The Effects of Acid Concentration, Temperature, and Time on the Acid Hydrolysis of Mango (Mangifera Indica) Seed Husk to Produce 5-HMF

Abstract:

The rising demand for fossil-derived feedstocks for plastics production poses a critical sustainability challenge. 5-Hydroxymethylfurfural (5-HMF) has emerged as a key platform chemical and a promising precursor to 2,5-furandicarboxylic acid (FDCA), which is used in the production of bio-based plastics. This study investigated the effects of acid concentration (1% and 5% w/w H₂SO₄), temperature (120°C, 140°C, and 160°C), and time (10–90 minutes) on the acid hydrolysis of mango seed husk for 5-HMF production. Results show that increasing acid concentration, reaction time, and temperature positively influence 5-HMF yields, with a maximum concentration of 0.00166 mmol/100 mL obtained under 5% acid at 140°C for 50 minutes. Kinetic and thermodynamic data of 5-HMF production and decomposition were also determined, providing insights into optimizing process conditions for efficient conversion of lignocellulosic biomass into this critical precursor for bio-based plastics.

• Periodical: Applied Mechanics and Materials (Volume 930)
• Pages: 31-55
• DOI: https://doi.org/10.4028/p-y2BLvW
• Online since: February 2026
• Authors: Ian Dominic F. Tabañag*, Janzzen Cruda, Kent Andrei S. Lu, Ritzel Marie B. Sapa
• Keywords: 5-Hydroxymethylfurfural, Acid Hydrolysis, Furfural, Glucose, Mango Seed Husk

References

[1] B. Kunwar, H. N. Cheng, S. R. Chandrashekaran, and B. K. Sharma, "Plastics to fuel: a review," Renew. Sustain. Energy Rev., vol. 54, p.421–428, 2016.

DOI: 10.1016/j.rser.2015.10.015

[2] K. C. Badgujar and B. M. Bhanage, "Dedicated and Waste Feedstocks for Biorefinery : An Approach to Develop a Sustainable Society," in Waste Biorefinery, Elsevier B.V., 2018, p.3–38.

DOI: 10.1016/b978-0-444-63992-9.00001-x

[3] J. C. Serrano-Ruiz, R. Luque, and A. Sepúlveda-Escribano, "Transformations of biomass-derived platform molecules: From high added-value chemicals to fuels via aqueous-phase processing," Chem. Soc. Rev., vol. 40, no. 11, p.5266–5281, 2011.

DOI: 10.1039/c1cs15131b

[4] R. Rinaldi and F. Schüth, "Acid hydrolysis of cellulose as the entry point into biorefinery schemes," ChemSusChem, vol. 2, no. 12, p.1096–1107, 2009.

DOI: 10.1002/cssc.200900188

[5] H. Chen, Lignocellulose biorefinery feedstock engineering. 2015.

[6] S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, and S. Royer, "How Catalysts and Experimental Conditions Determine the Selective Hydroconversion of Furfural and 5-Hydroxymethylfurfural," Chem. Rev., vol. 118, no. 22, p.11023–11117, 2018.

DOI: 10.1021/acs.chemrev.8b00134

[7] M. Sajid, X. Zhao, and D. Liu, "Production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): Recent progress focusing on the chemical-catalytic routes," Green Chem., vol. 20, no. 24, p.5427–5453, 2018.

DOI: 10.1039/c8gc02680g

[8] H. Rabemanolontsoa and S. Saka, "Various pretreatments of lignocellulosics," Bioresour. Technol., vol. 199, p.83–91, 2016.

DOI: 10.1016/j.biortech.2015.08.029

[9] J. Tang, X. Guo, L. Zhu, and C. Hu, "A Mechanistic Study of Glucose-to-Fructose Isomerization in Water Catalyzed by [ Al ( OH ) 2 ( aq )] +," ACS Catal., p.1–25, 2015.

DOI: 10.1021/acscatal.5b01237

[10] S. Yin, Y. Pan, and Z. Tan, "Hydrothermal conversion of cellulose to 5-hydroxymethyl furfural," Int. J. Green Energy, vol. 8, no. 2, p.234–247, 2011.

