Thermodynamic Analysis and Reduction of MnO2 by Methane–Hydrogen Gas Mixture

Abstract

Methane and hydrogen reduction has emerged as promising technology for clean and efficient metallurgy. To understand the reduction process of MnO2 by CH4-H2 gas mixture, the effects of various CH4/(CH4 + H2) molar ratios (0–1) and temperatures (1100°C–1250°C) on the reduction of pure MnO2 were researched. Characterization of the solid carbon derived from the decomposition of CH4 gas was also determined. Thermodynamic analysis indicated that the MnO2 was first reduced to MnO by CH4-H2 gas mixture, and then MnO was reduced to Mn7C3 according to this reaction, 7MnO(s) + 10CH4(g) = Mn7C3(s) + 7CO(g) + 20H2(g). Experimental results showed that under the CH4/(CH4 + H2) molar ratio of 0.2, the reduction extent of MnO2 increased with the rising of temperatures. Nevertheless, the deep reduction of MnO to Mn7C3 was retarded even by increasing the temperature and prolonging the time, which was a result of the formation of deposited solid carbon. The free carbon contents in the reduced samples increased with the increasing of the CH4/(CH4 + H2) molar ratio and reduction time. The reduction of MnO2 and formation of carbon can be regulated by adjusting the CH4/(CH4 + H2) molar ratio in a gas mixture. For example, when MnO2 was reduced by 50 vol.%CH4-50%N2, large amounts of MnO and Mn7C3 particles were wrapped by the platelike and rodlike carbon with nanoscale. Yet, the wrapping phenomenon cannot be observed under 10 vol.%CH4-40 vol.%H2-50 vol.%N2.