Sulfur transformation during rapid hydropyrolysis of coal under high pressure by using a continuous free fall pyrolyzer☆

The behavior of sulfur transformation during rapid hydropyrolysis of coal was investigated using a pressurized, continuous free fall pyrolyzer under the conditions of temperature ranging from 923 to 1123 K and hydrogen pressure up to 5 MPa. The yields of sulfur converted to gas, tar and char were determined, together with the analyses of sulfur form distributions in coals and chars. The results showed that the decomposition of inorganic sulfur species was affected only by the temperature, while the increases in temperature and hydrogen pressure obviously enhanced the removal of organic sulfur from coal. The extent of organic sulfur removal was proportional to the coal conversion, depending on coal type. A significant retention of gaseous sulfur products by the organic matrix of the char was observed during hydropyrolysis of a Chinese coal above 1023 K, even under the pressurized hydrogen atmosphere. The kinetic analysis indicates that the rate of organic sulfur removal from coal was 0.2th-order with respect to the hydrogen pressure, and the activation energy for total sulfur removal and organic sulfur removal is 17-26 and 13-55 kJ/mol, respectively. The low activation energies suggest that the transformation and removal of sulfur from coal might be controlled by the diffusion and/or thermodynamic equilibrium during hydropyrolysis under the pressurized conditions.