ORALS

SESSION: EnergyThuPM2-R11	6th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Thu Oct, 24 2019 / Room: Coralino
Session Chairs: Puzhen Gao; Sonja Stefanov; Session Monitor: TBA

16:45: [EnergyThuPM211]
Roles of Ni, Co and Cu Monometallic Catalysts Supported on ZrO2 for Green Diesel Production via the Palm Oil Hydrodeoxygenation
Nikolaos Charisiou¹ ; Steven J. Hinder² ; Mark A. Baker² ; Kyriaki Polychronopoulou³ ; Maria A. Goula¹ ; ¹Laboratory of Alternative Fuels and Environmental Catalysis, Department of Chemical Engineering, University of Western Macedonia, Kozani, Greece, Kozani, Greece; ²The Surface Analysis Laboratory, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, UK, Guildford, United Kingdom; ³Khalifa University, Abu Dhabi, United Arab Emirates;
Paper Id: 249 [Abstract]

Energy demand in the world is expected to increase by 59% by the year 2035 [1]. In addition, liquid transportation fuels from renewable resources are urgently needed due to the depletion of fossil resources. During the last 10 years intensive research efforts on biofuels, among them only green diesel, which can be synthesized either via catalytic hydrodeoxygenation or deoxygenation of triglycerides and fats, exhibits the same fuel properties as conventional diesel, since it has a similar composition. On the other hand, ethanol and butanol exhibit lower heating values and can suffer from incomplete burning thus forming oxygenated, harmful, gaseous by-products [2]. Moreover, biodiesel consisting of fatty acid methyl esters (FAMEs) has low oxidative stability, high viscosity and poor cold weather performance and is incompatible for large-scale use in conjunction with fossil fuels [3]. In the present work, we prepared ZrO₂-supported Ni, Co and Cu monometallic catalysts for the production of green diesel via hydrodeoxygenation of palm oil. The catalysts were prepared by the wet impregnation method and had the same metal loading (8 wt.%). The physical and chemical properties were determined by applying several characterization techniques including BET, XRD, NH3/CO2-TPD, TPR, XPS and TEM. Catalytic deoxygenation experiments were carried out in a fixed bed reactor (Autoclave Engineers BTRS) equipped with an HPLC pump. The SDO experiments were conducted using different operating parameters for the Ni/Zr catalyst, as follows: T=250-375°C, P=20-30 bar, LHSV=1.2-2.4 h^-1 and H₂/oil=250-2000 cm³/cm³, while for the Cu/Zr and Co/Zr samples the following operating parameters were used: T=300-400^oC, P=30 bar, LHSV=1.2 h^-1 and H₂/oil=1000 cm³/cm³. The results shows that the recommended conditions for the Ni/Zr were: I�=300 I�C, P = 30 bar, LHSV = 1.2 h^-1, H₂/oil ratio = 1000 cm³/cm³. Specifically, Palm oil was totally converted at 300 &#o176;C and the main reaction products were C₁₅ and C₁₇, with yields of 16 and 49 mol%, respectively, while C₁₅-C₁₈ n-alkane's yield was equal to 88 mol%. By comparing the three catalysts the deoxygenation activity decreased in the order of C₁₅-C₁₈ n-alkane's yield Ni > Cu > Co when compared at the same reaction temperatures. Also, to understand the roles of the three catalysts on the activity and selectivity in the deoxygenation reaction, the contributions of HDO and deCOx were estimated based on the mole balance corresponding to fatty acids in the oil feed. The Ni and Cu catalysts were favorable to the deCOx routes, whereas HDO was dominant over the Co catalyst.

References:
[1] X. Li, X. Luo, Y. Jin, J. Li, H. Zhang, A. Zhang, J. Xie, Renew. Sustain. Energy Rev. 82 (2018) 3762-3797.
[2] S. Douvartzides, N.D. Charisiou, K. N. Papageridis, M.A. Goula, Energies 12(5), 809 (2019).
[3] N.D. Charisiou, K. Polychronopoulou, A. Asif, M.A. Goula, Surf. Coatings Technol. (2018).