Toward Diesel-Range Fuel Properties: Catalytic Upgrading of Waste Cooking Oil Biodiesel over Acid-Activated Bentonite
Abstract
Waste cooking oil (WCO)-derived biodiesel represents a promising renewable fuel because it simultaneously supports waste valorization, reduces dependence on petroleum-derived diesel, and lowers feedstock costs. However, its relatively high viscosity, oxygenated ester structure, and lower energy density compared with conventional diesel can limit its fuel performance. Most existing upgrading strategies address these limitations through catalytic cracking or deoxygenation at temperatures above 250–350 °C, frequently involving pressurized hydrogen and extensive conversion of fatty acid methyl esters (FAME) into hydrocarbon-rich fuels, leaving limited understanding of whether biodiesel properties can instead be improved through low-severity treatment while preserving its FAME-rich character. This study investigated H₂-free mild catalytic upgrading of WCO-derived biodiesel using untreated bentonite and HCl-activated bentonite at catalyst loadings of 0.20, 0.40, 0.60, and 0.80 wt% in a rotary reactor operated at 150 °C for 1 h, followed by density, kinematic viscosity, calorific value, flash point, FTIR, and GC–MS analyses. The treatment caused only negligible variation in density, from 0.842 g/cm³ for the initial biodiesel to 0.843–0.844 g/cm³ after upgrading, indicating that the bulk molecular characteristics of the fuel were largely retained, while the kinematic viscosity decreased substantially from 4.94 cSt to minimum values of 3.54 and 3.55 cSt at 0.20 and 0.40 wt%, respectively. The calorific value increased from 41.46 MJ/kg to a maximum of 42.39 MJ/kg at 0.80 wt%, corresponding to an improvement of approximately 2.24%, while the 0.60 and 0.80 wt% samples exhibited flash points of 57.5 and 56.5 °C, respectively. GC–MS analysis revealed a compositional redistribution from 65.48% FAME and 16.13% aliphatic hydrocarbons in the initial biodiesel to approximately 53.46% FAME and 28.48% aliphatic hydrocarbons at 0.80 wt%; meanwhile, the 0.40 wt% sample showed the formation of approximately 3.80% C12 hydrocarbons, consistent with its lower viscosity and greater volatility. FTIR spectra retained the characteristic ester C=O and long-chain aliphatic bands, supporting limited molecular transformation rather than extensive destruction of the FAME framework. These findings demonstrate that low-temperature, low-catalyst-loading bentonite treatment can selectively redistribute biodiesel components and tune fuel properties without deep conversion, providing a low-severity upgrading pathway that bridges conventional biodiesel processing and high-temperature hydrocarbon-fuel production.
Keywords
Biodiesel; Waste cooking oil; Catalytic upgradingReferences
- [1] N. Ilminnafik, D. H. T. Prasetiyo, Welayaturromadhona, A. M. Kartini, B. Palupi, and Suyitno, “Optimization of biodiesel synthesis process from nyamplung (calophyllum inophyllum) oil using thermal air sparging method,” Mechanical Engineering for Society and Industry, vol. 6, no. 1, May 2026, doi: 10.31603/mesi.15335.
- [2] S. Devasthali, A. Kulkarni, N. Bhatkar, and U. Sankpal, “Metal Oxide Doped Egg Shell-Fly Ash Composite: An Effective Catalyst for Transesterification of Waste Oil,” ECS Transactions, vol. 107, no. 1, pp. 13103–13112, Apr. 2022, doi: 10.1149/10701.13103ecst.
- [3] R. C. Nnamani, P. N. Okwu, B. John, and O. J. Abayeh, “Preliminary Investigation of Transesterified Waste Cooking Oil (WCO) as a Biodiesel,” Journal of Chemical Society of Nigeria, vol. 45, no. 5, 2020, doi: 10.46602/jcsn.v45i5.515.
- [4] A. Kolakoti, M. Setiyo, and B. Waluyo, “Biodiesel Production from Waste Cooking Oil: Characterization, Modeling and Optimization,” Mechanical Engineering for Society and Industry, vol. 1, no. 1, pp. 22–30, Jul. 2021, doi: 10.31603/mesi.5320.
