A kinetic investigation of coal liquefaction at short reaction times

Coal liquefaction kinetics have been studied at very short reaction times (less than 250 seconds) in order to emphasize the initial underlying physical and chemical processes involved. These studies were made possible by the use of a continuous flow stirred tank reactor (CSTR) which avoids the problems of slow heat up and cool down associated with the massive equipment required for running high-temperature and high-pressure liquefaction reactions. Preliminary physical (NMR and ESR) and chemical analytical results are presented on the coal liquids and reaction residues from Illinois No. 6 hv bituminous and Wyodak Black Thunder subbituminous coals.

ESR results showed that radical concentration in the solid residue changed during coal liquefaction. These changes were accompanied by changes in the NMR-derived aromaticity. The rate of decrease of organic-based radicals was different for Wyodak Black Thunder and Illinois No. 6 coals, perhaps indicating a different mechanism for the quenching of radicals in these bituminous and subbituminous coals. NMR spectra of the liquid products indicated that the initially produced material was relatively aromatic, and that subsequent products had lower aromatic content. This is consistent with secondary hydrogenation of the primary liquefaction products. Finally, the total oxygen contents of the coal residues decreased gradually during the first three minutes of coal liquefaction at 390°C. A corresponding decrease in the hydroxyl content of these residues was also noted.