Chemical properties of superfine pulverized coal particles. Part 1. Electron paramagnetic resonance analysis of free radical characteristics

摘要

Superfine pulverized coal combustion is a new pulverized coal combustion technology with lots of advantages. A mechanochemical effect exists during the comminution process, which changes the chemical properties of coal significantly. Free radical concentrations and certain functional groups would increase with the decrease of particle sizes. In this paper, we combined electron paramagnetic resonance (EPR) and I3C solid-state nuclear magnetic resonance (NMR) techniques to study the free radical characteristics of superfine pulverized coal thoroughly. The final results indicate that the EPR spectra of coal are the superimpositions of several lines induced by different paramagnetic centers, which can be fitted by 1 Gaussian and 3 Lorentzian lines. The influences of coal maturities and particle sizes on EPR parameters, such as g-values, linewidths, and spin concentrations, are analyzed in detail. It is shown that with the decrease of particle sizes, more free radicals are induced through bond cleavages. Mechanical forces initiate the accumulation of free radicals in the fractures and inner pore surfaces of coal. Furthermore, the influence of particle sizes on oxygen-containing radicals (i.e., Lorentzian 1 types) is the greatest. This work provides a primary picture of the occurrence modes and spatial distributions of free radicals in superfine pulverized coal. The findings will help form the basis and provide guidance for further studies on revealing the correlations between the free radical reaction pathways and NO_x formation mechanisms.