Effects of Milling and UV Pretreatment on the Pyrolytic Behavior and Thermal Stability of Softwood and Hardwood

UV/visible light is a promising radiation source for biomass pretreatment, but very little knowledge is available on the effect of UV on the thermal behavior of lignocellulose in comparison with more classical, physical pretreatment methods. In this paper, we investigate the effects of ball-milling and UV irradiation on two species of softwood and two species of hardwood, using X-ray diffractometry (XRD), evolved gas analysis-mass spectrometry (EGA-MS), and pyrolysis-gas chromatography coupled to mass spectrometry (Py-GC/MS). The XRD data showed that the crystalline fraction of cellulose was destroyed by milling, but not by irradiation. The EGA-MS data and isoconversional kinetic analysis showed that both milling and irradiation can reduce the thermal stability of wood up to a limit value. The Py-GC/MS data showed that irradiation caused the most significant changes in the pyrolytic behavior of the wood species, increasing the ratio of holocellulose to lignin pyrolysis products and the reactivity of cellulose toward the derivatizing agent. Softwoods were more affected by irradiation than hardwoods. This paper shows that UV irradiation can decrease the recalcitrance of biomass toward pyrolysis, but its efficiency is highly dependent on the type of lignocellulosic substrate.