- [5] A. B. Pratama, S. M. Benu, E. P. D. Boangmanalu, S. Siahaan, and H. Ibrahim, “Analisis Laju Korosi Baja Karbon Ringan pada Biopelumas dari Limbah Minyak Goreng,” SINERGI POLMED: Jurnal Ilmiah Teknik Mesin, vol. 6, no. 1, pp. 7–18, Mar. 2025, doi: 10.51510/sinergipolmed.v6i1.1933.
- [6] S. M. Benu, E. P. D. Boangmanalu, A. B. Pratama, and M. A. Pulungan, “Sintesis Pelumas Biodegradable dari Limbah Minyak Goreng Melalui Pendekatan Respon Permukaan,” SINERGI POLMED: Jurnal Ilmiah Teknik Mesin, vol. 6, no. 1, pp. 19–27, Mar. 2025, doi: 10.51510/sinergipolmed.v6i1.1934.
- [7] S. Suherman et al., “A Review of Properties, Engine Performance, Emission Characteristics and Material Compatibility Biodiesel From Waste Cooking Oil (WCO),” Automotive Experiences, vol. 6, no. 3, pp. 624–651, Nov. 2023, doi: 10.31603/ae.10128.
- [8] S. Suherman, M. Muharnif, I. Abdullah, A. S. Silitonga, M. Yusfiani, and W. A. W. Hamzah, “Two Decades of Biodiesel Research from Waste Cooking Oil: A Bibliometric and Literature Review of Heterogeneous Catalysts,” Automotive Experiences, vol. 8, no. 3, pp. 573–598, Dec. 2025, doi: 10.31603/ae.14776.
- [9] D. Darwin, R. A. M. Harahap, A. Pratama, M. Thifa, and M. A. Alwi Fayed, “Enhanced biodiesel production from waste cooking oils catalyzed by sodium hydroxide supported on heterogeneous co-catalyst of bentonite clay,” Research in Agricultural Engineering, vol. 69, no. 3, pp. 124–131, Sep. 2023, doi: 10.17221/70/2022-RAE.
- [10] K. Maqsood and M. Alsaady, “Optimization using response surface methodology for producing biodiesel from waste cooking oil using fishbone catalyst,” Materialwissenschaft und Werkstofftechnik, vol. 53, no. 10, pp. 1242–1248, Oct. 2022, doi: 10.1002/mawe.202200138.
- [11] Y. Zetra et al., “Synthesis of 2-Hidroxyethyl Ester (2-HEE) and 2-Hydroxypropyl Ester (2-HPE) from Castor Oil as Bioadditives to Improve the Cold Flow Characteristic of Biodiesel,” Automotive Experiences, vol. 9, no. 1, May 2026, doi: 10.31603/ae.15860.
- [12] J. Milano et al., “Tribological study on the biodiesel produced from waste cooking oil, waste cooking oil blend with Calophyllum inophyllum and its diesel blends on lubricant oil,” Energy Reports, vol. 8, pp. 1578–1590, Nov. 2022, doi: 10.1016/j.egyr.2021.12.059.
- [13] V. G. Nguyen, M. T. Pham, N. V. L. Le, H. C. Le, T. H. Truong, and D. N. Cao, “A comprehensive review on the use of biodiesel for diesel engines,” International Journal of Renewable Energy Development, vol. 12, no. 4, pp. 720–740, Jul. 2023, doi: 10.14710/ijred.2023.54612.
- [14] E. Demir, S. D. Çalhan, and Ö. Sönmez, “Microwave-assisted biodiesel production from waste cooking oil using deep eutectic solvent catalyst: Kinetic and thermodynamic insights,” Biomass and Bioenergy, vol. 201, p. 108148, Oct. 2025, doi: 10.1016/j.biombioe.2025.108148.
- [15] M. Karthikeyan, S. Sathish, M. R. Soosai, D. Prabu, and D. Venkatesan, “Optimized production of biodiesel from used (waste) cooking oil by utilizing a heterogeneous catalyst, and its studies for sustainable development,” Fuel, vol. 403, p. 136091, Jan. 2026, doi: 10.1016/j.fuel.2025.136091.
