Pretreatment of pine needles via torrefaction, oxidation and hydrothermal carbonization at 250 °C impacts subsequent pyrolysis and activation in distinct ways

Abstract

Thermal pretreatment of biomass in varied medium (i.e. nitrogen, air or water) might further impact pyrolysis and activation in distinct ways. Herein, hydrothermal carbonization (HTC) or torrefaction of pine needles in nitrogen or air at 250 °C and further pyrolysis/activation of pretreated samples was conducted. The results indicated yield of solid followed the method of pretreatment: torrefaction > oxidation > HTC, due to significant oxidation of aliphatics in the pretreatment in air and structural reconstruction in HTC. Additionally, pretreatment in air remarkably increased overall production of biochar (35.1 %), owing to enhanced resistivity to cracking. HTC released nearly half of organics, leading to remarkably lower overall yields of biochar than that in blank experiment (24.7 % versus 30.6 %), but increased thermal stability of biochar through enhancing aromatic degree. Additionally, pretreatment in air removed some H species via oxidation but not nitrogen species while the HTC was the opposite while induced leaching of inorganics. In-situ IR characterization indicated conversion of aliphatic -OH to phenolic -OH in nitrogen-pretreatment, oxidation of ether bridging bond between benzene rings in air-pretreatment and formation of thermally carbonyls via HTC. During activation, all the pretreatments reduced specific surface area of activated carbon, following the order: blank (1351.1 m2 g−1) > torrefaction in N2 (1314.7 m2 g−1) > oxidation in air (1293.8 m2 g−1) > HTC (1218.2 m2 g−1). Oxidation or aromatization reactions in the pretreatment increased aromatic degree of the feedstock, making pore generation via cracking more difficult. Besides, pretreatments also changed morphologies of resulting biochar or activated carbon in distinct ways.