Hierarchical MnOx/ZSM-5 as Heterogeneous Catalysts in Conversion of Delignified Rice Husk to Levulinic Acid


Yuni Krisyuningsih Krisnandi(1*), Dita Arifa Nurani(2), Anastasia Agnes(3), Ralentri Pertiwi(4), Noer Fadlina Antra(5), Alika Rizki Anggraeni(6), Anya Prilla Azaria(7), Russell Francis Howe(8)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(5) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(6) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(7) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(8) Department of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland United Kingdom
(*) Corresponding Author


Hierarchical ZSM-5 zeolite was synthesized using a double template method using TPAOH and PDDA as templates, while microporous ZSM-5 was also prepared using only TPAOH as a template. The syntheses then were followed by impregnation with Mn(II) c.a. 2 wt.% and calcination at 550 °C to obtain MnOx/ZSM-5 zeolite catalysts. Extensive characterization of the zeolite catalysts was performed using XRD, SEM, AAS, EDX, FTIR and BET measurement. The characterization showed that hierarchical or mainly mesoporous ZSM-5 was successfully synthesized, having added features compared to the microporous counterpart. The catalysts then were used in conversion reaction of delignified rice husk to levulinic acid, a platform chemical. As a comparison, a certain amount of MnCl2.4H2O was used as a homogeneous catalyst in a similar reaction. The product of the reaction was separated and analyzed with HPLC. It showed that 8 h was the optimum condition for the conversion, with hierarchical MnOx/hi_ZSM-5 catalyst gave the highest amount of levulinic acid (%Y of 15.83%), followed by microporous MnOx/mi_ZSM-5 (%Y of 10%). The % yield of levulinic acid using homogeneous Mn(II) catalyst (%Y of 8.86%) gave more charcoal as a product. Meanwhile, the stability of the zeolite catalysts after the reaction has also been investigated, mainly by analyzing the FTIR spectra and EDX data of the used catalysts after separated and calcined at 550 °C. From the analysis, some of the silica and alumina are leached from the framework, as well as the manganese oxide due to acidic condition at the beginning of the reaction. Nevertheless, it can be concluded that the conversion took place as the interaction between the cellulose and either MnOx in zeolites or Mn2+ ions in the solution, with the support of porous ZSM-5 framework. Hierarchical system somehow assists the ZSM-5 structure stays intact.


hierarchical ZSM-5; biomass conversion; levulinic acid; rice husk cellulose; catalyst stability

Full Text:

Full Text PDF


[1] Fukuoka, A., and Dhepe, P.L., 2006, Catalytic conversion of cellulose into sugar alcohols, Angew. Chem., 45 (31), 5161–5163.

[2] Corma, A., Huber, G.W., Sauvanaud, L., and O’Connor, P., 2007, Processing biomass-derived oxygenates in the oil refinery: Catalytic cracking (FCC) reaction pathways and role of catalyst, J. Catal., 247 (2), 307–327.

[3] Wang, L., Zhang, Z., Yin, C., Shan, Z., and Xiao, F.S., 2010, Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers, Microporous Mesoporous Mater., 131 (1-3), 58–67.

[4] Hendriks, A., and Zeeman, G., 2009, Pretreatments to enhance the digestibility of lignocellulosic biomass: a review, Bioresour. Technol., 100 (1), 10–18.

[5] Bozell, J.J., Moens, L., Elliott, D.C., Wang, Y., Neuenscwander, G.G., Fitzpatrick, S.W., Bilski, R.J., and Jarnefeld, J.L., 2000, Production of levulinic acid and use as a platform chemical for derived products, Resour. Conserv. Recycl., 28 (3-4), 227–239.

[6] Sun, Y., and Cheng, J., 2002, Hydrolysis of lignocellulosic materials for ethanol production: A review, Bioresour. Technol., 83 (1), 1–11.

[7] Kobayashi, H., Ohta, H., and Fukuoka, A., 2012, Conversion of lignocellulose into renewable chemicals by heterogeneous catalysis, Catal. Sci. Technol., 2 (5), 869–883.

