Insights into pyrolysis process of coconut shell waste hydrochar: In-situ structural evolution and reaction kinetics

Abstract

Coconut shell (CS) can be efficiently utilized by coupling hydrothermal carbonization (HTC) pretreatment with pyrolysis to meet the goal of global green development. In-situ Raman spectroscopy and thermogravimetric analyzer (TGA) were adopted to investigate the structural evolutions and reaction kinetics characteristics of hydrochar during the pyrolysis process. According to the results, the intensity of peak D and peak G in Raman spectrum decreased with increasing hydrothermal degree. Mild HTC treatment (≤200 °C) led to an increase in ID/IG, indicating the formation of large aromatic rings through small ring condensation. In contrast, severe HTC treatment (≥220 °C) reduced the ID/IG ratio, indicating an increased polycondensation of aromatic compounds and a higher degree of aromatization, resulting in larger molecules sizes. The spectral area below 400 °C reduced with increasing pyrolysis temperature due to the reduction of oxygen-containing functional groups and thermal radiation. Above 400 °C, the total area remains stable as the Raman spectrum scattering ability increases due to char formation and aromatization reactions. HTC-200 exhibited an increase in ID/IG from 0.54 to 0.72 and ID/I(Me + Ke + GL) from 0.58 to 0.68 with increasing pyrolysis temperatures. The activation energy during pyrolysis ranged from 194.50 to 238.34 kJ/mol for CS and 217.51–259.51 kJ/mol for HTC-200. Hydrothermal carbonization had a significant effect on pyrolysis behavior of hydrochar, as it was found that the mild HTC hydrochar followed D-type diffusion models when conversion rate was less than 0.65, and transitioned to higher reaction order in the late-stage of pyrolysis.