Acid-Catalyzed Esterification for Biodiesel Production from Acid Oil

Golmakani, Mohammad-Taghi; Alishahi, Afsaneh; Raayatpisheh, Maryam; Riazi, Masoud; Ghobadian, Barat; Niakousari, Mehrdad

doi:10.22050/ijogst.2025.338908.1637

Acid-Catalyzed Esterification for Biodiesel Production from Acid Oil

Document Type : Research Paper

Authors

Mohammad-Taghi Golmakani ¹

Afsaneh Alishahi ²

Maryam Raayatpisheh ³

Masoud Riazi ⁴

Barat Ghobadian ⁵

Mehrdad Niakousari ¹

¹ Professor, Food Science and Technology Department, School of Agriculture, Shiraz University, Shiraz, Iran

² PhD, Food Science and Technology Department, School of Agriculture, Shiraz University, Shiraz, Iran

³ MS, Department of Food Science and Technology, Yasooj Branch, Islamic Azad University, Yasooj, Iran

⁴ Associate Professor, Enhanced Oil Recovery Research Centre, IOR/EOR Research Institute, Shiraz University, Shiraz, Iran

⁵ Professor, Department of Biosystems Engineering, Tarbiat Modares University, Tehran, Iran

https://doi.org/10.22050/ijogst.2025.338908.1637

Abstract

In this study, acid oil, which is a by-product of oil refinery waste was used for acid-catalyzed esterification to produce biodiesel. The reaction variables were methanol: acid oil molar ratio (1:1, 5:1, and 10:1), catalyst concentration (1%, 2%, and 3%), and reaction time (5, 30, and 60 min). Conversion yield, mass yield, free fatty acid (FFA) content, and physical properties (viscosity, density, refractive index, color attributes) of all the biodiesel samples were investigated. With increasing the methanol: acid oil molar ratio, catalyst concentration, and time, conversion yield and density increased, while free fatty acid content, viscosity and refractive index decreased, displaying an asymptotic trend toward equilibrium. At methanol: acid oil molar ratio of 10:1, catalyst concentration of 3%, and reaction time of 60 min, a near-maximum conversion yield of 95.3% was achieved. These conditions were considered optimum practical conditions, balancing biodiesel yield with operational and economic feasibility. Final yield of produced biodiesel at the practical optimum condition was 84.25%, which confirms that acid oil is a suitable feedstock for biodiesel production.

Highlights

· Acid-catalyzed esterification was employed to produce biodiesel from acid oil.

· Biodiesel yield increased with increasing methanol content, catalyst concentration, and reaction time.

· Conversion of acid oil to biodiesel decreased viscosity and refractive index, while increasing density.

Keywords

Acid oil

Biodiesel

Esterification

Waste

Subjects

Chemical Engineering

Akinfalabi, S. I., Rashid, U., Arbi Nehdi, I., Yaw Choong, T. S., Sbihi, H. M., and Gewik, M. M., Optimization and blends study of heterogeneous acid catalyst-assisted esterification of palm oil industry by-product for biodiesel production, Royal Society Open Science, Vol. 7, No. 1, p. 191592, 2020.

Alishahi, A., Golmakani, M. T., and Niakousari, M., Feasibility Study of Microwave‐Assisted Biodiesel Production from Vegetable Oil Refinery Waste, European Journal of Lipid Science and Technology, Vol. 123, No. 9, p. 2000377, 2021.

Alptekin, E., and Canakci, M., Determination of the density and the viscosities of biodiesel–diesel fuel blends, Renewable Energy, Vol. 33, p. 2623–2630, 2008.

AOCS, Official Methods and Recommended Practices of the American Oil Chemists' Society, AOCS press, Champaign, IL., 2000.

ASTM, Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels, ASTM International, West Conshohocken, PA., 2013.

Atabani, A. E., Silitonga, A. S., Badruddin, I. A., Mahlia, T., Masjuki, H., and Mekhilef, S., A comprehensive review on biodiesel as an alternative energy resource and its characteristics, Renewable and sustainable energy reviews, Vol. 16, No. 4, p. 2070–2093, 2012.

Bahadur, N. P., Boocock, D. G, and Konar, S. K., Liquid hydrocarbons from catalytic pyrolysis of sewage sludge lipid and canola oil: evaluation of fuel properties, Energy & fuels, Vol. 9, No. 2, p. 248–256, 1995.

Baig, A., and Ng, F. T., A single-step solid acid-catalyzed process for the production of biodiesel from high free fatty acid feedstocks, Energy & Fuels, Vol. 24, p. 4712–4720, 2010.

Beker, S. A., da Silva, Y. P., Bücker, F., Cazarolli, J. C., de Quadros, P. D., Peralba, M. D. C. R., Piatnicki, C. M. S., and Bento, F. M., Effect of different concentrations of tert-butylhydroquinone (TBHQ) on microbial growth and chemical stability of soybean biodiesel during simulated storage, Fuel, Vol. 184, p. 701–707, 2016.

Bello, E. I., Effects of transesterification on the color of biodiesel, Scientia Agriculture, Vol. 13, No. 1, p. 10–13, 2016.

