Structure and formation of cellulosic chars

The formation and structure of chars produced on heating of cellulose, lignin, and wood have been investigated by FTIR and CP/MAS 13C‐NMR, and the results have been discussed in conjunction with parallel permanganate oxidation studies reported before. These data show that when cellulose is heated for 5 min within the temperature range of 325–350°C, the IR bands associated with hydroxyl and glycosidic groups in cellulose disappear, and new bands signal the formation of unsaturation and carbonyl groups by dehydration and rearrangement. The NMR data also show the disappearance of the glycosyl carbons at 60–110 ppm and the appearance of methyl and other paraffinic carbons at 0–60 ppm, aromatic carbons at 110–170 ppm, carboxyl carbons at 170–190 ppm, and carbonyl carbons at 190–220 ppm. On heating at 400°C the IR and NMR signals for the glycosyl groups completely disappear, the signals for carbonyl and carboxyl groups diminish, and those for the aromatic and paraffinic groups expand. At this stage the char contains about 69% aromatic and 27% paraffinic carbons. At the temperature range of 400–500°C the paraffinic carbon content is reduced to 12%, and a highly aromatic (88%) char is produced. This is consistent with the permanganate oxidation studies which show the production of polycyclic aromatic structures resulting from extensive condensation and crosslinking at these temperatures. The chars produced from wood and lignin at 400°C had about the same aromatic carbon content as the corresponding cellulose char; however, the char yields were higher due to the presence of the methoxy phenyl groups that survive the heating process, as indicated by strong NMR signals at 55 and 148 ppm.