Effect of extracts of petroleum ether, dichloromethane and methanol on thiophenic sulfur release during coal pyrolysis

Abstract

The existing forms and thermal transformation of sulfur in high sulfur coal directly influence the efficiency of coal clean utilization by the staged pyrolysis conversion. Low molecular compounds distributed in coal are very different from the macromolecular structure of coal and play an important role during coal pyrolysis. In order to investigate the effects of low molecular compounds on the release of typical thiophenic sulfur species during coal pyrolysis by Py-GC/MS, petroleum ether, dichloromethane, and methanol were used for sequential ultrasonic extraction of Linfen coal (LFC). The compositions of extracts were detected by GC×GC/MS. Results show that three primary kinds of thiophenic sulfur species (2-methyl thiophene, benzothiophene, and dibenzothiophene) were released during coal pyrolysis and they are mainly derived from the cracking of macromolecular skeleton containing thiophenic sulfur in coal. The amounts of thiophenic sulfur released during raw coal and residues pyrolysis both increase with temperature. Besides, extracts with different compositions have different effects on the release of thiophenic sulfur during pyrolysis. In detail, the cyclization of aliphatic compounds could provide active hydrogen. On the one hand, the active hydrogen promotes the break of bridge bonds around thiophenic sulfur. On the other hand, active hydrogen may attack sulfur atoms of thiophenic sulfur, reducing the energy barriers of thiophenic sulfur decomposition. Aromatic compounds polymerize with sulfur-containing groups converting to benzothiophene and dibenzothiophene with larger molecular weight. In addition, thiophenic sulfur may be oxidized by esters to sulfones or sulfoxides, which further decompose, resulting in the inhibition effect on thiophenic sulfur formation during coal pyrolysis.