Binhweel, F., Hossain, M. S., and Ahmad, M. I., Recent trends, potentials, and challenges of biodiesel production from discarded animal fats: a comprehensive review, BioEnergy Research, Vol. 16, p. 778–800, 2023.

Cerón Ferrusca, M., Romero, R., Martínez, S. L., Ramírez-Serrano, A., and Natividad, R., Biodiesel production from waste cooking oil: a perspective on catalytic processes, Processes, Vol. 11, No. 7, p. 1952, 2023.

Cunha, C. L., Luna, A. S., Oliveira, R. C., Xavier, G. M., Paredes, M. L., and Torres, A. R., Predicting the properties of biodiesel and its blends using mid-FT-IR spectroscopy and first-order multivariate calibration, Fuel, Vol. 204, p. 185–194, 2017.

Dehghan, L., Golmakani, M. T., and Hosseini, S. M. H., Optimization of microwave-assisted accelerated transesterification of inedible olive oil for biodiesel production, Renewable Energy, Vol. 138, p. 915–922, 2019.

Ebrahimi, S. L., Khosravi-Nikou, M. R., and Hashemabadi, S. H., An experimental study on the operating parameters of ultrasoundassisted oxidative desulfurization, Iranian Journal of Oil & Gas Science and Technology, Vol. 8 (2019), No. 3, pp. 01–17

Gole, V. L., and Gogate, P. R., Intensification of synthesis of biodiesel from non-edible oil using sequential combination of microwave and ultrasound, Fuel Processing Technology, Vol. 106, p. 62–69, 2013.

Golmakani, M.T., Moosavi-Nasab, M., Raayatpisheh, M., and Dehghani, Z., Fatty acid methyl ester production from rainbow trout waste oil using microwave-assisted transesterification, Process Biochemistry, Vol. 139, p. 33–43, 2024.

Hayyan, A., Alam, M. Z., Mirghani, M. E., Kabbashi, N. A., Hakimi, N. I. N. M., Siran, Y. M., and Tahiruddin, S., Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production, Fuel Processing Technology, Vol. 92, p. 920–924, 2011.

Kosuru, S. M. Y., Delhiwala, Y., Koorla, P. B., and Mekala, M., A review on the biodiesel production: Selection of catalyst, pre-treatment, post treatment methods, Green Technologies and Sustainability, Vol. 2, No. 1, p. 100061, 2024.

Kulkarni, B. M., Pujar, B. G., and Shanmukhappa, S., Investigation of acid oil as a source of biodiesel, Indian Journal of Chemical Technology, Vol. 15, p. 467–471, 2008.

Leung, D. Y., Wu, X., and Leung, M. K. H., A review on biodiesel production using catalyzed transesterification, Applied Energy, Vol. 87, p. 1083–1095, 2010.

Lin, Y. C., Hsu, K. H., and Lin, J. F., Rapid palm-biodiesel production assisted by a microwave system and sodium methoxide catalyst, Fuel, Vol. 115, p. 306–311, 2014.

Litinas, A., Geivanidis, S., Faliakis, A., Courouclis, Y., Samaras, Z., Keder, A., Krasnoholovets, V., Ganfzha, I., Zabulonov, Y., Puhach, O., and Dmytriyuk, M., Biodiesel production from high FFA feedstocks with a novel chemical multifunctional process intensifier, Biofuel Research Journal, Vol. 7, No. 2, p.1170–1177, 2020.

Math, M. C., Kumar, S. P., and Chetty, S. V., Technologies for biodiesel production from used cooking oil—A review, Energy for Sustainable Development, Vol. 14, p. 339–345, 2010.

Mishra, V. K, and Goswami, R. A., A review of production, properties and advantages of biodiesel, Biofuels, Vol. 9, p. 273–289, 2018.

Mohammadi, S., Sobati, M. A., and Sadeghi, M. T., Viscosity reduction of heavy crude oil by dilution methods: new correlations for the prediction of the kinematic viscosity of blends, Iranian Journal of Oil & Gas Science and Technology, Vol. 8, No. 1, p. 60–77, 2019.

Nisar, A., Hashum, K., Bashir, M., Mubeen, N., Younus, S., Mehmood, S., Haq, F., and Haroon, M., Advancing sustainable biofuel production from agricultural residues: a comprehensive mini-review, Sustainable Chemical Engineering, p. 115–128, 2024.

Niu, S., Ning, Y., Lu, C., Han, K., Yu, H., and Zhou, Y., Esterification of oleic acid to produce biodiesel catalyzed by sulfonated activated carbon from bamboo, Energy Conversion and Management, Vol. 163, p. 59–65, 2018.

Osorio-González, C. S., Gómez-Falcon, N., Sandoval-Salas, F., Saini, R., Brar, S. K., and Ramírez, A. A, Production of biodiesel from castor oil: A review, Energies, Vol. 13, No. 10, p. 2467, 2020.

Oyekunle, D. T., Gendy, E. A., Barasa, M., Oyekunle, D. O., Oni, B., and Tiong, S. K., Review on utilization of rubber seed oil for biodiesel production: Oil extraction, biodiesel conversion, merits, and challenges, Cleaner Engineering and Technology, p. 100773, 2024.

