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Physical, Chemical and Thermal Changes of Coals and Coal Maceral Concentrates During Coke Formation

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Physical, Chemical and Thermal Changes of Coals and Coal Maceral Concentrates During Coke Formation Physical, chemical and thermal changes of coals and coal maceral concentrates during coke formation A thesis submitted in partial fulfilment of the Requirements for the degree of Doctor of Philosophy By Wei Xie Discipline of Chemical Engineering The University of Newcastle Australia March, 2013 This thesis contains no material which has been accepted for the award of any degree or diploma in any university or other tertiary institution and, to the best of my knowledge and belief, contains no material previously published or written by another person, except where due reference has been made in the text. I give consent to this copy of my thesis, when deposited in the University Library, being made available for loan and photocopying subject to the provisions of the Copyright Act 1968. Signed --------------------------------------- Wei Xie II Acknowledgements I wish to acknowledge the financial support provided by the Australian Research Council (ARC) for the fundamental understanding of cokemaking. There are many people I wish to thank for their help and support during my completing this thesis. Especially, I would like to express my sincere thanks to my principal supervisor Prof. Terry Wall, to whom I owe a great deal for the years scholarship, guidance, advice, criticism, help, motivation and inspiration he has provided. His wide variety of academic experiences in coal science and supervising PhD students are essential for the successful development of this thesis. The humble thanks I offer here cannot nearly express the depth of my gratitude. I would also like to express my profound gratitude to my co-supervisor A/Prof. John Lucas, his deep understanding in CATA technique and wide knowledge in cokemaking inspired me a lot throughout my thesis. Particularly I want to express my sincere thanks to him for his help, trust, encouragement and inspiration during this thesis. Dr. Rohan Stanger, one of my supervisors for advising and inspiring me during my thesis, is deeply thanked for his valuable supervision, the improvement of CATA technique and the development of DETA technique by him are essential for this thesis. I would extend my gratitude to my industrial supervisor Dr. Merrick Mahoney from BHP research for his advice during this thesis. His participation in the regular weekly meeting with Prof. Terry Wall, A/Prof. John Lucas and Dr. Rohan Stanger for supervising me is appreciated. Also, Prof. Jianglong Yu who was my supervisor during my Master degree from China is thanked for his assistance for recommending me to my principle supervisor Prof. Terry Wall, for which I had a chance to study as a PhD candidate in Australia. I owe my deep gratitude to Dr. Liza Elliot and Dr. Zeenathul Farida Abdul Gani for their help in reading my thesis through and for their valuable comments. They also provided such valuable help and motivation during my experiments and my PhD confirmation, which gave me a lot of confidence that this thesis would be achieved. Thanks also to Dr. Yinghui Liu and Dr. Harold Rogers for his assistance and advice during my experiments, to Dr. Kalpir Shah for his encouragement, and to Prof. Galvin Kevin, Dr. James Zhou, and Mr. Kelly Walton. Mr. Jamie Dickinson and Ms. Rashanthi Liyanaarachchi for the help during my using reflux classifier for coal macerals separation. I would also like to III thank Prof. Erich Kisi, Dr. Bob Loo and Mr Gareth for their assistance during my optical microscopy analysis for my coke samples. I am also grateful to Ms. Jenny Martin who helped me a lot for my experimental consumables. I would extend my gratitude to the laboratory and workshop staff members for their timely help, Mr. Darren McCarthy, Mr. Con Safouris, Mr. Lonn Cooper, Mr. John Richards, Mr. Robert Jones, Mr. Jim Wilson, Ms. Jane Hamson, Mr. Mark Mason and Mr. Neil Gardner. I wish I would never forget the help and the good company I shared with other PhD students in my lab; Renu Kumar, Zeenathul Farida Abdul Gani, Huali Cao, Hongyu Li, Dunyu Liu, Lawrance Belo, Tim Ting and Reinhold Spoerl; and the fourth year students, Jon Chao, Julian Zheng, Timothy Hopper and Andreas Scheyhing. Finally, I would like to thank my parents, my two brothers and my cousins for their strong support and encouragement which made my PhD possible. IV Table of contents Acknowledgements......................................................................................................III Table of contents...........................................................................................................V List of Figures...............................................................................................................X List of Tables .............................................................................................................XV Nomenclature............................................................................................................XVI Abstract..................................................................................................................XVIII Chapter 1 Introduction and Objectives ..........................................................................1 1.1 Introduction..........................................................................................................1 1.1.1 Coke in a blast furnace..................................................................................1 1.1.2 Coke transformation from coal .....................................................................1 1.2 Objectives ............................................................................................................4 1.3 Outline of the thesis .............................................................................................4 Chapter 2 Literature review ...........................................................................................6 2.1 Introduction..........................................................................................................6 2.2 Coal and its heterogeneity....................................................................................6 2.2.1 Coal and its organic constituents ..................................................................6 2.2.2 Coal maceral compositions...........................................................................8 2.2.2.1 Coal petrography....................................................................................8 2.2.2.2 Coal maceral separation.......................................................................10 2.2.2.3 Coal maceral properties .......................................................................11 2.2.3 Coal classification.......................................................................................12 2.2.4 Summary of coal and its heterogeneity.......................................................14 2.3 Changes in coal during heating..........................................................................15 2.3.1 Chemical changes .......................................................................................15 2.3.1.1 Devolatilisation....................................................................................15 2.3.2 Physical changes .........................................................................................16 2.3.2.1 Softening and fusion ............................................................................16 2.3.2.2 Plasticity and swelling .........................................................................17 2.3.2.3 Resolidification....................................................................................18 2.3.2.4 Shrinkage after resolidification............................................................19 2.3.3 Thermal changes .........................................................................................19 2.3.3.1 Endo/exothermic reactions...................................................................19 2.3.3.2 Thermal conductivity...........................................................................19 2.3.4 Summary of changes in coal during heating...............................................20 2.4 Methods used in coal coking experiments.........................................................21 2.4.1 Introduction.................................................................................................21 2.4.2 Fluidity and fusibility..................................................................................21 2.4.2.1 Gieseler plastometer.............................................................................21 2.4.2.2 Proton Magnetic Resonance Thermal Analysis (PMRTA) .................22 2.4.2.3 Permeability .........................................................................................24 2.4.2.4 Rheometry............................................................................................24 2.4.3 Swelling/shrinkage......................................................................................26 2.4.3.1 Crucible-swelling.................................................................................26 2.4.3.2 Audibert-Arnu dilatation......................................................................26 2.4.3.3 A combination measurement of swelling and rheometry ....................27 2.4.4 Gases, tars and organic structures analysis.................................................28 2.4.4.1 Thermogravimetric analysis (TGA).....................................................28 V 2.4.4.2 Matrix-Assisted Laser Desorption/Ionization
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