Catalytic function of ferric oxide and effect of water on the formation of sulfur trioxide.

Sulfur trioxide (SO3) is not only environmentally harmful but also highly corrosive, taking a great threat to the safe operation of coal-fired power plants. A dominant pathway of SO3 formation in coal-fired power plant is through the catalytic oxidation of SO2 (SO2+1/2O2→SO3) on the surfaces of ash particles containing Fe2O3. The catalytic formation of SO3 could be affected by complex atmosphere, where the effect from H2O is still debatable. In this paper, density functional theory (DFT) is employed to explore the reaction pathway of SO3 formation catalyzed by α-Fe2O3 in complex atmosphere containing O, O2, SO2 and H2O. In order to get the stable adsorption sites of these species, the adsorption energy of potential adsorption configurations on the α-Fe2O3 (001) surface is calculated. The dissociations of O2 molecule on complete and defect α-Fe2O3 (001) surfaces with O vacancy are calculated, and the Langmuir-Hinshelwood and Eley-Rideal mechanisms for the O(ads) reaction with SO2(ads) or SO2 are compared. The effect of H2O besides of SO2 and O2 on the formation of SO3 is especially discussed. The DFT calculation results show that for the formation of SO3 in gas phase, the energy barrier of 'SO2+1/2O2→SO3' is 436.75 kJ mol-1, in contrast, for the catalytic formation of SO3 on α-Fe2O3 surfaces, this energy barrier becomes an order of magnitude smaller, 24.82 kJ mol-1. O2 molecules can dissociate on the defect α-Fe2O3 (001) surface with O vacancy spontaneously, indicating that the defect α-Fe2O3 is favorable for the dissociation of O2, thereby promotes the formation of SO3. The energy barrier of 'SO2(ads)+O(ads)→SO3(ads)' through Langmuir-Hinshelwood mechanism is much higher than that of 'SO2+O(ads)→SO3(ads)' through Eley-Rideal mechanism. The adsorption energy on the α-Fe2O3 (001) surface of H2O is much smaller than that of SO2 and O2, indicating that H2O has little effect on the adsorption of O, O2, SO2 and eventually the heterogeneous formation of SO3. The DFT analysis results in this study provide a deep understanding on the reaction pathway of SO3 catalytic formation by Fe2O3.

Combustibility analysis of high-carbon fine slags from an entrained flow gasifier.

The fine slag produced from the entrained flow gasifier in coal chemical industry contains a high amount of unburned carbon content, which can reach more than 40%. The coal gasification fine slag is dissipated just by land filling which occupies a lot of land. Consequently, it causes the pollution of soil, water and wastes the combustible carbon in coal gasification fine slag. It is crucial to develop an environmental friendly and economical scheme for the utilization of coal gasification fine slag. To achieve this aim, it is significant to investigate the combustibility of coal gasification fine slag and then propose a comprehensive utilization technology. In this study, the physical and chemical properties of the raw bituminous coal and the produced coal gasification fine slag, including proximate and ultimate analysis, particle size distribution, ash composition, morphology, and specific area were investigated. The combustion and co-combustion characteristics of coal gasification fine slag were analyzed by a thermo-gravimetric analyzer. A drop tube furnace and a fluidized bed reactor were employed to test the combustibility of coal gasification fine slag in a pulverized furnace and a fluidized bed furnace, respectively. Results show that the carbon content in dried coal gasification fine slag is >40% with a heating value > 16 MJ kg-1. Further, thermo-gravimetric analyzer test showed that the combustion property of coal gasification fine slag is worse than that of anthracite and close to that of high ash coal, and there is a non-negligible synergistic effect for raw bituminous coal and coal gasification fine slag co-firing. The combustibility test in drop tube furnace and fluidized bed reactor showed that coal gasification fine slag can be well burned in a pulverized furnace requiring combustion temperature >900 °C and oxygen concentration >10 vol%. However, the fluidized bed furnace was not appropriate for high efficiency coal gasification fine slag burning, because the unburned carbon content of fly ash after coal gasification fine slag combustion is still >14%, even at 900 °C, 21% oxygen concentration and a low fluidization number. It is suggested that coal gasification fine slag will be better to burned it in a pulverized furnace rather than fluidized furnace.