Pali, H. S., Sharma, A., Kumar, M., Annakodi, V. A., Nguyen, V. N., Singh, N. K., Singh, Y., Balasubramanian, D., Deepanraj, B., Truong, T. H., and Nguyen, P. Q. P., Enhancement of combustion characteristics of waste cooking oil biodiesel using TiO2 nanofluid blends through RSM, Fuel, Vol. 331, P. 125681, 2023.

Peng, B. X., Shu, Q., Wang, J. F., Wang, G. R., Wang, D. Z., and Han, M. H., Biodiesel production from waste oil feedstocks by solid acid catalysis, Process Safety and Environmental Protection, Vol. 86, p. 441–447, 2008.

Phan, A. N., and Phan, T. M., Biodiesel production from waste cooking oils, Fuel, Vol. 87, No. 17–18, p. 3490–3496, 2008.

Rajkumari, K., and Rokhum, L., A sustainable protocol for production of biodiesel by transesterification of soybean oil using banana trunk ash as a heterogeneous catalyst, Biomass Conversion and Biorefinery, Vol. 10, p. 839–848, 2020.

Sajjadi, B., Aziz, A. A., and Ibrahim, S., Investigation, modelling and reviewing the effective parameters in microwave-assisted transesterification, Renewable and Sustainable Energy Reviews, Vol. 37, p. 762–777, 2014.

Shibasaki-Kitakawa, N., Hiromori, K., Ihara, T., Nakashima, K., and Yonemoto, T., Production of high-quality biodiesel from waste acid oil obtained during edible oil refining using ion-exchange resin catalysts, Fuel, Vol. 139, p. 11–17, 2015.

Srivastava, A., and Prasad, R, Triglycerides-based diesel fuels, Renewable and Sustainable Energy Reviews, Vol. 4, No. 2, p. 111–133, 2000.

Suen, T. J., and Chien, T. P., Reaction mechanism of the acid hydrolysis of fatty oils, Industrial & Engineering Chemistry, Vol. 33, p. 1043–1045, 1941.

Talavari, R., Hosseini, S., and Moradi, G. R., Low-cost biodiesel production using waste oil and catalyst, Waste Management & Research, Vol. 39, No. 2, p. 250–259, 2021.

Valizadeh, S., Valizadeh, B., Khani, Y., Jae, J., Ko, C. H., and Park, Y.-K., Production of biodiesel via esterification of coffee waste-derived bio-oil using sulfonated catalysts, Bioresource Technology, p. 130908, 2024.

Veillette, M., Giroir-Fendler, A., Faucheux, N., and Heitz, M., Esterification of free fatty acids with methanol to biodiesel using heterogeneous catalysts: from model acid oil to microalgae lipids, Chemical Engineering Journal, Vol. 308, p. 101–109, 2017.

Veljković, V. B., Lakićević, S. H., Stamenković, O. S., Todorović, Z. B, and Lazić, M. L., Biodiesel production from tobacco (Nicotiana tabacum L.) seed oil with a high content of free fatty acids, Fuel, Vol. 85, p. 2671–2675, 2006.

Wang, Z. M., Lee, J. S., Park, J. Y., Wu, C. Z., and Yuan, Z. H., Novel biodiesel production technology from soybean soap stock, Korean Journal of Chemical Engineering, Vol. 24, p. 1027–1030, 2007.

Wei, H., Wang, Q., Zhang, R., Liu, M., and Zhang, W., Efficient biodiesel production from waste cooking oil by fast co-immobilization of lipases from Aspergillus oryzae and Rhizomucor miehei in magnetic chitosan microcapsules, Process Biochemistry, Vol. 125, p. 171–180, 2023.

Yazdani, B., and Saeedi Dehaghani, A. H., Experimental analysis of the effect of microwaves on the oil properties in the presence of different minerals, Iranian Journal of Oil & Gas Science and Technology, Vol. 11 (2022), No. 3, pp. 67–79.

Yusuf, B. O., Oladepo, S. A., and Ganiyu, S. A., Efficient and sustainable Biodiesel Production via Transesterification: catalysts and operating conditions, Catalysts, Vol. 14, No. 9, p. 581, 2024.

Zhang, H., Ding, J., and Zhao, Z., Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production, Bioresource Technology, Vol. 123, p. 72–77, 2012.

Zhou, Y., Li, K., and Sun, S., Simultaneous esterification and transesterification of waste phoenix seed oil with a high free fatty acid content using a free lipase catalyst to prepare biodiesel, Biomass and Bioenergy, Vol. 144, p. 105930, 2021.

Zhu, J., Jiang, W., Yuan, Z., Lu, J., and Ding, J., Esterification of tall oil fatty acid catalyzed by Zr4+-CER in fixed bed membrane reactor, Renewable Energy, Vol. 221, p. 119760, 2024.

Zou, H. S., and Chai, J., A novel ultrasonic reactor for continuous production of biodiesel from waste acid oil, Korean Journal of Chemical Engineering, Vol. 34, p. 353–359, 2017.