Analysis and distribution of volatile gases from catalytic pyrolysis of Sulcis low-rank coal

Abstract

Catalytic pyrolysis of Sulcis low-rank coal over naturally occurring olivine, and home-made 15 wt%Ni/γ-Al2O3 catalyst was conducted for the upgrading of coal pyrolysis volatile gases in the temperature range ambient-900 °C under atmospheric pressure. Raw coal and mixtures of coal-additive (90:10 wt%) were slowly heated in temperature programmed mode using a laboratory-scale quartz furnace coupled in parallel to Fourier transform infrared (FTIR) spectrometer and GC chromatograph for quantitative analysis of flue gas. Coal pyrolysis with and without additives was also conducted by TG/DTG/DSC analysis at different heating rate (β = 15, 20, 30 °Cmin−1). DSC results clearly indicated some extra exothermic events during catalytic coal pyrolysis. Quantitative gaseous products distribution with temperature showed yields significantly and selectively improved with additives. Generally, more CO and CO2 were emitted under catalytic coal pyrolysis. Meanwhile, nickel catalyst exerted a marked positive effect on H2 yield overall in the temperature range 400–500 °C. The light hydrocarbons such as methane, ethane, propane and n-hexane substantially remaining unchanged, whereas a remarkable increase of emitted ethene was originated from catalytic pyrolysis. A deeper SO2 evolution was observed over olivine, whereas the N-containing compounds (NH3, NOx) were also modified in catalytic pyrolysis. Formaldehyde was also monitored, which represents a fragment originating from polycyclic aromatic side chains. Reaction kinetic study by a model-free isoconversional method indicated a complex multiple-step mechanism of coal pyrolysis, exception made for conversion values between 5% and 50% where a single-step reaction path was operating. The calculated average Ea and the pre-exponential factor were markedly reduced by the presence of additives. Meanwhile the compensation effect was also existing.