- [16] A. Kolakoti, M. Setiyo, and M. L. Rochman, “A Green Heterogeneous Catalyst Production and Characterization for Biodiesel Production using RSM and ANN Approach,” International Journal of Renewable Energy Development, vol. 11, no. 3, pp. 703–712, 2022, doi: 10.14710/ijred.2022.43627.
- [17] S. O. Effiom et al., “Cost, Emission, and Thermo-Physical Determination of Heterogeneous Biodiesel from Palm Kernel Shell Oil: Optimization of Tropical Egg Shell Catalyst,” Indonesian Journal of Science and Technology, vol. 9, no. 1, pp. 1–32, Nov. 2023, doi: 10.17509/ijost.v9i1.64006.
- [18] N. A. A. Rahman, F. Cardenas-Lizana, and A. Sanna, “Lithium–Sodium Fly Ash-Derived Catalyst for the In Situ Partial Deoxygenation of Isochrysis sp. Microalgae Bio-Oil,” Catalysts, vol. 13, no. 7, p. 1122, Jul. 2023, doi: 10.3390/catal13071122.
- [19] T. Maluangnont, P. Praserthdam, and T. Sooknoi, “Catalytic deoxygenation of fatty acids via ketonization and α-carbon scissions over layered alkali titanate catalysts under N 2,” RSC Advances, vol. 12, no. 53, pp. 34293–34302, 2022, doi: 10.1039/D2RA06530D.
- [20] W. He et al., “Synthesis of Chainlike ZSM-5 with a Polyelectrolyte as a Second Template for Oleic Acid and Ethanol Cracking into Light Olefins,” ACS Omega, vol. 7, no. 44, pp. 40520–40531, Nov. 2022, doi: 10.1021/acsomega.2c05763.
- [21] F. P. de Sousa, G. P. dos Reis, and V. M. D. Pasa, “Catalytic pyrolysis of vegetable oils over NbOPO4 for SAF and green diesel production,” Journal of Analytical and Applied Pyrolysis, vol. 177, p. 106314, Jan. 2024, doi: 10.1016/j.jaap.2023.106314.
- [22] F. Shi et al., “Green diesel-like hydrocarbon production by H2-free catalytic deoxygenation of oleic acid via Ni/MgO-Al2O3 catalysts: Effect of the metal loading amount,” Journal of Environmental Chemical Engineering, vol. 11, no. 5, 2023, doi: 10.1016/j.jece.2023.110520.
- [23] Y. Buyang et al., “Dolomite catalyst for fast pyrolysis of waste cooking oil into hydrocarbon fuel,” South African Journal of Chemical Engineering, vol. 45, pp. 60–72, Jul. 2023, doi: 10.1016/j.sajce.2023.04.007.
- [24] B. F. H. de Oliveira, B. M. Viegas, M. Velasquez, and E. N. Macêdo, “Sustainable Valorization of Palm Fatty Acid Distillate into Green Diesel Using Ni–Co Catalysts Supported on Zeolite from Kaolin Waste under Solvent- and Hydrogen-Free Conditions,” ACS Omega, vol. 10, no. 45, pp. 54967–54977, Nov. 2025, doi: 10.1021/acsomega.5c08463.
- [25] R. khan, S. Kaithwas, P. Choudhary, R. Anant, and S. H. Dhawane, “Synergistic thermocatalytic cracking and in-situ hydrogenation of waste cooking oil for co-production of sustainable aviation fuel and clean hydrogen,” International Journal of Hydrogen Energy, vol. 191, p. 152189, Nov. 2025, doi: 10.1016/j.ijhydene.2025.152189.
- [26] K. B. Tan et al., “Catalytic deoxygenation of stearic acid into olefins over Pt catalysts supported on MOF-derived metal oxides,” Catalysis Science & Technology, vol. 14, no. 12, pp. 3436–3447, 2024, doi: 10.1039/D4CY00189C.
