Evolution of fuel nitrogen in coal devolatilization

The distribution of fuel nitrogen in the devolatilization products of a lignite and 12 bituminous coals has been observed experimentally. For these coals under isothermal conditions (300 < T < 1000 °Cand 5 < t < 80 s) the behaviour of the nitrogen evolution was found to be similar. Nitrogen which is initially released is contained almost entirely in the tar. The chemical composition, ¹³C-n.m.r. spectra and infrared spectra of the tars and parent coals are strikingly similar and it is reasonable to suspect that the tar nitrogen occurs in the same structures as in the parent coal. Secondary release of nitrogen into nontar volatiles occurs only at high temperature. Results can be described with first-order kinetics using the same rate constant for all the coals studied. Initial nitrogen release is described by the tar release rate constant, k = 81 exp (−5800/T) (s⁻¹), which is similar to the rate constant for initial nitrogen release measured by Pohl and Sarofim. Secondary release of nitrogen is described with a rate constant which is similar to the results measured by Blair, Wendt and Bartok. This rate is smaller than that measured for the decomposition of nitrogen-ring compounds such as pyridines or pyrroles. The results suggest that coal nitrogen is contained almost entirely in tightly bound rings which are released without breakage in the tar during the initial stage of devolatilization; the remainder is released at higher temperatures when rings are ruptured.