Department of Chemical Engineering Centre for Fuels and Energy Catalytic Partial Oxidation of Propylene to Acrolein: The Catalyst Structure, Reaction Mechanisms and Kinetics Hamzah Fansuri This thesis is presented for the Degree of Doctor of Philosophy of Curtin University of Technology June 2005 Declaration This thesis contains no material which has been accepted for the award of any other degree or diploma in any university. To the best of my knowledge and belief this thesis contains no material previously published by any other person except where due acknowledgment has been made. Signature: …………………………………………. Date: ………………………... i Acknowledgments First, I would like to thank The AusAID for sponsoring my studies at Curtin University of Technology; AINSE for grants awarded (grant AINGRA03132, AINGRA04177 and AINGRA 04191) which enable me to carry out neutron diffraction experiments at ANSTO and CHEMEQ Company for funding which has partially supported the research. I would also like to thank Institute of Technology Sepuluh November (ITS), Surabaya and Direktorat Jenderal Pendidikan Tinggi (DIKTI) who gave me the opportunity to pursue a higher degree education. However, this dissertation could not have been completed without the assistance and support of many people and institutions. Countless thanks to Professor Dong-ke Zhang, the Supervisor of my research, for his intense interest and patience in supervising my research, and his valuable guidance as well as his constructive comments at all stages of the research. In addition, his financial support enabled me to attend conferences, giving me opportunities to expand my knowledge about research and to exchange ideas with other scholars. I would also like to thank Dr. Gia Hung Pham of CHEMEQ Company for his invaluable help at the early stage of my candidature. Both Professor Dong-ke Zhang and Dr. Gia Hung Pham are my guru in this research and always be my guru. I am very lucky to have been associated with them, because without their encouragement, invaluable advice and criticism, this thesis could never have come into existence. I would also like to thank other students who were involved in the same project. To be mentioned here are: Ms Sandra Wibawanta, Ms Linlin Yang, Ms Audrey Boehly, Mr. Jasson Muirhead, and Mr. Bendan Lynch. Thank you all for your contribution in the lab work, preparation, and discussions regarding the research ii subjects. I would also like to thank my colleagues in the CHEMEQ, including Andrew Huxham, Steve Jarkovic, and Ben De Pinto for their insightful discussions. I also need to acknowledge the useful assistance provided by all academic and administrative staff in the Centre for Fuels and Energy and Department of Applied Physics at Curtin University of Technology and Bragg Institute at ANSTO. In particular Ms Angelina Rositter for the lab support, Mr. Geoffrey Han for his computer and network support, Ms Elaine Miller for her assistance with my SEM work, Professor Brian O’Connor and Dr. Suminar Pratapa for their assistance with XRD analyses, Dr. Margaret Elcombe, Dr. Andrew Studer and Mr. Michael Prior for assistance with my Neutron Diffraction analysis, and Dr. David French for his help with high temperature X-ray Diffraction analysis. This thesis will also not exist without support, understanding, patience, and love from my family, my wife Nurul Widiastuti and my son Zahrul Atharinafi. Without their unconditional support, endless patience and constant encouragement during my stay in Perth, Western Australia, it would have been very difficult for me to finish this work. Finally, this work would not have been possible without the previous works of other researchers cited within the body of the thesis. For this, I am also grateful. iii Dedications High above all be Allah, the King, the Truth! be not in haste with the Quran before its revelation to thee is completed but say, "O my Lord! Advance me in knowledge." The Holy Quran - Thaha 114. For Nurul and Zahrul, my beloved wife and son iv Publications Journals 1. Fansuri, H., G. H. Pham, S. Wibawanta, D.K. Zhang and D. French, The Relationship Between Structural Change in a and g-Bismuth Molybdate at High Temperature and Their Selectivity and Activity on Catalytic Partial Oxidation of Propylene to Acrolein, Surface Review and Letters, Vol. 10 Nos. 2-3 (2003) 549- 553. 2. Fansuri, H., G. H. Pham, S. Wibawanta, R. Radford, and D.K. Zhang, Catalytic Activity of Propylene to Acrolein: The Activity of Bismuth Molybdate Catalysts under Oxygen-Rich Conditions, DCEMP, vol 12 No 3/4 (2004) 333-340 Conference Proceedings 1. Fansuri, H., D.K. Zhang, D. French, M. Elcombe, A. Studer, An X-ray and Neutron Diffraction Study of the Structure of α-Bi2Mo3O12 as Catalyst for Partial Oxidation of Propylene to Acrolein, CHEMECA 2004, Sydney, 26-29 September 2004. 