[8] Dhepe, P.L., and Fukuoka, A., 2008, Cellulose conversion under heterogeneous catalysis, ChemSusChem, 1 (12), 969–975.

[9] Wettstein, S.G., Bond, J.Q., Alonso, D.M., Pham, H.N., Datye, A.K., and Dumesic, J.A., 2012, RuSn bimetallic catalysts for selective hydrogenation of levulinic acid to γ-valerolactone, Appl. Catal., B, 117-118, 321–329.

[10] Pasquale, G., Vázquez, P., Romanelli,G., and Baronetti, G., 2012, Catalytic upgrading of levulinic acid to ethyl levulinate using reusable silica-included Wells-Dawson heteropolyacid as catalyst, Catal. Commun., 18, 115–120.

[11] Rackemann, D.W., and Doherty,W.O.S., 2011, The conversion of lignocellulosics to levulinic acid, Biofuels, Bioprod. Biorefin., 5 (2), 198–214.

[12] Chen, Y., Li, G., Yang, F., and Zhang, S.M., 2011, Mn/ZSM-5 participation in the degradation of cellulose under phosphoric acid media, Polym. Degrad. Stab., 96 (5), 863–869.

[13] Krisnandi, Y.K., Putra, B.A.P., Bahtiar, M., Abdullah, I., and Howe, R.F., 2015, Partial oxidation of methane to methanol over heterogeneous catalyst Co/ZSM-5, Procedia Chem., 14, 508–515.

[14] Dence, C.W. 1992, “The Determination of Lignin” in Methods in Lignin Chemistry, Lin, S.Y., and Dence, C.W., (eds.), Springer-Verlag, Heidelberg, Germany, 33–61.

[15] The ASTM International standard D1104-46, 1978, Method of test for Holocellulose in Wood.

[16] The ASTM International standard D1103-60, 1978, Method of test for Alpha-cellulose in Wood.

[17] Taherzadeh, M.J., and Karimi, K., 2008, Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: A review, Int. J. Mol. Sci., 9 (9), 1621–1651.

[18] Krisnandi, Y.K., Samodro, B.A., Sihombing, R., and Howe, R.F., 2015, Direct synthesis of methanol by partial oxidation of methane with oxygen over cobalt modified mesoporous H-ZSM-5 catalyst, Indones. J. Chem., 15 (3), 263–268.

[19] Treacy, M.M.J., and Higgins, J.B., 2001, Collection of Simulated XRD Powders for Zeolites, 4th rev. ed., Elsevier Science B.V.

[20] Zhou, M., Rownaghi, A.A., and Hedlund, J., 2013, Synthesis of mesoporous ZSM-5 zeolite crystals by conventional hydrothermal treatment, RSC Adv., 3 (36), 15596–15599.

[21] Wang, D., Liu, Z., Wang, H., Xie, Z.,and Tang, Y., 2010, Shape-controlled synthesis of monolithic ZSM-5 zeolite with hierarchical structure and mechanical stability, Microporous Mesoporous Mater.,132 (3), 428–434.

[22] Hassaninejad-Darzi, S.K., 2015, Fabrication of a non-enzymatic Ni(II) loaded ZSM-5 nanozeolite and multi-walled carbon nanotubes paste electrode as a glucose electrochemical sensor, RSC Adv., 5, 105707–105718.

[23] Karge, H.G., Verified Syntheses of Zeolitic Materials, Characterization by IR Spectroscopy, 2nd Revised Edition, http://www.iza-online.org/synthesis/VS_2ndEd/IR_Spectroscopy.htm, accessed on 28 January 2018.

[24] Rohayati, Krisnandi, Y.K., and Sihombing, R., 2017, Synthesis of ZSM-5 zeolite using Bayat natural zeolite as silica and alumina source, AIP Conf. Proc., 1862, 030094.

DOI: https://doi.org/10.22146/ijc.28332

Article Metrics

Abstract views : 1374 | views : 1150

Copyright (c) 2018 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 / 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.