CHEMICAL ENGINEERING TRANSACTIONS VOL. 56, 2017 A publication of The Italian Association of Chemical Engineering Online at www.aidic.it/cet Guest Editors: Jiří Jaromír Klemeš, Peng Yen Liew, Wai Shin Ho, Jeng Shiun Lim Copyright © 2017, AIDIC Servizi S.r.l., ISBN 978-88-95608-47-1; ISSN 2283-9216 Thermodynamic Analysis of Hydrogen Production from Methanol-Ethanol-Glycerol Mixture through Dry Reforming Nur Nazlina Saimon, Mazura Jusoh, Mohd Johari Kamarudin, Agus Arsad, Zaki Yamani Zakaria* Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor zakiyamani@utm.my Thermodynamic properties of methanol-ethanol-glycerol dry reforming have been studied with the method of Gibbs free energy minimisation for hydrogen production from methanol-ethanol-glycerol mixture. Equilibrium compositions were determined as a function of CO2/methanol-ethanol-glycerol molar ratios (CMEG) (1 : 6 – 6 : 1) where methanol-ethanol-glycerol is 1 : 1 : 1; reforming temperatures (573 – 1,273 K) at atmospheric pressure (unless stated otherwise). Optimum conditions for hydrogen production are CMEG 1 : 6, temperature 1,273 K, 1 bar pressure. This point is also optimum for the production of synthesis gas. Comparison of the moles of hydrogen produced from methanol-ethanol-glycerol mixture versus ethanol-glycerol mixture was made and exhibit paradoxical effects. Higher pressure and higher CMEG ratio does not encourage hydrogen formation. Under identified optimum conditions, carbon formation can be thermodynamically inhibited. The carbon yield can be reduced through reforming at higher temperatures. 1. Introduction The global increase in energy consumption and environmental pollution raise the need for cleaner and sustainable fuel. In pursuit of that, hydrogen is considered as the most suitable alternative for future energy to reduce the dependence on fossil fuels and carbon emissions. Hydrogen is produced from hydrocarbon reforming and electrolysis processes (Rostrup-Nielsen, 2001). Both processes are practical but involved high processing cost due to the expensive feed price. A more reliable cheaper option to attain hydrogen is required, thus leading to new processes which are more environmentally friendly and economical for hydrogen production. Glycerol, a derivative of biodiesel production by transesterification of vegetable oils and acyl acceptor, has been considered a brilliant candidate for hydrogen production. Numerous on-going studies for the catalytic glycerol steam and dry reforming to hydrogen have been reported (Balat et al., 2010). This includes a study on glycerol steam reforming at low pressure which showed astonishing result (Zakaria et al., 2016). The combination of glycerol and ethanol to produce hydrogen via steam and dry reforming routes have been investigated and could potentially reduce the production costs of biodiesel (Zakaria et al., 2015). This production cost could be further reduced if we incorporate another cheaper feedstock. One such way is by introducing methanol to the glycerol/ethanol mixture. Methanol is far cheaper than both glycerol and ethanol. It has similar basic hydroxyl property as it belongs in the same functional group. Production of hydrogen by glycerol steam reforming (Dou et al., 2014), ethanol steam reforming (Trane- Restrup et al., 2013) and methanol steam reforming (Palo et al., 2007) have been widely investigated. Little is known about glycerol and ethanol dry reforming. None has been found about methanol dry reforming to hydrogen. The combination of methanol-ethanol-glycerol reforming with CO2 to produce hydrogen could be an attractive process. This is because theoretically methanol-ethanol-glycerol dry reforming will convert CO2 into hydrogen and CO (synthesis gas) or high value-added inert carbon and remove it from the carbon biosphere cycle. Ethanol dry reforming studies show that CO2 can be sequestered and carbon deposits in the form of marketable carbon nanofilaments (CNF) (Jankhah et al., 2008). The methanol-ethanol-glycerol dry reforming is expected to show similar properties mainly due to their similar hydroxyl functional group availability. An important advantage from dry reforming of this process compared to steam reforming is that CO2 can be DOI: 10.3303/CET1756162 Please cite this article as: Saimon N.N., Jusoh M., Kamaruddin M.J., Arsad A., Zakaria Z.Y., 2017, Thermodynamic analysis of hydrogen production from methanol-ethanol-glycerol mixture through dry reforming, Chemical Engineering Transactions, 56, 967-972 DOI:10.3303/CET1756162 967