CHARACTERIZATION OF THE STRUCTURAL FEATURES OF OXIDIZED BEYPAZARI LIGNITE USING DECONVOLUTED SOLID STATE 13C NMR SPECTRA

ABSTRACT

The solid state ¹³C NMR method have been used to investigate the structural changes occurred in Beypazari lignite while oxidizing at 150°C in a dynamic air atmosphere. Least squares curve fitting techniques have been used to resolve the overlapping bands in the 0-220 ppm region of the 13_c NMR spectra. Measurements of the relative intensities of the functional groups observed in the oxidized coals were used to follow the progress of air oxidation. Oxidation reactions seemed to decrease the total intensities of both aliphatics and aromatics, though the reduction in aliphatics was more pronounced. The relative intensities of the total aliphatics decreased from 1.0 to 0.9 and 0.6 in the original and lignites oxidized for 12 and 312 hours, respectively. The relative intensities of Ar-C-C in the 130-148 ppm region for the same set of samples were 1.0, 0.9 and 0.8. The least-squares bands resolved in the carbonyl region were at 175 ppm and 190 ppm in the original lignite; at 180 ppm (carboxylic acids), 195 ppm (meta substituted ketones) 210 ppm (di orto substituted ketones) in the lignite oxidized for 12 hours and at 170 ppm (esters), 180 ppm, 200 ppm (aldehydes) and 210 ppm in the lignite oxidized for 312 hr. Carbonyl intensity increased from 1.0 in the original lignite to 2.3 and 3.3 in the oxidized lignites. The intensity of aromatic ethers increased from 1.0 in the original lignite to 1.9 and 1.6 for the oxidized samples. The mechanism of oxidation ether. Aldehydes are easily oxidized to carboxylic acids in the presence of air by the free radical formation of a peroxy acid. The carboxylic acid formed by disproportionation reactions between the peroxy acid and aldehydes might combine with phenols to produce esters as it was observed in the present work. The presence of high free radical concentration in the oxidation atmosphere probably caused to abstract hydrogen atoms from the aromatic structures thus degrading aromatics to produce hydroperoxides which acted later as it was described above. The gradual degradation of aromatic structures observed in the present study indicated that the oxidation reactions of the aromatic rings should less probable when compared to the oxidation of aliphatic structures.