Staged evolutionary features of the aromatic structure in high volatile A bituminous coal (hvAb) during gold tube pyrolysis experiments

Abstract

Low-temperature pyrolysis of coal is a crucial step in the coal thermal conversion process and involves very complex physical and chemical reactions that can have different effects on the coal's structure. The thermal evolution behavior and transformation mechanism of the coal microstructure are not yet fully understood, which also limits the efficient utilization of coal to a certain extent. The aromatic structural features (including size, molecular ordering, nematic symmetry, stacking, and curvature) of the char produced from low-temperature pyrolysis of high volatile A bituminous coal (hvAb) from the Xutuan coal mine, China, were quantitatively assessed via high-resolution transmission electron microscopy (HRTEM) image processing and analytical techniques. The thermal transformation process and the mechanisms controlling it were explored. The results show that, except for the unexpected slight growth of aromatic sheets at 440 °C, the lower pyrolysis temperature (< 521 °C) contributed weakly to their size growth, whereas at higher temperatures (561–600 °C), it significantly increased their size. The aromatic molecular ordering tended to gradually change in three stages: increasing between 340 and 440 °C, decreasing between 440 and 521 °C and increasing again between 521 and 600 °C. The nematic symmetry strength of aromatic fringes also followed a similar pattern with temperature at different scales. Additionally, in addition to a very minor development trend at 440 °C, the stacking did not significantly change at temperatures below 521 °C but developed appreciably further with increasing temperatures at 561–600 °C; however, the average spacing of the stacks did not appear to be significantly reduced at all temperatures. The curvature of the aromatic sheets also varied in different temperature stages, i.e., initially slightly increasing (340–380 °C), then gradually decreasing (380–480 °C), later increasing again (480–521 °C), and eventually decreasing (521–600 °C). The properties of the chemical composition and structure of the initial coal play important roles in the thermal reaction behavior, and the physical and chemical reactions that dominate at the different temperature stages may be responsible for such wiggly trends in the evolution of the aromatic structure. Notably, the properties of the mesophase (approximately 440 °C) strongly influence the subsequent structural transformation. These findings could provide useful information for the microstructure–property relationships and preparation of coal-based carbon materials.