Characterisation of mineral matter in South African coals using micro-raman spectroscopy and other techniques

Thesis submitted in fulfilment of the requirements for the degree of Doctor of Philosophy to the Faculty of Engineering and the Built Environment, School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2017Three medium rank C coals and a discard coal from different coalfields within the Karoo Basin were investigated. In this study, physico-chemical properties, ash fusion tests, quantitative single particle -electron probe X-ray microanalysis (SPAEPXMA), petrography, X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), and micro-Raman spectroscopy (mRs) were used as analytical techniques of choice to investigate the heterogeneous nature of coals, including mineralogical structure, mode of occurrence, and association of mineral matter in coals. The aim of the work was to highlight the significance of understanding the heterogeneous nature of coals, and to develop comprehensive and reliable approaches of characterising coals, coal ashes, and predict the behaviour of coals in coal conversion processes. The FTIR technique identified a well ordered kaolinite of authigenetic origin, characterised by inner hydroxyl group with H2O vibration at 3618 cm-1 absorption bands as the major mineral. Smectite and muscovite were identified at peaks 797 cm-1 and 799 cm-1 respectively, with quartz confirmed by the υ (Si-O-Si) and δ (Si-O) bands. The SPA-EPXMA data, modelled using principal component analysis (PCA) and chemical boundary classification (CBC), identified a diverse range of minerals such as alunite, chlorite, fayalite, almandine, anatase, ilmenite, brushite, goyazite, gypsum, dolomite, calcite, sodalite, rhodochrocite, and halite in raw coal samples. The mRs technique showed that in addition to bassinite, other oxidation products that formed at low temperature included lepidocrite and coquimbite. The technique proved to be ideal for the characterisation of high temperature ashes. High spatial resolution of mRs confirmed the presence of mixtures of anatase, brookite, and rutile, hematite, nephaline, apatite, crednerite and apatite in high temperature ashes. The SPA-EPMXA and mRs technique probed minerals on a micro-scale and their application could be extended to prediction of slagging and fouling behaviour in coals. The multiple technique approach revealed the importance of using a combination of techniques to characterise coals, and provided useful information that can help understand and relate the mineralogical and elemental composition of coals. This knowledge could be useful in designing conversion processes, and necessary downstream manipulations.XL201