- [27] K. R. Rao, R. B. Pace, H. Suarez, E. Santillan-Jimenez, and C. Risko, “Carboxylic Acid Decarbonylation on Nickel: The Critical Role of the Acid Binding Geometry,” ACS Catalysis, vol. 13, no. 13, pp. 9102–9112, Jul. 2023, doi: 10.1021/acscatal.3c01489.
- [28] R. Wei et al., “Hydrodeoxygenation of oleic acid over NiCu bimetallic catalysts supported on Mo-modified niobium phosphate,” New Journal of Chemistry, vol. 49, no. 12, pp. 4849–4859, 2025, doi: 10.1039/D4NJ04885G.
- [29] E. O. Schipanskaya et al., “Catalytic Biomass Transformation to Hydrocarbons under Supercritical Conditions over Nickel Supported on Schungite,” Processes, vol. 12, no. 7, p. 1503, Jul. 2024, doi: 10.3390/pr12071503.
- [30] M. Slezáčková, A. Peller, J. Mikulec, M. Banič, J. Blaško, and E. Hájeková, “Catalytic hydroprocessing of camelina oil/AGO mixtures over NiMoP/γ-Al2O3 catalysts,” Catalysis Today, vol. 423, p. 113953, Nov. 2023, doi: 10.1016/j.cattod.2022.11.014.
- [31] A. I. Tsiotsias et al., “Selective catalytic deoxygenation of palm oil to produce green diesel over Ni catalysts supported on ZrO2 and CeO2–ZrO2: Experimental and process simulation modelling studies,” Renewable Energy, vol. 206, pp. 582–596, Apr. 2023, doi: 10.1016/j.renene.2023.02.038.
- [32] M. Lalitpattarakit et al., “Effects of operating parameters on green diesel production via deoxygenation of triglycerides,” Chemical Engineering Journal, vol. 508, 2025, doi: 10.1016/j.cej.2025.161125.
- [33] K. Wu et al., “In-situ preparation of MnFeCoNiCu/C for the sustainable co-production of bio-jet fuel and green diesel under solvent-free and low hydrogen pressure conditions,” Energy Conversion and Management, vol. 318, p. 118875, Oct. 2024, doi: 10.1016/j.enconman.2024.118875.
- [34] S. Palanisamy and K. Kandasamy, “Direct Hydrogenation and Hydrotreating of Neat Vegetal Oil into Renewable Diesel Using Alumina Binder with Zeolite,” Revista de Chimie, vol. 71, no. 9, pp. 98–112, Sep. 2020, doi: 10.37358/RC.20.9.8321.
- [35] C. Jia, C. Zhang, S. Xie, W. Zhang, Z. Wang, and H. Lin, “One-pot production of jet fuels from fatty acids and vegetable oils in biphasic tandem catalytic process,” Fuel, vol. 302, p. 121060, Oct. 2021, doi: 10.1016/j.fuel.2021.121060.
- [36] X. Wang et al., “Catalytic pyrolysis of microalgal lipids to liquid biofuels: Metal oxide doped catalysts with hierarchically porous structure and their performance,” Renewable Energy, vol. 212, pp. 887–896, Aug. 2023, doi: 10.1016/j.renene.2023.05.119.
- [37] H. Saad, T. Turki, M. Mezni, S. Sellimi, A. Garbout, and E. Srasra, “Acid-activated clay-polyphenols hybrids from pomegranate peel waste: Towards multifunctional optical and antioxidant materials,” Chemical Physics Impact, vol. 12, p. 101000, Jun. 2026, doi: 10.1016/j.chphi.2026.101000.
- [38] W. Wahyudi, M. Nadjib, and A. Faizi, “Physical property analysis of biodiesel from nyamplung and used cooking oil: density, viscosity, calorific value, and flash point,” Jurnal Polimesin, vol. 22, no. 2, p. 206, Apr. 2024, doi: 10.30811/jpl.v22i2.4565.
