
Molecular Characterisation and Modelling for Refining Processes A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences 2015 Luyi Liu Under the supervision of Dr. Nan Zhang Centre for Process Integration School of Chemical Engineering and Analytical Science Table of Contents Molecular Characterisation and Modelling for Refining Processes ........................... 1 Table of Contents ..................................................................................................... 2 List of Tables ........................................................................................................... 7 List of Figures ........................................................................................................ 10 Abstract ................................................................................................................. 12 DECLARATION ................................................................................................... 14 Copyright Statement .............................................................................................. 15 Acknowledgement ................................................................................................. 17 Chapter 1 Introduction ........................................................................................... 18 1.1 Introduction to Petroleum Refining Scheme ................................................. 18 1.2 Current Trends in the Refining Industry ........................................................ 20 1.3 Challenges in Refinery Modelling ................................................................ 25 1.4 Introduction and Challenges in Molecular Characterisation of Petroleum Fractions and Its Application .............................................................................. 27 1.4.1 Complexity of Petroleum Mixtures ........................................................ 27 1.4.2 Introduction of Petroleum Characterisation ............................................ 28 1.4.3 Challenges in Petroleum Characterisation .............................................. 30 1.5 Motivation and Objective of Present Research .............................................. 31 1.6 Structure of the Thesis .................................................................................. 32 Chapter 2 Existing Work on Petroleum Characterisation and Its Applications ......... 34 2.1 Introduction .................................................................................................. 34 2 2.2 Modern Analytical Laboratory Methods ....................................................... 35 2.3.1 GC......................................................................................................... 36 2.3.2 HPLC .................................................................................................... 36 2.3.3 MS ........................................................................................................ 37 2.3.4 NMR ..................................................................................................... 37 2.3 Review of Existing Characterisation Work ................................................... 38 2.3.1 Lumping Methods ................................................................................. 39 2.3.2 Molecular-level Characterisation Methods ............................................. 40 2.4 The Development of the MTHS Matrix Method ........................................... 41 2.4.1 Transformation to Predict Molecular Composition ................................. 43 2.4.2 Representation Methods ........................................................................ 47 2.5 The Application of Existing MTHS Matrix Method ...................................... 48 2.6 Summary ...................................................................................................... 49 Chapter 3 New Molecular Characterisation Method with Modified MTHS Matrix . 51 3.1 Introduction .................................................................................................. 51 3.2 New Molecular Characterisation Method with Modified MTHS Matrix: Representation Framework ................................................................................. 51 3.3 New Molecular Characterisation Method with Modified MTHS Matrix: Transformation methodology ............................................................................. 56 3.3.1 General procedure ................................................................................. 56 3.3.2 Key assumptions.................................................................................... 58 3.3.3 Properties of interest and their calculations ............................................ 60 3 3.3.4 Transformation preparation .................................................................... 62 3.3.5 Transformation methodology ................................................................. 72 3.4 Case studies ................................................................................................. 79 Case study 1: Straight-run naphtha (SRN) ...................................................... 80 Case study 2: An FCC product gasoline .......................................................... 87 Case study 3: Straight run gas oil characterisation .......................................... 90 3.5 Summary ...................................................................................................... 94 3.6 Nomenclature ............................................................................................... 94 Chapter 4 Molecular Modelling of Catalytic Reforming ......................................... 96 4.1 Introduction .................................................................................................. 96 4.2 Catalytic Reforming Process ........................................................................ 97 4.3 Process Variables .......................................................................................... 98 4.4 Reformate Properties .................................................................................. 100 4.5 Review of Existing Modelling Work ........................................................... 102 4.6 Chemical Reactions Network ..................................................................... 103 4.6.1 Dehydrogenation of Naphthenes to Aromatics ..................................... 104 4.6.2 Isomerisation and of Paraffins and Naphthenes .................................... 105 4.6.3 Dehydrocyclisation of Paraffins ........................................................... 107 4.6.4 Hydrocracking and Dealkylation ......................................................... 107 4.7 Development and Validation of MTHS Based Catalytic Reforming Model . 108 4.7.1 Kinetic Network and Parameter Regression ......................................... 108 4.7.2 Mathematical Model of Catalytic Reformer .......................................... 111 4 4.7.3 Validation and Result Discussion ......................................................... 113 4.8 Sensitivity Analysis of Operating Conditions .............................................. 119 4.8.1 Reactor Pressure .................................................................................. 119 4.8.2 WHSV ................................................................................................. 120 4.8.3 Reactor Temperature ............................................................................ 121 4.9 Summary .................................................................................................... 123 4.10 Nomenclature ........................................................................................... 123 Chapter 5 Molecular Modelling of Gasoline Blending.......................................... 125 5.1 Introduction ................................................................................................ 125 5.2 Gasoline Product Specifications ................................................................. 127 5.3 Review of Researches on Gasoline Blending .............................................. 130 5.3.1 Octane Number ................................................................................... 134 5.3.2 RVP ..................................................................................................... 135 5.4 Development and Validation of MTHS Based Gasoline Blending Model .... 137 5.4.1 Mathematical Model ............................................................................ 138 5.4.2 Validation of MTHS Based Gasoline Blending Model ......................... 140 5.5 Case Study ................................................................................................. 142 5.6 Summary .................................................................................................... 144 5.7 Nomenclature ............................................................................................. 145 Chapter 6 Conclusions and Future Work .............................................................. 146 6.1 Conclusions ................................................................................................ 146 6.2 Future Work ............................................................................................... 147 5 Abbreviations .....................................................................................................
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