Influence of calcium promoter on catalytic pyrolysis characteristics of iron-loaded brown coal in a fixed bed reactor

The Fe–Ca catalysts in catalytic pyrolysis of brown coals were studied to investigate the catalytic activity of the Fe–Ca in a fixed-bed reactor. Experimental results showed the maximum yields of the light aromatic hydrocarbons (LAHs) were 5.90 wt% (0.88 wt% of benzene, toluene and xylene ‘BTX’, 4.10 wt% of phenol and cresol ‘PC’ and 0.92 wt% of naphthalene) when the 1.5% Ca was added into 5% Fe-loaded brown coal. The yields of water and gas significantly reduced, the tar yield gradually increased with increasing heating rate. The characterization results indicated that when calcium promoter was impregnated with iron, Ca₂Fe₂O₅, CaO, Fe₂O₃ and α-Fe were formed on the surface of the coal char, Ca₂Fe₂O₅ and α-Fe decomposed polyaromatic tar, CaO and Fe₂O₃ accelerated water gas shift reaction to enhance the H₂ yield, the Fe₂O₃ and Ca₂Fe₂O₅ could be reduced to α-Fe by volatiles (C, CO and H₂) under high temperature catalytic pyrolysis. The synergistic effects between iron and calcium improved brown coal pyrolysis and the volatiles such as free radical fragments were further pyrolyzed, indicating that Fe–Ca catalysts inhibited α-Fe deactivation by tar and carbon deposition, thus promoting brown coal pyrolysis and formation of CO_x, H₂ and LAHs.