Molecular structure characterization of low-medium rank coals via XRD, solid state 13C NMR and FTIR spectroscopy

Abstract In-depth understanding of coal molecular structures is crucial to the clean and efficient coal conversion, as they are the dominant factors determining the reactivity and reaction behaviors of coals in thermal conversions such as combustion, pyrolysis, gasification and liquefaction. However, the molecular structures of coals are still far from clear due to the intrinsic complexity and heterogeneity of coals. This work probes the molecular structures of eight coals of various metamorphic grades with combined spectral techniques of X-ray diffraction (XRD), solid state 13C NMR and FTIR spectra. The structural parameters were correlated with the coalification indicator R o to investigate the structural evolutions during coal metamorphism. Consistent results concerning the structural evolution during coalification were obtained with different techniques. From the parameters of proximate and ultimate analysis, the increasing aromaticity and decreasing aliphatic fractions with rising coalification degree are observed. XRD patterns show the ubiquitous presence of amorphous carbon, the gradually condensing aromatic layers, and the size-growing but graphitizing crystallites during coalification. 13C NMR spectra reveal different types of carbons presented, the increasing aromatic and decreasing aliphatic components, the growing size and weight but reducing number of side-chains of the aromatic clusters. FTIR spectra indicate shortening and reducing of aliphatic chains, as well as enhancing aromaticity with the deepening metamorphism. These findings shed light on the structure features of coals and are potentially useful to the clean and efficient coal utilization.