Catalytic Pyrolysis of Naomaohu Coal Using Combined CaO and Ni/Olivine Catalysts for Simultaneously Improving the Tar and Gas Quality

Abstract

Catalytic pyrolysis of low-rank coal is currently an effective method for producing 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 combined CaO and Ni/olivine (Ni-loaded olivine) catalysts. The effect of catalyst distribution modes and catalytic temperature on the tar and gas quality has been investigated. Simulated distillation and GC-MS analysis have been used to investigate the distribution of tar components. The results indicated that the light oil fraction in tar dramatically increased due to the combination of CaO and Ni/olivine. The CaO-Ni/olivine mode is especially better compared to the layouts of the Ni/olivine-CaO mode and the mixed mode. The CaO-Ni/olivine mode ensures a higher light fraction in tar at 69.3% and a light oil fraction at 29.8% at a catalytic temperature of 450 °C, while the heavy tar fraction decreased to 30.7%. Meanwhile, the contents of benzene (heteroatomic substituents) in tar significantly increased from 2.55% to 6.45% compared with the blank test. In this scenario, CaO breaks down macromolecular compounds in tar and cleaves long-chain esters to produce aliphatic hydrocarbons. These hydrocarbons are then dehydrogenated to produce lighter aromatic hydrocarbons over the CaO surface. Subsequently, the volatiles pass through the Ni/olivine catalysis, where ether compounds are produced by means of dehydration reactions. In addition, the CaO absorbs the CO2 in the pyrolysis gas, leading to an elevation of CH4 and H2 concentration. Particularly, the concentration of H2 significantly increased from 16.2% to 30.37%, while the concentration of CO2 significantly decreased from 37.9% to 10.57%. These findings suggest that the usage of combined CaO and Ni/olivine catalysts is beneficial for improving both the tar and gas quality.