Production of aromatic hydrocarbons from catalytic fast pyrolysis of microalgae over Fe-modified HZSM-5 catalysts

Abstract

In this study, catalytic fast pyrolysis of the microalga C. pyrenoidosa over Fe-modified HZSM-5 catalysts was performed to produce aromatic hydrocarbons using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Fe-modified HZSM-5 catalysts were prepared using wet impregnation and characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), N₂ adsorption–desorption and temperature-programmed desorption of ammonia (NH₃-TPD) analysis. The effect of Fe loading (3, 5, 8, and 12 wt%) and pyrolysis temperature (450, 500, 550, 600 °C) on the content of pyrolysis products and the content and selectivity of aromatics was examined. Results showed that the parent HZSM-5 catalyst structure remained intact upon increasing Fe loading, although its specific surface area, micropore volume and average pore diameter decreased. In addition, its external specific surface area and total pore volume increased. The modification of Fe metal increased the total acid amount, especially strong acid sites, which were highest when Fe loading was 8 wt%. The prepared Fe-modified HZSM-5 catalysts exhibited pronounced deoxygenation and denitrogenation effects, which significantly decreased the acid, aldehyde, ketone, furan and nitrogenous compounds, thus improving the production of monocyclic aromatic hydrocarbons (MAHs) while effectively suppressing the formation of polycyclic aromatic hydrocarbons (PAHs). The highest content of aromatic hydrocarbons was obtained with an Fe loading of 8 wt% and pyrolysis temperature of 500 °C, which was 42.5%. As Fe loading increased, benzene selectivity decreased, while the selectivity of toluene and xylene first increased and then decreased. With an increase in pyrolysis temperature, benzene selectivity increased, whereas toluene and xylene selectivity increased at first and then decreased. Reaction mechanisms for the formation of aromatic hydrocarbons during the catalytic pyrolysis of microalgae are put forward. This research revealed that catalytic fast pyrolysis of microalgae over Fe-modified HZSM-5 catalysts is an effective method to produce MAHs.