Search for retrogressive reactions accompanying demineralization in native and air-oxidized coals

This solid state 13C NMR study confirms, for coals, and extends, for air-oxidized coals, the claim that the Bishop and Ward strong aqueous-acid coal demineralization procedure [M. Bishop, D.L. Ward, Fuel 37 (1958) 191.] does not lead to the formation of detectable levels of cross-links in the organic matrix of these materials. The study was prompted by the demonstration that polymerization accompanies strong acid demineralization in lignin, and the recognition that the chemical environment created in air-oxidized coals contains introduced reactive functionality similar to that in the lignin. In particular, both contain oxidized benzylic carbon functionality that can undergo acid-catalyzed polymerization reactions. For two coals of differing rank, no acid-induced cross-link formation has been observed in the pristine or air-oxidized coals, within the 5 parts per thousand (ppt) sensitivity of the NMR technique used in this study.