Catalytic upgrading of Naomaohu coal pyrolysis volatiles over NiAl and NiLiAl oxides

Catalytic upgrading of volatiles is an essential technology to improve the product distribution of pyrolysis for the clean and efficient utilization of low-rank coals. In this work, novel acid-base bifunctional catalysts composed of Ni/Li/Al oxides were designed and prepared using LDH precursors with tunable chemical composition and structural properties. The catalysts were systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), physisorption, NH3-temperature programmed desorption (NH3-TPD), CO2-temperature programmed desorption (CO2-TPD), H2-temperature programmed reduction (H2-TPR), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). A two-stage fixed bed reactor was employed to evaluate the performance of the catalysts. Characterization results suggest that the crystal size of NiO and the surface area of the catalyst decreased with increasing Li content and decreasing Ni content in the catalyst, while the pore volume and pore diameter were positively correlated with Li content. Moreover, the addition of Li reduced the amount of weak acid sites and raised the amount of total basic sites. Consequently, the bifunctional catalysts boosted the yield of light tar and the contents of aromatics and phenols in tar. Specifically, with the highest total acid sites (569 μmol/g) promoting the cracking of heavy pitch components, Ni2.5Li0.5Al1 decreased the content of pitch in tar to 23.8 wt%, representing a 42.7 % drop from the corresponding non-catalytic pyrolysis. Accordingly, it improved the light tar yield to 7.2 wt%, which was 18 % higher than non-catalytic pyrolysis. 450 °C is identified as a suitable temperature for the catalytic upgrading of volatiles from Naomaohu coal; higher catalysis temperatures at 500 °C and 550 °C led to lower tar yield and lower phenols content, along with higher gas yield and more carbon deposition.