Catalytic upgrading of Naomaohu coal pyrolysis volatiles over CaO catalyst

Abstract

Catalytic upgrading of coal pyrolysis volatiles is one the promising way to achieve high quality tar and gas. In this study, catalytic upgrading of volatiles from Naomaohu (NMH) coal pyrolysis has been conducted in a two-stage fixed bed reactor using CaO as catalyst. The aim of this work was to investigate the catalytic effect of CaO on the gas and liquid product distribution, as well as the variations in gas and coal tar components. Simulated distillation and GC-MS analysis has been used to understand the distribution of tar component. On the one hand, CaO exhibits selective cleavage of large molecules, such as long-chain esters, leading to the production of aromatics through the processes of dehydrocyclization and aromatization. CaO has the ability to stabilize free radicals that are generated during the cleavage of large molecules, thereby promoting the formation of light aromatic hydrocarbons. Consequently, the light tar fraction (boiling point <360 °C) increased from 64.4 % to 74.6 %, while the heavy tar fraction (boiling point＞360 °C) decreased from 35.6 % to 25.4 % in the pyrolysis tar. The compounds with long ester chains in the tar composition decreased by 24.4 %. The content of light components, such as benzenes, naphthalene, and phenols, increased significantly with the increasing catalytic temperature. Specifically, the content of benzenes, naphthalene, and phenols increased by 11.83 %, 17.73 %, and 4.41 % respectively at the coal to CaO ratio of 1/0.5 and the catalytic temperature of 600 °C. On the other hand, the CaO absorbs the CO2 pyrolysis gas leading to an elevation in the concentration of CH4 and H2 in the pyrolysis gas. The concentration of CO2 decreased from 37.9 % to 16.58 % compared to without the catalyst while the concentrations of H2 and CH4 increased to 26.24 % and 31.15 % at the catalytic temperature of 450 °C. The CO2 absorption ratio reached a maximum value of 97.16 % at a coal to CaO ratio of 1/2. These findings suggest that the CaO catalyst beneficial both for improving the tar and gas quality.