ARTICLE IN PRESS JID: JTICE [m5G;December 31, 2014;15:58] Journal of the Taiwan Institute of Chemical Engineers 000 (2014) 1–11 Contents lists available at ScienceDirect Journal of the Taiwan Institute of Chemical Engineers journal homepage: www.elsevier.com/locate/jtice Hydrodeoxygenation of oleic acid into n- and iso-paraffin biofuel using zeolite supported fluoro-oxalate modified molybdenum catalyst: Kinetics study O.B. Ayodele a,d,∗ , Hamisu U. Farouk b , Jibril Mohammed c , Y. Uemura d , W.M.A.W. Daud a,∗ a Department of Chemical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia b Department of Pure and Industrial Chemistry, Faculty of Science, Bayero University Kano, P.M.B. 3011, Kano State, Nigeria c Department of Chemical Engineering, Abubakar Tafawa Balewa University, P.M.B 0248, Bauchi, Bauchi State, Nigeria d Centre for Biofuel and Biochemical Research, Department of Chemical Engineering, Universiti Teknologi PETRONAS, Tronoh, Perak, Malaysia article info Article history: Received 18 August 2014 Revised 11 December 2014 Accepted 14 December 2014 Available online xxx Keywords: Molybdenum oxalate Hydrodeoxygenation Oleic acid Isomerization Biofuel abstract The activity of zeolite supported fluoride-ion functionalized molybdenum-oxalate catalyst (FMoOx/Zeol) and its kinetic study on the hydrodeoxygenation (HDO) of oleic acid (OA) is presented in this report. The FMoOx/Zeol was synthesized via simple dissolution method and characterized. The results revealed forma- tion of highly reactive octahedral Mo species with enhanced textural and morphological properties. The FMoOx/Zeol activity on the HDO of OA at the best observed experimental conditions of 360°C, 30 mg FMoOx/Zeol and 20 bar produces 64% n-C 18 H 38 and 30% iso-C 18 H 38 in 60 min. The acidity of FMoOx/Zeol was responsible for the production of the iso-C 18 H 38 . The kinetic data showed that sequential hydrogenation of OA into stearic acid (SA) was faster than the HDO of SA into biofuel with activation energies of 98.7 and 130.3 kJ/mol, respectively. The reusability studies showed consistency after three consecutive runs amounting to 180 min reaction time. The results are encouraging towards industrial application. © 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved. 1. Introduction Globally, attention is fast shifting to the application of biomass as a source of fuel for the nearest future especially for transporta- tion due to the projected decline in fossil fuel reserves. Other reasons include rise in petroleum prices and the attendant environmental impact of its exploration, processing and especially the exhaust gases from petrol/diesel engines [1,2]. As an alternative to this fossil fuel shortcoming, production of both bio-ethanol fuel (BEF) from carbo- hydrate especially corn via enzymatic transformation, and fatty acid methyl ester (FAME) biodiesel from transesterification of triglycerides with methanol have received tremendous attention in recent years. However, the conflict of BEF from carbohydrate feedstock has lim- ited the expected popularity of its production since most developing countries still largely rely on carbohydrate as the commonest staple food source. On the other hand, the shortcoming of FAME biodiesel such as higher viscosity, higher cloud point temperature, poor oxi- dation stability, poor storage ability, glycerol by-product menace and lower energy density is challenging its future economic and tech- nical reliability [3,4]. Consequently, it is blended with conventional ∗ Corresponding author. Tel:. +60 164955453. E-mail address: ayodele_olumide@yahoo.com (O.B. Ayodele). petroleum diesel to produce a blended fuel of 20% biodiesel and coded B20 in the US. In an attempt to achieve a 100% renewable fuel, catalytic deoxy- genation of triglycerides and free fatty acids (FFAs) has been proposed and is currently being widely studied both in the presence of hydro- gen gas – hydrodeoxygenation (HDO) [1,3–6] and in the absence of hydrogen gas – decarboxylation and decarbonylation (Decarbs) [7,8]. Details of the two processes that have been carefully reviewed [6] and compared [8] showed that HDO is more prospective because its prod- ucts are mostly paraffin with similar properties to the conventional diesel fuel compared to mixtures of paraffin and other condensation products such as esters and ketones observed in Decarbs which ad- versely reduces the energy density [1,4,8]. In addition, HDO process can be adapted into hydrotreating units (HDTU) of existing conven- tional refineries without serious modification [9]. Finally, the fast rate of catalyst deactivation in Decarbs processes has eventually made it less attractive as compared to the HDO [7]. In attempt to deepen research into the HDO process, effects of pro- cess variables such as temperature, H 2 gas flow rate, pressure and type of the catalyst have been well studied [1–4,9]. However, since it has been considered that the existing HDTU of conventional refineries can be adapted, studies on developing suitable catalysts such as types of the support and metals [10], catalyst preparation procedure [2,9] and additives such as sulfur [2] and phosphorus [11] are currently at the http://dx.doi.org/10.1016/j.jtice.2014.12.014 1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Please cite this article as: O.B. Ayodele et al., Hydrodeoxygenation of oleic acid into n- and iso-paraffin biofuel using zeolite sup- ported fluoro-oxalate modified molybdenum catalyst: Kinetics study, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.014