DOI: 10.1080/15435075.2010.548888

[11] A. Herbst and C. Janiak, "Selective glucose conversion to 5-hydroxymethylfurfural (5-HMF) instead of levulinic acid with MIL-101Cr MOF-derivatives," New J. Chem., vol. 40, no. 9, p.7958–7967, 2016.

DOI: 10.1039/c6nj01399f

[12] A. K. Chandel, S. S. da Silva, and O. V. Singh, "Detoxification of Lignocellulose Hydrolysates: Biochemical and Metabolic Engineering Toward White Biotechnology," Bioenergy Res., vol. 6, no. 1, p.388–401, 2013.

DOI: 10.1007/s12155-012-9241-z

[13] Y. H. Jung and K. H. Kim, Acidic Pretreatment. Elsevier B.V., 2015.

[14] S. Sasmal and K. Mohanty, "Pretreatment of Lignocellulosic Biomass Toward Biofuel Production," no. November, p.33–60, 2018.

[15] N. K. Mekala, R. Potumarthi, R. R. Baadhe, and V. K. Gupta, Current Bioenergy Researches: Strengths and Future Challenges. Elsevier, 2014.

DOI: 10.1016/b978-0-444-59561-4.00001-2

[16] M. J. Antal, W. S. L. Mok, and G. N. Richards, "Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from d-fructose and sucrose," Carbohydr. Res., vol. 199, no. 1, p.91–109, 1990.

DOI: 10.1016/0008-6215(90)84096-d

[17] F. Menegazzo, E. Ghedini, and M. Signoretto, "5-Hydroxymethylfurfural (HMF) production from real biomasses," Molecules, vol. 23, no. 9, p.1–18, 2018.

DOI: 10.3390/molecules23092201

[18] S. Cheng and S. Zhu, "Lignocellulosic feedstock biorefinery-the future of the chemical and energy industry," BioResources, vol. 4, no. 2, p.456–457, 2009.

DOI: 10.15376/biores.4.2.456-457

[19] A. Shahbazi and B. Zhang, "Dilute and concentrated acid hydrolysis of lignocellulosic biomass," Bioalcohol Prod. Biochem. Convers. Lignocellul. Biomass, p.143–158, 2010.

DOI: 10.1533/9781845699611.2.143

[20] L. A. B. Cortez and R. Quintero-Ramirez, "Hydrolysis of Lignocellulosic Biomass," Sugarcane bioethanol — R&D Product. Sustain., p.717–732, 2014.

DOI: 10.5151/blucheroa-sugarcane-sugarcanebioethanol_60

[21] A. Verardi, I. De, E. Ricca, and V. Calabr, "Hydrolysis of Lignocellulosic Biomass: Current Status of Processes and Technologies and Future Perspectives," Bioethanol, 2012.

DOI: 10.5772/23987

[22] A. Mukherjee, M. J. Dumont, and V. Raghavan, "Review: Sustainable production of hydroxymethylfurfural and levulinic acid: Challenges and opportunities," Biomass and Bioenergy, vol. 72, p.143–183, 2015.

DOI: 10.1016/j.biombioe.2014.11.007

[23] A. T. W. M. Hendriks and G. Zeeman, "Pretreatments to enhance the digestibility of lignocellulosic biomass," Bioresour. Technol., vol. 100, no. 1, p.10–18, 2009.

DOI: 10.1016/j.biortech.2008.05.027

[24] X. Song, M. Zhang, K. Zhang, Z. J. Pei, and D. Wang, "Effects of screen size on biochemical conversion of big bluestem biomass for biofuel production," Adv. Mater. Sci. Eng., vol. 2015, 2015.

DOI: 10.1155/2015/947350

[25] I. P. Hernández, J. A. Pérez-Pimienta, S. Messina, and C. E. Saldaña Durán, "Dilute sulfuric acid hydrolysis of tropical region biomass," J. Renew. Sustain. Energy, vol. 4, no. 2, 2012.