2. Fansuri, H., G. H. Pham, S. Wibawanta, D. K. Zhang, The Effect of Phosphorous Addition on the Activity of Bismuth Molybdate Catalyst for Partial Oxidation of Propylene to Acrolein, Australian Symposium on Combustion and The 8th Australian Flames Days, Melbourne, December 2003. 3. Fansuri, H., D. K. Zhang, M. Elcombe, and A. Studer, In-Situ Neutron Diffraction Study of α-Bismuth Molybdate, CHEMECA 2003, Adelaide- Australia, September 2003. 4. Fansuri, H., G. H. Pham, S. Wibawanta, R. Radford, and D.K. Zhan, Catalytic Activity of Propylene to Acrolein: The Activity of Bismuth Molybdate Catalysts v under Oxygen-Rich Conditions, 9th APCChE Congress and CHEMECA 2002, Christchurch-New Zealand, September 2002. Power point Presentation and Posters 1. Fansuri, H., D.K. Zhang, M. Elcombe, A. Studer, In-situ Structural Studies of Bismuth Molybdate Catalysts for Partial Oxidation of Propylene to Acrolein using Neutron Diffraction, SSC 2004, Praha, 12-15 September 2004. 2. Fansuri, H., D.K. Zhang, M. Elcombe, A. Studer, D. French, Structure Determination of Powder α-Bi2Mo3O12 by Joint Refinements of its Cu and Co Source X-ray and Neutron Diffractogram, EPDIC-IX, Praha, 2-5 September 2004. 3. Fansuri, H., D.K. Zhang, M. Elcombe, A. Studer, In-situ Neutron Diffraction Study of alpha Bismuth Molybdate, (Poster), EPDIC-IX, Praha, 2-5 September 2004. 4. Fansuri, H., G. H. Pham, S. Wibawanta, D.K. Zhang and D. French, The Relationship Between Structural Change in a and g-Bismuth Molybdate at High Temperature and Their Selectivity and Activity on Catalytic Partial Oxidation of Propylene to Acrolein, (Poster), ICSOS 7, Newcastle, 21-27 July 2002. vi Table of content Declaration .................................................................................................................... i Acknowledgments........................................................................................................ii Dedications..................................................................................................................iv Publications.................................................................................................................. v Table of content .........................................................................................................vii List of Figures .............................................................................................................. x List of Tables ............................................................................................................ xiv Abbreviations ............................................................................................................ xvi Summary .................................................................................................................xviii Chapter 1...................................................................................................................... 1 INTRODUCTION ....................................................................................................... 1 Chapter 2...................................................................................................................... 7 LITERATURE REVIEW ............................................................................................ 7 2.1 Acrolein ............................................................................................................... 7 2.2 Partial Oxidation of Propylene to Acrolein ......................................................... 8 2.3 Acrolein Production........................................................................................... 10 2.4 Active Catalyst Systems .................................................................................... 11 2.5 Bismuth Molybdates.......................................................................................... 13 2.5.1 Crystal Structure of Bismuth Molybdates.............................................. 13 2.5.2 Relationship between Structure of Bismuth Molybdate and Catalytic Activity................................................................................................... 21 2.6 Diffraction Techniques for Characterisation of Heterogeneous Catalyst.......... 23 2.7 The Rietveld Analysis ....................................................................................... 25 2.8 The Reaction Mechanisms of Partial Oxidation of Propylene to Acrolein on Bismuth Molybdate Catalysts............................................................................ 27 2.8.1 Propylene Activation.............................................................................. 27 vii 2.8.2 Oxygen Insertion...................................................................................