A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO2 in the flue gases from fossil fuel-based power plants without CO2 separation [C. Song, Chemical Innovation 31 (2001) 21-26]. The proposed tri-reforming process is a synergetic combination Of CO2 reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas). Both experimental testing and computational analysis show that tri-reforming can not only produce synthesis gas (CO + H-2) with desired H-2/CO ratios (1.5-2.0), but also could eliminate carbon formation which is usually a serious problem in the CO2 reforming of methane. These two advantages have been demonstrated by tri-reforming of CH4 in a fixed-bed flow reactor at 850 degreesC with supported nickel catalysts. Over 95% CH4 conversion and about 80% CO2 conversion can be achieved in tri-reforming over Ni catalysts supported on an oxide substrate. The type and nature of catalysts have a significant impact on CO2 conversion in the presence of H2O and O-2 in tri-reforming in the temperature range of 700-850 degreesC. Among all the catalysts tested for tri-reforming, their ability to enhance the conversion of CO2 follows the order of Ni/MgO > Ni/MgO/CeZrO > Ni/CeO2 approximate to Ni/ZrO2 approximate to Ni/Al2O3 > Ni/CeZrO. The higher CO2 conversion over Ni/MgO and Ni/MgO/CeZrO in tri-reforming may be related to the interaction of CO2 with MgO and more interface between Ni and MgO resulting from the formation of NiO/MgO solid solution. Results of catalytic performance tests over Ni/MgO/CeZrO catalysts at 850 degreesC and 1 atm with different feed compositions confirm the predicted equilibrium conversions based on the thermodynamic analysis for tri-reforming of methane. Kinetics of tri-reforming were also examined. The reaction orders with respect to partial pressures Of CO2 and H2O are different over Ni/MgO, Ni/MgO/CeZrO, and Ni/Al2O3 catalysts for tri-reforming. (C) 2004 Elsevier B.V. All rights reserved.