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Effect of Water Quality on Coal Thermoplasticity Feng Zhang

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Effect of Water Quality on Coal Thermoplasticity Feng Zhang Effect of water quality on coal thermoplasticity Feng Zhang A thesis in fulfilment of the requirements for the degree of Master of Philosophy in Engineering School of Minerals and Energy Resources Engineering Faculty of Engineering June 2018 II III Acknowledgements I would like to thank my supervisors Associate Professor Seher Ata and Dr. Ghislain Bournival for their support, guidance and encouragement throughout my research study. I am especially grateful to Seher, who was the supervisor of my undergraduate thesis, for trusting my ability to complete this research degree. Special thanks to Professor Alan Buckley for his help with my understanding on coal surface chemistry and surface analysis. Also, many thanks to Mr. Noel Lambert, for providing valuable information related to this research topic, as well as preparing and transporting the coal and process water samples. I appreciate Dr. Bin Gong, Dr. Yin Yao for their help with the XPS analysis and SEM analysis. I would like to thank Australian Coal Association Research Program (ACARP) for funding this research project and providing the coal and process water samples. Lastly, thanks to my family and friends, especially to my girlfriend, Hongni Yin, for their endless support throughout these two years. IV Abstract Process water reuse is a common practice in Australian coal preparation plants. It is an effective solution to on-site water scarcity and to minimize environmental impacts. This study investigates the effect of inorganic mineral salts in the process water on the thermoplastic properties of metallurgical coals after a short period of mild oxidation. Two different Australian metallurgical coals were treated with the process water received from a coal preparation plant based in Queensland, AU, and exposed to air at ambient temperature. Artificial inorganic salt solutions and process water with adjusted salt dilution ratio were also used to treat the coal samples. The selection of the inorganic salt solutions was based on the concentrations of the major ions found in the process water. The inorganic salts used in the study include some sodium salts, e.g. sodium carbonate and sodium sulfate, as well as potassium and magnesium salts. Coal samples were treated with the different solutions following several different procedures respectively. The thermoplastic properties of the samples treated with designated solutions were measured using a Gieseler plastometer, which measures the fluidity of the coal samples. The results suggested that the fluidity of coal decreased as the concentration of inorganic salts in the solution increased. When different salt solutions were used, the degree of fluidity reduction was found to be similar at the same concentration. The effect of inorganic salt on coal thermoplastic behaviours was found to be dependent on the total salt concentration in the solution used in the treatment. Examination of the coal surface with a scanning electron microscope equipped with energy dispersive x-ray spectroscopic probe (SEM-EDS) showed the existence of both sodium and chlorine on the surface of process water treated coal. The surface analysis by X-ray photoelectron spectroscopy (XPS) indicated a relatively insignificant chemical reaction between the inorganic ions present in the water and the coal surface after rinsing the samples. Salts appeared to precipitate on non-maceral matter and act as an inert (non-plastic) additive. V Table of Contents Acknowledgements................................................................................................................ I Abstract ................................................................................................................................. V List of Figures .................................................................................................................. VIII List of Tables ...................................................................................................................... XI Chapter 1 Introduction .....................................................................................................1 1.1 Introduction to coal preparation, coke making and thermoplastic properties ......... 1 1.2 Statement of the problem ........................................................................................ 4 1.3 Objectives ................................................................................................................ 6 1.4 Thesis structure ........................................................................................................ 8 Chapter 2 Literature review .............................................................................................9 2.1 Introduction ............................................................................................................. 9 2.2 Coal thermoplastic properties ................................................................................ 10 2.2.1 Coal molecular transformations during pyrolysis .......................................... 12 2.2.2 Theories of coal thermoplastic properties ...................................................... 17 2.3 Factors affecting coal thermoplastic properties ..................................................... 21 2.3.1 Coal rank and maceral compositions ............................................................. 22 2.3.2 Inorganic matter ............................................................................................. 27 2.3.3 Oxidation ........................................................................................................ 33 2.3.4 Cross-linking .................................................................................................. 39 2.3.5 Coal blend and additives ................................................................................ 42 2.3.6 Techniques for coal thermoplasticity examination ........................................ 44 2.4 Process water chemistry and coal thermoplasticity ............................................... 52 2.4.1 Process water chemistry ................................................................................. 52 2.4.2 Interaction between inorganic substances and coal surface ........................... 53 2.5 Literature review summary.................................................................................... 56 Chapter 3 Methodology ..................................................................................................58 3.1 General experimental considerations .................................................................... 58 3.2 Characterisation of coal samples ........................................................................... 59 VI 3.3 Characterisation of water samples ......................................................................... 61 3.3.1 Process water sample ..................................................................................... 61 3.3.2 Chemical solutions ......................................................................................... 67 3.4 Experimental and analytical methods .................................................................... 68 3.4.1 Salt solution soaking ...................................................................................... 68 3.4.2 Oxidation ........................................................................................................ 68 3.4.3 Inorganic electrolyte removal ........................................................................ 70 3.4.4 Ash analysis ................................................................................................... 71 3.4.5 Surface analysis .............................................................................................. 73 3.4.6 Coal thermoplastic properties analysis........................................................... 76 Chapter 4 Results and discussions .................................................................................79 4.1 Effect of Na2CO3 soaking on coal fluidity ............................................................ 79 4.2 Effect of oxidation on coal fluidity ....................................................................... 83 4.3 Effect of oxidation on water chemistry ................................................................. 87 4.4 XPS analysis of treated coal surface ..................................................................... 91 4.5 SEM-EDS Analysis of Oxidised Coal Surface ..................................................... 96 4.6 Effect of total concentration of inorganic salt on coal fluidity ............................ 101 4.7 Mechanism of fluidity reduction in coal preparation plant ................................. 103 4.8 Concluding remarks ............................................................................................ 105 Chapter 5 Conclusions and recommendations ...........................................................106 5.1 Conclusions ......................................................................................................... 106 5.2 Recommendations ............................................................................................... 109 References ..........................................................................................................................110 Appendix ............................................................................................................................125 VII List of Figures Figure 1.1 Illustration
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