Fuel Processing Technology, Vol.168, 84-96, 2017
An assessment of pinecone gasification in subcritical, near-critical and supercritical water
Pinecone is a lignocellulosic forest residue with value-added industrial importance in terms of energy and materials production. Although promising, pinecone has received inadequate attention as a biofuel feedstock for thermochemical conversion. Water above its critical temperature (T-c >= 374 degrees C) and critical pressure (P-c >= 22.1 MPa), termed as supercritical water, has high kinetic energy and densities similar to that of gases and liquids, respectively. When employed in gasification, supercritical water has an ability to completely dissolve organics and gases. Therefore, this study identifies the candidacy of pinecone as a precursor for conversion to hydrogen through hydrothermal gasification. Pinecone was gasified in subcritical water (300 and 350 degrees C; 21 MPa), near-critical water (370 degrees C; 22 MPa) and supercritical water (450 and 550 degrees C; 23 MPa) to investigate wthe impacts of temperature (300-550 degrees C), feed concentration (10-25 wt%) and residence time (15-60 min). The impacts of alkali catalysts (e.g., Na2CO3, NaOH and KOH) at a loading of 30 wt% were examined to maximize hydrogen yields. The hydrochar generated from gasification in subcritical water, near-critical water and supercritical water were physico-chemically characterized through proximate and ultimate analysis (carbon-hydrogen-nitrogen-sulfur-oxygen), thermogravimetric analysis, X-ray diffraction, Fourier transform infra-red spectroscopy, Raman spectroscopy, Scanning electron microscopy and Nuclear magnetic resonance spectroscopy. In the non-catalytic gasification of pinecone, highest hydrogen (1.42 mmol/g) and total gas yields (6.6 mmol/g) with lower heating value (488 kJ/Nm(3)) of the gas products were obtained in supercritical water at 550 degrees C with 10 wt% feed concentration for 60 min. Moreover, at 30 wt% catalyst loading, highest hydrogen yield was obtained from KOH (3.26 mmol/g) followed by NaOH (2.71 mmol/g) and Na2CO3 (1.96 mmol/g). Hydrochars generated in supercritical water at 550 degrees C had a greater content of aromatic carbon and were thermally stable. The findings reveal, for the first time, the potential of pinecone for hydrogen production through subcritical, near-critical and supercritical water gasification, as well as the prospective of its hydrochar for environmental and material applications.