Iron-Tellurium and Iron-Tellurium-Selenium Mixed Oxide Catalysts for the Selective Oxidation of 1-Butene to 1,3-Butadiene and Propylene to Acrolein
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1990 Iron-Tellurium and Iron-Tellurium-Selenium Mixed Oxide Catalysts for the Selective Oxidation of 1-Butene to 1,3-Butadiene and Propylene to Acrolein. Bharat M. Patel Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Patel, Bharat M., "Iron-Tellurium and Iron-Tellurium-Selenium Mixed Oxide Catalysts for the Selective Oxidation of 1-Butene to 1,3-Butadiene and Propylene to Acrolein." (1990). LSU Historical Dissertations and Theses. 5013. https://digitalcommons.lsu.edu/gradschool_disstheses/5013 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. 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Order Number 9112260 Iron-tellurium and iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of 1-butene to 1,3-butadiene and propylene to acrolein Patel, Bharat M., Ph.D. The Louisiana State University and Agricultural and Mechanical Col., 1990 300 N. Zeeb Rd. Ann Arbor, M I 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Iron-Tellurium and Iron-Tellurium-Selenium mixed oxide catalysts for the Selective Oxidation of 1-Butene to 1,3-Butadiene and Propylene to Acrolein. A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemical Engineering by Bharat M. Patel B .E .(Ch.E.), University of Mysore, 1978 M.Ch.E., Illinois Institute of Technology, 1980 Summer 1990 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgement The author would like to acknowledge his indebtness to Dr. Geoffrey L. Price for his professional guidance and constant encouragement throughout this work. The time Dr. Price spent to review this manuscript is deeply appreciated. The author is indebted to Dr. Kerry M. Dooley and wishes to thank both Dr. Dooley and Dr. Gregory L. Griffin for their invaluable suggestions during the progress of this work. The author would like to express his gratitute to the dissertation committee, Dr. K. M. Dooley, Dr. G. L. Griffin, Dr. D. P. Harrison in the Chemical Engineering Department, and Dr. C. M. Parks in the Industrial Engineering Department for their time spent in developing constructive comments on this work. The author wishes to thank Dr. Amitava Roy in the Mechanical Engineering Department for SEM and EDAX experiments, Mr. Paul Rodriguez and Robert Perkins in the Chemical Engineering Department for their assistance, whenever needed. The author would also like to thank his fellow graduate students, specially Chi Cheng and Yeung Park for their stimulating discussions in the area of catalysis and general help in the laboratory. Last, but not the least, the author would like to ( i i ) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. thank his parents and his wife, Rita, whose encouragement and understanding during his college education provided a constant source of motivation which led to the completion of this work. ( i i i ) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents Page Acknowledgements ....................................... ii Table of Contents ...................................... iv List of Figures ........................................ x List of Tables ......................................... xv ABSTRACT ................................................ xvii I INTRODUCTION ........................................ 1 1-1 Executive Summary ................................ 4 1-2 Literature Review ................................ 8 1-2.1 General ....................................... 8 1-2.2 Molybdenum Based Allylic Oxidation Catalysts 8 1-2.2.1 Molybdenum Oxides ....................... 8 1-2.2.2 Binary Molybdates ....................... 9 1-2.2.3 Ternary Molybdates ...................... 20 1-2.3 Antimony Based Allylic Oxidation Catalysts 21 1-2.3.1 Antimony Oxides ......................... 21 1-2.3.2 Mixed Antimonates ....................... 22 1-2.4 Iron Based Allylic Oxidation Catalysts .... 25 1-2.4.1 Iron Oxides .............................. 25 1-2.4.2 Mixed Oxides of Iron .................... 27 1-2.4.2.1 Ferrites ............................. 27 1-2.4.2.2 Antimonates ......................... 29 1-2.4.2.3 Other Catalysts ..................... 30 1-2.5 Tellurium Based Allylic Oxidation Catalysts 31 1-2.5.1 Tellurium Oxides ........................ 31 ( lv ) Reproduced with permission of the copyright owner. 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Page 1-2.5.2 Binary Mixed Oxides of Tellurium ...... 32 1-2.5.3 Multicomponent Mixed Oxides of Tellurium 35 I-2.6 Selenium Based Allylic Oxidation Catalysts . 40 1-2.6.1 Selenium Oxide ........................... 40 I-2.6.2 Other Mixed Oxides of Selenium ........ 40 1-3 Research Goal and Plan ........................... 42 II EXPERIMENTAL APPARATUS AND PROCEDURES ............ 45 II-l Materials ...................................... 45 II-2 Equipment ...................................... 47 II-2.1 Catalyst Preparation ..................... 47 II-2.2 Catalyst Characterization and Analytical Facilities ................................ 47 II-2.2.1 Recirculation Batch Reactor ....... 47 II-2.2.2 Volumetric Adsorption Apparatus ... 52 II-2.2.3 Gas Chromatograph and Integrator .. 53 II-2.2.4 Pycnometer and Porosimeter ......... 55 II-2.2.5 Optical Microscope ................. 55 II-2.2.6 Scanning Electron Microscope (SEM) and Electron Dispersive X-ray Ana lysis (EDAX) ........................ 60 II-2.2.7 Atomic Absorption Spectrophotometer 61 II-2.2.8 X-ray Powder Diffractometer ...... 61 II-2.2.9. Fourier-Transform Infrared Spectrometer (FT-IR) ............... 61 II-2.2.10 Gas Chromatograph-Mass Spectrometer (GC-MS) ........................... 63 II-3 Procedures ....................................... 63 (v) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page II-3.1 Catalyst Preparation ....................... 63 II-3.1.1 Synthesis by Hydrothermal Crystal lization ................................ 63 II-3.1.2 Synthesis by Coprecipitaion from Aqueous Solution ....................... 71 II-3.1.3 Synthesis by Solid State Thermal Reaction ........... .................. 71 II-3.1.4 Catalysts ............................. 72 II-3.2 Characterization ......................... 72 II-3.2.1 Physical Characterization ........... 72 II-3.2.1.1 Optical and Scanning Electron Microscopy ....................... 72 II-3.2.1.2 Surface Area Measurements ...... 72 II-3.2.2 Chemical Analysis ................... 74 II-3.2.2.1 Fe and Te Ratio by Atomic Absorp tion Analysis .................... 74 II-3.2.2.2 Fe, Te, Na and Se determination by EDAX Analysis ................ 77 II-3.2.3 Structural Characterization ......... 77 II-3.2.3.1 Infrared Spectroscopy .......... 77 II-3.2.3.2 X-ray Diffraction ............... 77 II-3.2.4 Catalytic Characterization ......... 82 II-3.2.4.1 1-Butene Reaction Studies ...... 82 II-3.2.4.1.1 Catalyst Pretreatment for 1- Butene Oxidation ........... 82 II-3.2.4.1.2 Reaction Studies ........... 83 II-3.2.4.2