Michigan Technological University Digital Commons @ Michigan Tech Dissertations, Master's Theses and Master's Reports 2017 Catalytic Hydrotreatment for the Development of Renewable Transportation Fuels LiLu Funkenbusch Michigan Technological University, [email protected] Copyright 2017 LiLu Funkenbusch Recommended Citation Funkenbusch, LiLu, "Catalytic Hydrotreatment for the Development of Renewable Transportation Fuels", Open Access Dissertation, Michigan Technological University, 2017. https://doi.org/10.37099/mtu.dc.etdr/501 Follow this and additional works at: https://digitalcommons.mtu.edu/etdr Part of the Catalysis and Reaction Engineering Commons CATALYTIC HYDROTREATMENT FOR THE DEVELOPMENT OF RENEWABLE TRANSPORTATION FUELS By LiLu Tian Funkenbusch A DISSERTATION Submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY In Chemical Engineering MICHIGAN TECHNOLOGICAL UNIVERSITY 2017 © 2017 LiLu Tian Funkenbusch This dissertation has been approved in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY in Chemical Engineering. Department of Chemical Engineering Dissertation Advisor: Dr. Michael E. Mullins Committee Member: Dr. David R. Shonnard Committee Member: Dr. Tony N. Rogers Committee Member: Dr. Audrey L. Mayer Department Chair: Dr. Pradeep Agrawal Table of Contents List of Figures .................................................................................................................. viii List of Tables .................................................................................................................... xii Preface............................................................................................................................. xvii Acknowledgements ........................................................................................................ xviii Abstract ............................................................................................................................ xix 1. Introduction & Motivation .......................................................................................... 1 1.1 References ........................................................................................................... 7 2. Kinetic Modeling of the Hydrotreatment of Oleic Acid over a Pt/Al2O3 Catalyst ..... 8 2.1 Introduction ......................................................................................................... 8 2.2 Literature Review.............................................................................................. 10 2.3 Proposed Reaction Network ............................................................................. 12 2.4 Materials & Methods ........................................................................................ 16 2.5 Experimental Results ........................................................................................ 18 2.6 Process Modeling .............................................................................................. 20 2.7 Model Test Cases .............................................................................................. 25 2.8 Conclusions ....................................................................................................... 35 2.9. References ......................................................................................................... 37 3. Catalytic Hydrotreatment of Pyrolysis Oil Literature Review .................................. 42 3.1 Pyrolysis Oil...................................................................................................... 42 3.2 Model Compounds ............................................................................................ 44 3.3 Catalytic Hydrotreatment .................................................................................. 47 iii 3.4 Reactor Types ................................................................................................... 49 3.5 Reactor Pressures & Temperatures ................................................................... 50 3.6 Hydrotreatment Catalysts.................................................................................. 51 3.7 References ......................................................................................................... 54 4. Catalytic Hydrotreatment of Pyrolysis Oil Model Compounds over Pt/Al2O3 and Pd/C Part I: Batch Reactors ....................................................................................... 64 4.1 Introduction ....................................................................................................... 64 4.2 Materials & Methods ........................................................................................ 66 4.3 Results ............................................................................................................... 68 4.4 Reaction Kinetics & Model .............................................................................. 79 4.5 Conclusions ....................................................................................................... 92 4.6 References ......................................................................................................... 95 5. Catalytic Hydrotreatment of Pyrolysis Oil Model Compounds over Pt/Al2O3 and Pd/C Part II: Continuous Reactors ............................................................................ 98 5.1 Introduction ....................................................................................................... 98 5.2 Materials & Methods ...................................................................................... 100 5.3 Results ............................................................................................................. 102 5.4 Reaction Kinetics & Model ............................................................................ 107 5.5 Conclusions ..................................................................................................... 111 5.6 References ....................................................................................................... 114 6. Assessment of Hydrothermal Liquefaction Oil with Catalytic Upgrading for Renewable Fuel and Chemical Production.............................................................. 116 iv 6.1 Introduction ..................................................................................................... 116 6.1.1 Process Chemistry ....................................................................................... 119 6.1.2 Homogeneous alkali catalysts ..................................................................... 122 6.1.3 Heterogeneous HTL catalysts ..................................................................... 122 6.2 Materials & Methods ...................................................................................... 125 6.2.1 HTL reactor design and operation .............................................................. 126 6.2.2 Product separation and extraction ............................................................... 127 6.2.3 Hydrotreatment/hydrodeoxygenation of products ...................................... 128 6.2.4 Model synthesis .......................................................................................... 129 6.2.5 Proposed route and feedstock selection ...................................................... 129 6.2.6 Analysis for environmental impact ............................................................. 136 6.3 Technoeconomic Assessments........................................................................ 136 6.3.1 Near-critical water hydrothermal liquefaction reactor ................................ 137 6.3.2 Centrifuge ................................................................................................... 142 6.3.3 LLE Separation Process .............................................................................. 142 6.3.4 HDO1 Reactor ............................................................................................ 145 6.3.5 HDO2 Reactor ............................................................................................ 147 6.4 Results & Discussion ...................................................................................... 151 6.5 Sustainability & Life Cycle Assessments ....................................................... 159 6.6 Conclusions ..................................................................................................... 160 6.7 References ....................................................................................................... 164 7. Conclusions and Future Work ................................................................................. 172 v 7.1 Conclusions ..................................................................................................... 172 7.1.1 Plant Oils ..................................................................................................... 172 7.1.2 Pyrolysis Oils - Batch ................................................................................. 172 7.1.3 Pyrolysis Oil - Continuous .......................................................................... 173 7.1.4 TEA ............................................................................................................. 174 7.1.5 Overall Conclusions .................................................................................... 175 7.2 Recommendations for Future Work...............................................................