
    [19]

    Manikandan, K., Cheralathan, K.K., 2017. Heteropoly acid supported on silicalite-1 possesing intracrystalline nanovoids prepared using biomass - an efficient and recyclable catalyst for esterification of levulinic acid. Appl. Catal. A:Gen. 547, 237-247.
    [20]

    Marcel, R., Durillon, T., Djakovitch, L., Fache, F., Rataboul, F., 2019. First example of the use of biosourced alkyl levulinates as solvents for synthetic chemistry:application to the heterogeneously catalyzed heck coupling. ChemistrySelect 4, 3329-3333.
    [21]

    Morawala, D., Dalai, A., Maheria, K., 2019. Rice husk mediated synthesis of meso-ZSM-5 and its application in the synthesis of n-butyl levulinate. J. Porous Mater. 26, 677-686.
    [22]

    Morawala, D.H., Dalai, A.K., Maheria, K.C., 2020. Synthesis of n-butyl levulinate using mesoporous zeolite H-BEA catalysts with different catalytic characteristics. Catal. Lett. 150, 1049-1060.
    [23]

    Mukherjee, A., Dumont, M.J., Raghavan, V., 2015. Review:sustainable production of hydroxymethylfurfural and levulinic acid:challenges and opportunities. Biomass Bioenergy 72, 143-183.
    [24]

    Nandiwale, K.Y., Bokade, V.V., 2015. Esterification of renewable levulinic acid to n-butyl levulinate over modified H-ZSM-5. Chem. Eng. Technol. 38, 246-252.
    [25]

    Pachamuthu, M.P., Srinivasan, V.V., Karvembu, R., Luque, R., 2019. Preparation of mesoporous stannosilicates SnTUD-1 and catalytic activity in levulinic acid esterification. Microporous Mesoporous Mater. 287, 159-166.
    [26]

    Pavlovic, J., Popova, M., Mihalyi, R.M., Mazaj, M., Mali, G., Kovač, J., Lazarova, H., Rajic, N., 2019. Catalytic activity of SnO2- and SO4/SnO2-containing clinoptilolite in the esterification of levulinic acid. Microporous Mesoporous Mater. 279, 10-18.
    [27]

    Pileidis, F.D., Titirici, M.M., 2016. Levulinic acid biorefineries:new challenges for efficient utilization of biomass. ChemSusChem 9, 562-582.
    [28]

    Shirini, F., Mamaghani, M., Atghia, S.V., 2011. Sulfonic acid-functionalized ordered nanoporous Na+-montmorillonite (SANM):a novel, efficient and recyclable catalyst for the chemoselective N-Boc protection of amines in solventless media. Catal. Commun. 12, 1088-1094.
    [29]

    Su, F., Wu, Q.Y., Song, D.Y., Zhang, X.H., Wang, M., Guo, Y.H., 2013. Pore morphology-controlled preparation of ZrO2-based hybrid catalysts functionalized by both organosilica moieties and Keggin-type heteropoly acid for the synthesis of levulinate esters. J. Mater. Chem. 1, 13209-13221.
    [30]

    Sun, X.L., Zhao, X.H., Zu, Y.G., Li, W.G., Ge, Y.L., 2014. Preparing, characterizing, and evaluating ammoniated lignin diesel from papermaking black liquor. Energy Fuels 28, 3957-3963.
    [31]

    Tian, Y., Zhang, R.Q., Zhao, W.G., Wen, S., Xiang, Y.P., Liu, X.X., 2020. A new sulfonic acid-functionalized organic polymer catalyst for the synthesis of biomass-derived alkyl levulinates. Catal. Lett. 15, doi:10.1007/s10562-020-03253-5.
    [32]

    Varadwaj, G.B.B., Parida, K., Nyamori, V.O., 2016. Transforming inorganic layered montmorillonite into inorganic-organic hybrid materials for various applications:a brief overview. Inorg. Chem. Front. 3, 1100-1111.
    [33]

    Xu, X.L., Zhang, X.L., Zou, W.J., Yue, H.J., Tian, G., Feng, S.H., 2015. Conversion of carbohydrates to methyl levulinate catalyzed by sulfated montmorillonite. Catal. Commun. 62, 67-70.
    [34]

    Yan, L., Yao, Q., Fu, Y., 2017. Conversion of levulinic acid and alkyl levulinates into biofuels and high-value chemicals. Green Chem. 19, 5527-5547.
    [35]

    Yang, F., Tang, J.J., 2019. Catalytic upgrading of renewable levulinic acid to levulinate esters using perchloric acid decorated nanoporous silica gels. ChemistrySelect 4, 1403-1409.
    [36]

    Yang, J.F., Li, G.Y., Zhang, L.L., Zhang, S.F., 2018. Efficient production of N-butyl levulinate fuel additive from levulinic acid using amorphous carbon enriched with oxygenated groups. Catalysts 8, 14.
    [37]

    Yi, X.L., He, W., Zhang, X.D., Yue, Y.Z., Yang, G.H., Wang, Z.Y., Zhou, M.J., Wang, L.Z., 2017. Graphene-like carbon sheet/Fe3O4 nanocomposites derived from soda papermaking black liquor for high performance lithium Ion batteries. Electrochimica Acta 232, 550-560.
    [38]

    Zhang, H., Li, H., Hu, Y.L., Venkateswara Rao, K.T., Xu, C., Yang, S., 2019. Advances in production of bio-based ester fuels with heterogeneous bifunctional catalysts. Renew. Sustain. Energy Rev. 114, 109296.
    [39]

    Zhang, J., Wu, S., Li, B., Zhang, H., 2012. Advances in the catalytic production of valuable levulinic acid derivatives. ChemCatChem 4, 1230-1237.
    [40]

    Zhou, L.Y., He, Y., Ma, L., Jiang, Y.J., Huang, Z.H., Yin, L.Y., Gao, J., 2018. Conversion of levulinic acid into alkyl levulinates:Using lipase immobilized on meso-molding three-dimensional macroporous organosilica as catalyst. Bioresour. Technol. 247, 568-575.
    [41]

    Zhou, S.L., Liu, X.X., Lai, J.H., Zheng, M., Liu, W.Z., Xu, Q., Yin, D.L., 2019. Covalently linked organo-sulfonic acid modified titanate nanotube hybrid nanostructures for the catalytic esterification of levulinic acid with n-butyl alcohol. Chem. Eng. J. 361, 571-577.
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Esterification of Levulinic Acid into n-Butyl levulinate Catalyzed by Sulfonic Acid-Functionalized Lignin-Montmorillonite Complex

  • National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China
Fund Project:  The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Nos. 21606082, 21776068 and 21975070), Hunan Provincial Natural Science Foundation of China (No. 2018JJ3334), and China Postdoctoral Science Foundation (No. 2019M662787).

Abstract: In this study, sulfonic acid-functionalized lignin-montmorillonite complex (LMT-SO3H) was prepared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid (LA) into n-butyl levulinate (BL). An intermediate pseudo-butyl levulinate (p-BL) was determined by distilled water treatment and nuclear magnetic resonance (NMR) analysis, and a possible mechanism for the esterification of LA is proposed. The effects of various process parameters were studied and the results showed that the LMT-SO3H catalyst had the excellent catalytic performance for esterification of the LA. Under optimum reaction conditions, the yield of BL was 99.3% and the conversion of LA was 99.8%. The LMT-SO3H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage. Furthermore, esterification of the LA with various alcohols over the LMT-SO3H was further investigated.

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