DOI: 10.1063/1.3663878

[26] R. M. Briones, P. A. S. Turingan, and M. A. Rakotoarisoa, Fao Commodity and Trade Policy Market Structure and Distribution of Benefits From Agricultural Exports : the Case of the Philippine Mango, no. 42. 2013.

[27] L. A. Andrade, M. A. S. Barrozo, and L. G. M. Vieira, "Thermo-chemical behavior and product formation during pyrolysis of mango seed shell," Ind. Crops Prod., vol. 85, p.174–180, 2016.

DOI: 10.1016/j.indcrop.2016.03.004

[28] S. H. Duque, C. A. Cardona, and J. Moncada, "Techno-economic and environmental analysis of ethanol production from 10 agroindustrial residues in Colombia," Energy and Fuels, vol. 29, no. 2, p.775–783, 2015.

DOI: 10.1021/ef5019274

[29] B. C. Saha, L. B. Iten, M. A. Cotta, and Y. V. Wu, "Dilute acid pretreatment, enzymatic saccharification and fermentation of wheat straw to ethanol," Process Biochem., vol. 40, no. 12, p.3693–3700, 2005.

DOI: 10.1016/j.procbio.2005.04.006

[30] H. William, O. F. B., G. Stephane, S. Bernard, F. Elisabete, and C. Alain, "Fiberboards Based on Sugarcane Bagasse Lignin and Fibers," Macromol. Mater. Eng., vol. 291, no. 7, p.829–839, 2006.

[31] E. V. Anoop, V. Ajayghosh, J. M. Nijil, and C. M. Jijeesh, "Evaluation of pulp wood quality of selected tropical pines raised in the high ranges of Idukki district, Kerala," J. Trop. Agric., vol. 52, no. 1, p.59–66, 2014.

[32] B. Z. Tizazu and V. S. Moholkar, "Kinetic and thermodynamic analysis of dilute acid hydrolysis of sugarcane bagasse," Bioresour. Technol., vol. 250, no. October 2017, p.197–203, 2018.

DOI: 10.1016/j.biortech.2017.11.032

[33] G. Jackson et al., "Dilute mixed-acid pretreatment of sugarcane bagasse for ethanol production," Biomass and Bioenergy, vol. 35, no. 1, p.663–670, 2010.

DOI: 10.1016/j.biombioe.2010.10.018

[34] K. Rajan and D. J. Carrier, "Effect of dilute acid pretreatment conditions and washing on the production of inhibitors and on recovery of sugars during wheat straw enzymatic hydrolysis," Biomass and Bioenergy, vol. 62, p.222–227, 2014.

DOI: 10.1016/j.biombioe.2014.01.013

[35] E. Guerra-Rodríguez, O. M. Portilla-Rivera, L. Jarquín-Enríquez, J. A. Ramírez, and M. Vázquez, "Acid hydrolysis of wheat straw: A kinetic study," Biomass and Bioenergy, vol. 36, p.346–355, 2012.

DOI: 10.1016/j.biombioe.2011.11.005

[36] Y. López, A. García, K. Karimi, M. J. Taherzadeh, and C. Martín, "Chemical characterisation and dilute-acid hydrolysis of rice hulls from an Artisan Mill," BioResources, vol. 5, no. 4, p.2268–2277, 2010.

DOI: 10.15376/biores.5.4.2268-2277

[37] R. R. Gonzales, P. Sivagurunathan, and S. Kim, "Effect of severity on dilute acid pretreatment of lignocellulosic biomass and the following hydrogen fermentation," Int. J. Hydrogen Energy, vol. 41, no. 46, p.21678–21684, 2016.

DOI: 10.1016/j.ijhydene.2016.06.198

[38] J. B. Sluiter, R. O. Ruiz, C. J. Scarlata, A. D. Sluiter, and D. W. Templeton, "Compositional analysis of lignocellulosic feedstocks. 1. Review and description of methods," J. Agric. Food Chem., vol. 58, no. 16, p.9043–9053, 2010.

