DOI: https://doi.org/10.9767/bcrec.12.2.861.157-166

Measurement of Antioxidant Effects on the Auto-oxidation Kinetics of Methyl Oleate – Methyl Laurate Blend as a Surrogate Biodiesel System

1Chemical Engineering Program, Faculty of Industrial Technology, Bandung Institute of Technology, Jalan Ganesha 10 Bandung 40132, Indonesia

2Research Center for New Fuels and Vehicle Technology, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba East, 1-2-1 Namiki, Tsukuba, Ibaraki 8564, Japan

Received: 6 Jul 2016; Revised: 7 Dec 2016; Accepted: 30 Jan 2017; Available online: 8 May 2017; Published: 1 Aug 2017.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2017 by Authors, Published by BCREC Group under http://creativecommons.org/licenses/by-sa/4.0.

Citation Format:
Cover Image
Abstract

This research investigates the feasibility of methyl oleate-methyl laurate blend as a surrogate biodiesel system which represents jatropha-coconut oil biodiesel, a potentially suitable formulation for tropical climate, to quantify the efficacy of antioxidant additives in terms of their kinetic parameters. This blend was tested by the Rancimat EN14112 standard method. The Rancimat tests results were used to determine the primary oxidation induction period (OIP) and first-order rate constants and activation energies. Addition of BHT and EcotiveTM antioxidants reduces the rate constants (k, h-1) between 15 to 90% in the 50-200 ppm dose range, with EcotiveTM producing significantly lower k values. Higher dose reduces the rate constant, while oleate/laurate ratio produces no significant impact. Antioxidants increase the oxidation activation energy (Ea, kJ/mol) by 180 to almost 400% relative to the non-antioxidant value of 27.0 kJ/mol. EcotiveTM exhibits lower Ea, implying that its higher efficacy stems from a better steric hindrance as apparent from its higher pre-exponential factors. The ability to quantify oxidation kinetic parameters is indicative of the usefulness of methyl oleate-laurate pure FAME blend as a biodiesel surrogate offering better measurement accuracy due to the absence of pre-existing antioxidants in the test samples. 

Fulltext View|Download
Keywords: Biodiesel; Oxidation kinetics; Antioxidant; Rancimat

Article Metrics:

Article Info
Section: Original Research Articles
Language : EN
Recent articles
A Review on Catalytic Membranes Production and Applications Oxidation Kinetics of Propane-Air Mixture over NiCo2O4 Catalyst Emitted from LPG Vehicles Synthesis, Crystal Structure, Catalytic Properties, and Luminescent of a Novel Eu(III) Complex Material with 4-Imidazolecarboxaldehyde-pyridine-2-carbohydrazone Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst Biodiesel Production from Nyamplung (Calophyllum inophyllum) Oil using Ionic Liquid as A Catalyst and Microwave Heating System Front-matter Corrigendum / Erratum / Retraction More recent articles
  1. Vijayavenkataraman, S., Iniyan, S., Goic, R. (2012). A Review of Climate Change, Mitigation and Adaptation. Renewable and Sustainable Energy Review, 16: 878-897
  2. Anonymous. (2007). Climate Change 2007, Synthesis Report, Intergovernmental Panel on Climate Change
  3. Anonymous. (2012). Turn Down the Heat: Why a 4o Warmer World Must be Avoided, Technical Report, The World Bank
  4. Anonymous. (2015). CO2 Emissions from Fuel Combustion, Technical Report, International Energy Agency
  5. Anonymous. (2002). Analysis of Biodiesel Impact on Emissions, Technical Report, United States Environmental Protection Agency
  6. Frankel, E.N. (1980). Lipid Oxidation. Progress in Lipid Research, 19: 1-22
  7. Knothe, G. (2007). Some Aspects of Biodiesel Stability. Fuel Processing Technology, 88: 669-677
  8. Lin, C.Y., Chiu, C.C. (2009). Effects of Oxidation During Long-Term Storage on the Fuel Properties of Palm Oil-Based Biodiesel. Energy and Fuels, 23: 3285-3289
  9. Canakci, M., Monyem, A., van Gerpen, J. (1999). Accelerated Oxidation Processes in Biodiesel. Transactions of the ASAE, 42: 1565-1572
  10. Leung, D.Y.C., Koo, B.C.P., Guo, Y. (2006). Degradation of Biodiesel Under Different Storage Conditions. Bioresource Technology, 97: 250-256
  11. Du Plessis, L.M., de Villiers, J.B.M., van der Walt, W.H. (1985). Stability Studies on Methyl and Ethyl Fatty Acid Esters of Sunflo-werseed Oil. Journal of the American Oil Chemists Society, 62: 748-752
  12. Dunn, R.O. (2005). Effect of Antioxidants on the Oxidative Stability of Methyl Soyate (Biodiesel). Fuel Processing Technology, 86: 1071-1085
  13. Schober, S., Mittelbach, M. (2004). The Impact of Antioxidants on Biodiesel Oxidation Stability. European Journal of Lipid Science and Technology, 106: 382-389
  14. Liang, Y.C., May, C.Y., Foon, C.S., Ngan, M.A., Hock, C.C., Basiron, Y. (2006). The Effect of Natural and Synthetic Antioxidants on the Oxidative Stability of Palm Diesel. Fuel, 85: 867-870
  15. McCormick, R.L., Ratcliff, M., Moens, L., Lawrence, R. (2007). Several Factors Affecting the Stability of Biodiesel in Standard Accelerated Tests. Fuel Processing Technology, 88: 651-657
  17. Herbinet, O., Pitz, W.J., Westbrook, C.K. (2008). Detailed Chemical Kinetic Oxidation Mechanism for a Biodiesel Surrogate. Combustion and Flame, 154: 507-528
  18. Tao, H., Lin, K.C. (B2014). Pathways, Kinetics and Thermochemistry of Methyl-Ester Peroxy Radical Decomposition in the Low-Temperature Oxidation of Methyl Butanoate: A Computational Study of a Biodiesel Fuel Surrogate. Combustion and Flame, 161: 2270-2287
  19. Xin, J., Imahara, H., Saka, S. (2009). Kinetics on the Oxidation of Biodiesel Stabilized with Antioxidant. Fuel, 88: 282-286
  20. Chen, Y., Luo, Y. (2011). Oxidation Stability of Biodiesel Derived from Free Fatty Acids Associated with Kinetics of Antioxidants. Fuel Processing Technology, 92: 1387-1393
  21. Borsato, D., Rafael, J., Cini, D.M., Cremasco, H., Coppo, R.L., Angilelli, K.G., Moreira, I., Cristina, E., Maia, R. (2014). Oxidation Kinetics of Biodiesel from Soybean Mixed with Synthetic Antioxidants BHA, BHT and TBHQ: Determination of Activation Energy. Fuel Processing Technology, 127: 111-116
  22. Knothe, G. (2002). Structure Indices in FA Chemistry: How Relevant is the Iodine Value? Journal of the American Oil Chemists Society, 79: 847-854
  23. Ramos, M.J., Fernandez, C.M., Casas, A., Rodriguez, L., Perez, A. (2009). Influence of Fatty Acid Composition of Raw Materials on Biodiesel Properties. Bioresource Technology, 100: 261-268
  24. Nguyen, M.H. (2009). Effect of Storage Temperature and Antioxidants on Biodiesel Blends. In Asia Biomass Energy Researchers Invitation Program 2008, Collected Papers of Invited Research. Tokyo: New Energy Foundation
  25. Frohlich, A., Schober, S. (2007). The Influence of Tocopherols on the Oxidation Stability of Methyl Esters. Journal of the American Oil Chemists Society, 84: 579-585
  26. Wang, R., Hanna, M.A., Zhou, W., Bhadury, P.S., Chen, Q., Song, B., Yang, S. (2011). Production and Selected Fuel Properties of Biodiesel from Promising Non-Edible Oils: Euphorbia Lathyris L., Sapium Sebiferum L. and Jatropha Curcas L. Bioresource Technology, 102: 1194-1199
  27. Nakatani, N., Tachibana, Y., Kikuzaki, H. (2001) Establishment of a Model Substrate Oil for Antioxidant Activity Assessment by Oil Stability Index Method. Journal of the American Oil Chemists Society, 78: 19-23
  28. Jain, S., Sharma, M.P. (2012). Application of Thermogravimetric Analysis for Thermal Stability of Jatropha Curcas Biodiesel. Fuel, 93: 252-257

Last update:

No citation recorded.

Last update:

No citation recorded.