Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step

Herein, for the first time, we demonstrate a novel continuous flow process involving the application of tetralin as a hydrogen donor solvent for the catalytic conversion of oleic acid to diesel-like hydrocarbons, using an efficient and stable carbon-supported bimetallic PdCu catalyst. Using Pd60Cu40...

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Main Authors: Cheah, K.W., Yusup, S., Taylor, M.J., How, B.S., Osatiashtiani, A., Nowakowski, D.J., Bridgwater, A.V., Skoulou, V., Kyriakou, G., Uemura, Y.
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Institution: Universiti Teknologi Petronas
Record Id / ISBN-0: utp-eprints.30045 /
Published: Royal Society of Chemistry 2020
Online Access: https://www.scopus.com/inward/record.uri?eid=2-s2.0-85092565096&doi=10.1039%2fd0re00214c&partnerID=40&md5=e05df0970fd39f3f30bc5f3455b2740f
http://eprints.utp.edu.my/30045/
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spelling utp-eprints.300452022-03-25T03:22:26Z Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step Cheah, K.W. Yusup, S. Taylor, M.J. How, B.S. Osatiashtiani, A. Nowakowski, D.J. Bridgwater, A.V. Skoulou, V. Kyriakou, G. Uemura, Y. Herein, for the first time, we demonstrate a novel continuous flow process involving the application of tetralin as a hydrogen donor solvent for the catalytic conversion of oleic acid to diesel-like hydrocarbons, using an efficient and stable carbon-supported bimetallic PdCu catalyst. Using Pd60Cu40/C, where 60�:�40 is the molar ratio of each metal, at optimum reaction conditions (360 °C and WHSV = 1 h-1), 90.5 oleic acid conversion and 80.5 selectivity to C17 and C18 paraffinic hydrocarbons were achieved. Furthermore, a comprehensive mechanistic based kinetic modelling-considering power rate law, L-H and E-R models was conducted. Kinetic expressions derived from the three kinetic models were investigated in rate data fitting through nonlinear regression using a Levenberg-Marquardt algorithm. Based on the statistical discrimination criteria, the experimental data of the dehydrogenation reaction of tetralin were best fitted by an L-H rate equation assuming the surface reaction as the rate controlling step. In contrast, the kinetic data of the oleic acid deoxygenation reaction were well correlated with an L-H rate equation assuming single site adsorption of oleic acid with dissociative H2 adsorption. It was found that the rate limiting step of the overall reaction was the hydrogenation of oleic acid with an activation energy of 75.0 ± 5.1 kJ mol-1 whereas the dehydrogenation of tetralin had a lower activation energy of 66.4 ± 2.7 kJ mol-1. This journal is © The Royal Society of Chemistry. Royal Society of Chemistry 2020 Article NonPeerReviewed https://www.scopus.com/inward/record.uri?eid=2-s2.0-85092565096&doi=10.1039%2fd0re00214c&partnerID=40&md5=e05df0970fd39f3f30bc5f3455b2740f Cheah, K.W. and Yusup, S. and Taylor, M.J. and How, B.S. and Osatiashtiani, A. and Nowakowski, D.J. and Bridgwater, A.V. and Skoulou, V. and Kyriakou, G. and Uemura, Y. (2020) Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step. Reaction Chemistry and Engineering, 5 (9). pp. 1682-1693. http://eprints.utp.edu.my/30045/
institution Universiti Teknologi Petronas
collection UTP Institutional Repository
description Herein, for the first time, we demonstrate a novel continuous flow process involving the application of tetralin as a hydrogen donor solvent for the catalytic conversion of oleic acid to diesel-like hydrocarbons, using an efficient and stable carbon-supported bimetallic PdCu catalyst. Using Pd60Cu40/C, where 60�:�40 is the molar ratio of each metal, at optimum reaction conditions (360 °C and WHSV = 1 h-1), 90.5 oleic acid conversion and 80.5 selectivity to C17 and C18 paraffinic hydrocarbons were achieved. Furthermore, a comprehensive mechanistic based kinetic modelling-considering power rate law, L-H and E-R models was conducted. Kinetic expressions derived from the three kinetic models were investigated in rate data fitting through nonlinear regression using a Levenberg-Marquardt algorithm. Based on the statistical discrimination criteria, the experimental data of the dehydrogenation reaction of tetralin were best fitted by an L-H rate equation assuming the surface reaction as the rate controlling step. In contrast, the kinetic data of the oleic acid deoxygenation reaction were well correlated with an L-H rate equation assuming single site adsorption of oleic acid with dissociative H2 adsorption. It was found that the rate limiting step of the overall reaction was the hydrogenation of oleic acid with an activation energy of 75.0 ± 5.1 kJ mol-1 whereas the dehydrogenation of tetralin had a lower activation energy of 66.4 ± 2.7 kJ mol-1. This journal is © The Royal Society of Chemistry.
format Article
author Cheah, K.W.
Yusup, S.
Taylor, M.J.
How, B.S.
Osatiashtiani, A.
Nowakowski, D.J.
Bridgwater, A.V.
Skoulou, V.
Kyriakou, G.
Uemura, Y.
spellingShingle Cheah, K.W.
Yusup, S.
Taylor, M.J.
How, B.S.
Osatiashtiani, A.
Nowakowski, D.J.
Bridgwater, A.V.
Skoulou, V.
Kyriakou, G.
Uemura, Y.
Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
author_sort Cheah, K.W.
title Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
title_short Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
title_full Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
title_fullStr Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
title_full_unstemmed Kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic Pd60Cu40catalyst: An investigation of the surface reaction mechanism and rate limiting step
title_sort kinetic modelling of hydrogen transfer deoxygenation of a prototypical fatty acid over a bimetallic pd60cu40catalyst: an investigation of the surface reaction mechanism and rate limiting step
publisher Royal Society of Chemistry
publishDate 2020
url https://www.scopus.com/inward/record.uri?eid=2-s2.0-85092565096&doi=10.1039%2fd0re00214c&partnerID=40&md5=e05df0970fd39f3f30bc5f3455b2740f
http://eprints.utp.edu.my/30045/
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score 11.62408

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