DOI: 10.1021/jf1008023

[39] W. G. Trindade, W. Hoareau, J. D. Megiatto, I. A. T. Razera, A. Castellan, and E. Frollini, "Thermoset phenolic matrices reinforced with unmodified and surface-grafted furfuryl alcohol sugar cane bagasse and curaua fibers: Properties of fibers and composites," Biomacromolecules, vol. 6, no. 5, p.2485–2496, 2005.

DOI: 10.1021/bm058006+

[40] M. Dubois, K. A. Gilles, J. K. Hamilton, P. A. Rebers, and F. Smith, "Calorimetric Method for Determination of Sugars and Related Substances," Microb. Cell Fact., vol. 8, p.59, 2009.

[41] A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter, and D. Templeton, "Determination of structural carbohydrates and lignin in biomass," 2012.

[42] R. J. A. Chato, C. C. R. Cuevas, J. S. N. Tangpuz, L. K. Cabatingan, A. W. Go, and Y.-H. Ju, "Dilute acid hydrolysis as a method of producing sugar-rich hydrolysates and lipid-dense cake residues from copra cake," J. Environ. Chem. Eng., vol. 6, no. 5, p.5693–5705, 2018.

DOI: 10.1016/j.jece.2018.08.072

[43] I. N. Ahmed, S. Sutanto, L. H. Huynh, S. Ismadji, and Y. H. Ju, "Subcritical water and dilute acid pretreatments for bioethanol production from Melaleuca leucadendron shedding bark," Biochem. Eng. J., vol. 78, p.44–52, 2013.

DOI: 10.1016/j.bej.2013.03.008

[44] S. Shi, W. Guan, L. Kang, and Y. Y. Lee, "Reaction kinetic model of dilute acid-catalyzed hemicellulose hydrolysis of corn stover under high-solid conditions," Ind. Eng. Chem. Res., vol. 56, no. 39, p.10990–10997, 2017.

DOI: 10.1021/acs.iecr.7b01768

[45] M. P. Elizalde-González and V. Hernández-Montoya, "Characterization of mango pit as raw material in the preparation of activated carbon for wastewater treatment," Biochem. Eng. J., vol. 36, no. 3, p.230–238, 2007.

DOI: 10.1016/j.bej.2007.02.025

[46] F. A. Ola and S. O. Jekayinfa, "Ref : C0605 Pyrolysis of mango stone shell:effect of heating temperature and residence time on product yields," p.1–8, 2014.

[47] A. A. Rentizelas, Biomass storage. Elsevier Ltd, 2016.

[48] P. Basu, Biomass characteristics. 2018.

[49] E. Małachowska, M. Dubowik, A. Lipkiewicz, K. Przybysz, and P. Przybysz, "Analysis of cellulose pulp characteristics and processing parameters for efficient paper production," Sustain., vol. 12, no. 17, p.1–12, 2020.

DOI: 10.3390/su12177219

[50] K. Thammasouk, D. Tandjo, and M. H. Penner, "Influence of Extractives on the Analysis of Herbaceous Biomass," J. Agric. Food Chem., vol. 45, no. 2, p.437–443, 1997.

DOI: 10.1021/jf960401r

[51] C. Liang, Y. Hu, L. Guo, L. Wu, and W. Zhang, "Kinetic Study of Acid Hydrolysis of Corncobs to Levulinic Acid," BioResources, vol. 12, no. 2, p.4049–4061, 2017.

DOI: 10.15376/biores.12.2.4049-4061

[52] M. T. Maloney, T. W. Chapman, and A. J. Baker, "Dilute Acid Hydrolysis," vol. XXVII, p.355–361, 1985.

[53] G. Swati, S. Haldar, A. Ganguly, and P. K. Chatterjee, "Investigations on the kinetics and thermodynamics of dilute acid hydrolysis of Parthenium hysterophorus L. substrate," Chem. Eng. J., vol. 229, p.111–117, 2013.

DOI: 10.1016/j.cej.2013.05.111

[54] J. N. Chheda, Y. Román-Leshkov, and J. A. Dumesic, "Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides," Green Chem., vol. 9, no. 4, p.342–35, 2007.

DOI: 10.1039/b611568c