- [39] S. Thanikodi, S. Rathinasamy, J. Giri, A. K. Jagadeesan, and E. Makki, “Biodiesel Production from Food Industrial Waste of Soybean Oil using a Lipase-nanoparticle Bio-composite Catalyst,” Automotive Experiences, vol. 7, no. 2, pp. 189–206, Aug. 2024, doi: 10.31603/ae.10707.
- [40] B. O. Yusuf, S. A. Ganiyu, A. M. P. Peedikakkal, and S. A. Oladepo, “ZnO/Cu-BTC metal-organic frameworks as a heterogeneous catalyst for efficient transformation of waste cooking oil into biodiesel,” Biomass and Bioenergy, vol. 204, p. 108381, Jan. 2026, doi: 10.1016/j.biombioe.2025.108381.
- [41] K. Yadav, S. Almansour, L. M. Alkwai, A. Yadav, and F. Ranjbar, “Reliable models for density in waste cooking oil biodiesel-alcohol mixtures using advanced learning techniques,” Industrial Crops and Products, vol. 234, p. 121602, Oct. 2025, doi: 10.1016/j.indcrop.2025.121602.
- [42] J. Guo et al., “Kinetic Evidence of Most Abundant Surface Intermediates Variation over Pt n and Pt p : Few-Atom Pt Ensembles Enable Efficient Catalytic Cyclohexane Dehydrogenation for Hydrogen Production-II,” ACS Catalysis, vol. 12, no. 12, pp. 7248–7261, Jun. 2022, doi: 10.1021/acscatal.2c01420.
- [43] M. L. Rochman, N. Hamidi, F. Gapsari, and W. Winarto, “Green diesel and its role as a drop-in renewable diesel alternative to FAME-based biodiesel,” Mechanical Engineering for Society and Industry, vol. 5, no. 2, pp. 288–291, Jan. 2026, doi: 10.31603/mesi.13658.
- [44] J. Fu, “Flash points measurements and prediction of biofuels and biofuel blends with aromatic fluids,” Fuel, vol. 241, pp. 892–900, 2019, doi: 10.1016/j.fuel.2018.12.105.
- [45] M. H. Al-Abdullah, G. T. Kalghatgi, and H. Babiker, “Flash points and volatility characteristics of gasoline/diesel blends,” Fuel, vol. 153, pp. 67–69, 2015, doi: 10.1016/j.fuel.2015.02.070.
- [46] J. M. Da Costa et al., “Characterization of Biodiesel from Animal Fat, Vegetable Oil, and Adulterants by Infrared Spectroscopy Combined with Chemometric Methods,” Energy and Fuels, vol. 35, no. 17, pp. 13801–13812, 2021, doi: 10.1021/acs.energyfuels.1c00911.
- [47] I. C. Castellanos Cuellar, E. Avella-Moreno, P. M. Vargas-Molina, and A. M. Bejarano, “An Interference Free Absorption In The Mid-Infrared to Follow the Obtaining of Biodiesel by Transesterification of Waste Frying Oils,” Momento, vol. 2023, no. 67, pp. 39–54, Jul. 2023, doi: 10.15446/mo.n67.107249.
- [48] V. Sathiyaseelan, S. Chinnasamy, V. D. Tamilarasan, A. Sampathkumar, M. Manikandan, and S. Veeraraghavan, “Comprehensive Spectroscopic and Chromatographic Analysis of Waste Fish Oil Biodiesel using NMR, GC-MS, and FTIR Techniques for Sustainable Alternative Fuel Production,” Malaysian Journal of Chemistry, vol. 27, no. 3, pp. 370–390, 2025, doi: 10.55373/mjchem.v27i3.370.
- [49] M. Ahda, A. Guntarti, A. Kusbandari, and A. Safitri, “Identification of Lard Adulteration of Cooking Oil Products Using Fourier Transform Infrared Spectroscopy Combined with Chemometrics,” Food Analytical Methods, vol. 17, no. 3, pp. 366–372, 2024, doi: 10.1007/s12161-024-02576-y.
- [50] W. Du et al., “Combined determination analysis of surface properties evolution towards bentonite by pH treatments,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 626, p. 127067, Oct. 2021, doi: 10.1016/j.colsurfa.2021.127067.
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